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BACKGROUND OF THE INVENTION
[0001] The present invention relates to a process for the manufacture of a moldable non-woven short or long lignocellulosic fiber thermoset resin impregnated mat and where after compression molded into composite product with improved properties, preferably flexural modulus of 14 GPa and flexural strength of 94 MPa. The said process consisting of three stages: forming non-woven plant fiber mat in a perforated screen, further impregnating the mat with the resin solution, circulation of the solution to obtain uniform distribution and further applying vacuum to drain excess solution and drying to a moldable cellulosic thermoset impregnated mat. The present invention also related to said polymer composite product manufactured by the said process and to the use of the product within cosmetic, semi-structural and structural applications of automotive, furniture and other industries.
[0002] Natural fiber reinforced composites are an emerging area in polymer science. By embedding natural fibers into polymeric matrix; a new fiber reinforced material were formed and are still being developed. The natural fibers serve as reinforcement by enhancing the strength and stiffness to the resulting composite structure. Their moderate mechanical properties prevent the fibers from using them in high-performance applications, but for many reasons they can compete with glass fibers. For instance, their low specific weight result in higher specific strength and stiffness than those for glass. Natural fibers are also renewable resources and their production requires low energy along with CO 2 consumption and oxygen production. Natural fibers are producible with low investment and at low cost which makes the material an interesting product on large scales.
[0003] The matrix plays an important role in the performance of the composites. Both thermosets and thermoplastics are attractive as matrix materials for composites. Lots of work has been done on different methods for producing fiber reinforced materials. Most of the work reported involves in thermoplastics such as polyethylene, polypropylene and poly vinyl chloride. Li et.al in U.S. Pat. No. 4,393,020 claimed a method for manufacturing a molded article from a fiber-reinforced thermoplastic polymer. This method involves two steps: first polymerization of the monomers and second compression molding of the product. A natural fiber composite was produced using a starch ester as a matrix and microfibers of cellulose as reinforcement and a composite with superior mechanical properties was obtained by Narayan in U.S. Pat. No. 5,728,824. Moreover, DuCharme et.al in U.S. Pat. No. 5,603,884 disclosed a method of preparing an extruded cellulosic film which contains a uniform dispersion of hemp fibers and a molten aqueous solution of cellulose and amine oxide cellulose solvent as a thermoplastic matrix.
[0004] Thermoset composite materials are chemically cured to a highly cross-linked three-dimensional network structure. Due to this structure, thermoset composites are highly solvent resistant with superior mechanical properties. For example, a method for producing natural fiber reinforced thermoset materials was explained by Skwiercz et.al in U.S. Pat. No. 6,682,673. The matrix was provided by radical polymerization reactions using monomers from natural resources and reinforced with flax fibers. Also, Taylor in U.S. Pat. No. 6,204,312 developed a process for manufacturing organic and inorganic compositions with thermoset resins and formed to desired shape using injection molding and extrusion. Most of the work on thermoset composites used resin transfer molding (RTM) process to manufacture the composites. Rouison et.al, (Composites Science and technology, 64, 5, 629-644, 2004), manufactured hemp/kenaf fiber-unsaturated polyester composites using RTM process and obtained fast and homogeneous curing of the part. Also, Williams et.al, (Applied Composite Materials, 7, 421-432, 2000), developed a new composite contains fibers and thermoset resin from natural resources using RTM process. The maximum fiber content in RTM process can not be more than 40% because of difficulty in filling the mold.
[0005] There is a large potential for energy saving and reduction of environmental impact in the use of natural fibers as reinforcements in polymer composites for many applications, provided that the full reinforcement potential of these fibers is exploited. One of the major issues in development of composites is dispersion of the fibers in the matrix. The incorporation of cellulosic fibers in polymers leads to poor dispersion of the fibers due to strong inter-fiber hydrogen bonding, which holds the fibers together. This lack of fiber dispersion can result in clumping and agglomeration of cellulose fibers which lead to inferior mechanical properties. In the case of using thermoplastic polymers as a matrix, this problem can be overcome by pretreatment of the fibers with polymer coating. Polymer coatings on fiber surfaces help to separate fibers from each other, eliminating the hydrogen bonding. This approach also induces bond formation between fibers and the matrix which have different polarities. For example, Scandola et.al in U.S. Pat. No. 6,667,366 described the chemical modification of the surface of natural fibers to enhance the adhesion between matrix and fibers. However, in the case of using thermoset polymers as a matrix, eliminating the hydroxyl groups on the surface of fibers also will decrease the interaction between fibers and matrix which result poor composite properties. In the present research, different processes were conducted to prepare resin impregnated lignocellulosic mats using for compression molding processes. Hence, a unique processing technique has been developed for manufacturing natural fiber composites using thermoset resins and non-woven lignocellulosic/ cellulosic fibers.
BRIEF SUMMARY OF THE INVENTION
[0006] The present invention is a process for manufacturing improved moldable thermoset material, where short or discontinuous natural fibers are properly impregnated with thermoset polymer, subsequently compression molded into composite product with improved properties, with a flexural strength of 94 MPa and a flexural modulus of 14 GPa. More specifically, the present invention relates to a process for the manufacture of a polymer composite product with acceptable properties, said product consisting of one or more layers of thermoset impregnated natural fiber mat, in which the fibers are in the form of non-woven mats where after, the lay-up is subjected to an elevated temperature, pressure and time followed by cooling under pressure to produce a composite product. The process of the invention is characterized in that the fibrous layers are impregnated by circulating the diluted solution of thermoset polymer through the fibers and employing a vacuum pressure simultaneously to obtain a uniform penetration of polymer through the layer and drain the excess solution. After impregnation, the prepreg mats are dried at specific temperature and time and then ready to cure at the specific temperature and pressure for certain time using compression molding process followed by cooling stage to obtain the final composite products. This approach will be extendable to a wide variety of fiber/polymer combinations.
[0007] The thermoset material is preferably water based polymer such as acrylic polymer, but other water soluble and insoluble resins and low viscose thermoset materials are useful as well, typically vinyl ester resin, unsaturated polyesters and their low molecular weight precursors. Precursors are further prone to polymerization.
[0008] The fibrous reinforcement in the composite product manufactured by the process of the invention consists of either:
[0000] Plant fibers selected among hemp, flax, jute, sisal, kenaf.
[0000] Wood or cellulose fibers
[0000] Blends of the natural fibers mentioned in [1] and /or [2] or
[0009] The said object of the present invention is the manufacturing process comprising the following steps:
[0000] Formation of the plant fiber mat in a perforated screen which is connected to a vacuum system and dilution of the polymer at a specific resin content ranging between 5 to 30 weight percentages.
[0010] Circulation of the polymer solution through the fibers to obtain uniform distribution of wetting in the mat for 0.5-15 minutes and where after application of the vacuum pressure in the range of 50-1000 pound per square inch (psi) to drain the excess solution for 0.1-10 minutes.
[0000] Drying the prepreg mat at a temperature range of 30-100 degree centigrade for 0.5 to 48 hours to evaporate all of the water contents.
[0011] Compression molding of the moldable resin impregnated lignocellulosic fiber mat at a temperature range of 50 to 240 degree centigrade under pressure ranging from 10 to 50 tones for 1 to 30 minutes and cooling to a temperature less than 60 degree centigrade under the same pressure in to composite products.
[0012] The present invention provides a number of advantages over the prior process, including:
[0000] Using non-woven fibers versus woven mat improve the penetration uniformity of the polymer through the fibers because of the lower compaction of the fibers
[0000] Using the vacuum pressure increase the wetting surface of fibers
[0000] Better performance of the composite through better interfacial wetting of the natural fibers with the thermoset
[0000] Simple and practical method for high production rate
[0000] Manufacturing composites with high fiber content is applicable
[0000] Non-woven fibers are more randomly oriented as a result the final product is more isotropic
[0000] Extra solution of thermoset solution can be recycled
[0013] The process and the products according to the invention will find use within a number of different fields of industry. One of the key areas will be the automotive industry. In Europe the automotive industry has taken a major lead in using plant fiber composites in automotive interiors. The industry has been particularly interested in the environmental advantages of such composites. The weight and cost advantages of these composites are also particularly important to the industry.
[0014] The main benefit of the technology that forms the basis of the present invention in contrast to the known techniques is the ability to maximize the mechanical properties through the vacuum impregnation technique. Although this is practiced manually in laboratory scale, the process will be amenable to semi-continuous and continuous application through feeding of loose fibers and circulation of polymer solution to provide prepreg mat and then drying and final compression molding.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 : Spray lay-up system
[0016] FIG. 2 : Blower system
[0017] FIG. 3 : Spray-drying system
[0018] FIG. 4 : a) Mat formation, b) Mat impregnation, and c) Vacuum filtration
[0019] FIG. 5 : Tensile and flexural strength of the composite versus temperature
[0020] FIG. 6 : Tensile and flexural modulus of the composite versus temperature
[0021] FIG. 7 : Tensile and flexural strength of the composite versus time
[0022] FIG. 8 : Tensile and flexural modulus of the composite versus time
[0023] FIG. 9 : Tensile and flexural strength of the pure polymer and composite versus fiber length
[0024] FIG. 10 : Tensile and flexural modulus of the pure polymer and composite versus fiber length
DETAILED DESCRIPTION OF THE INVENTION
[0025] As mentioned earlier, the key aspect of the present invention is based upon a specific technique to produce composites with optimum properties which consists of one or more layers of prepreg natural fibers mats. It is primarily the reinforcing fibers which give the composite product its desirable properties, where as the matrix material must be capable of transferring any stress between the fibers. The adhesion and wetting surface between the fibers and the matrix material is therefore crucial to the properties of the product. In natural fibers, strong inter-fiber hydrogen bonding leads to a poor dispersion of fibers into the matrix and as a result less wetting of fibers. To overcome this problem, different processes were conducted for diluted thermoset polymers to prepare resin impregnated mats followed by compression molding process. Finally a unique process technique has been developed using vacuum impregnation. The processing techniques are described as follow:
[0000] 1. Spray Hand Lay-Up Process
[0026] In this process, the required non-woven natural fibers were divided equally into 1-13 layers into square shapes manually. A 1-30 wt % diluted solution of resin were prepared and sprayed over the upper surface of each layer ( FIG. 1 ). The layers were kept at room temperature for 0-48 hrs to dry and then laid together to prepare a composite with 50% resin and 50% fiber contents. The composite was cured at 50-180° C. for 1-60 min at 10 to 50 tones pressure using a hydraulic hot press. Due to the lack of resin dispersion and non uniformity of the composite the inferior mechanical properties were obtained. For instance, the flexural strength was approximately 5 MPa.
[0000] 2. Air Blowing System
[0027] In this technique, a circulated pipe system was designed to separate fibers by blowing force. Steel pipes with the inner diameter of 6 inches were connected to each other and two exits were considered at two different points. A blower with 2-3.5 hp was utilized to supply required force to separate the fibers and drying them after spraying the resin solution. A small transparent window was placed to observe movement of fibers. A nozzle was located at the corner point of the system to spray the resin solution while fibers were circulating ( FIG. 2 ). Small amount of fibers were placed into the system and exits were closed and the blower was switched on. Due to high hygroscopic and hydrophilic nature of cellulose fibers even with high power of blower, the fibers were entangled and moved together. As a result, a poor distribution of resin and fiber were obtained.
[0000] 3. Spray-Drying of the Resin Fiber Slurry
[0028] In this technique, slurry of fiber was prepared by dispersing the fibers in the diluted resin solution with a consistency of 1-5 wt %. A compressed air gun with a maximum inner diameter of 4 mm was used to spray the slurry ( FIG. 3 ). By regulating the air pressure, a venture effect is created by which suction is generated in the tube which connected to the gun. The slurry was sprayed toward a heated surface, which allowed the fibers to partially dry before coming into contact with each other and finished with a fluffy of resin impregnated fibers. Because of using relatively long fibers, the fibers were twisted inside the gun and then blocked the outlet of the gun after few minutes spraying. Although with this method a good distribution of fibers and resin can be obtained, it will be practical in the case of using very short fibers in a very low consistency of slurry. Therefore, this process is not suitable for industrial purposes due to low production rate (5 g/hr) and limitation.
[0000] 4. Vacuum Impregnation
[0029] Non-woven lignocellulosic fibers were randomly oriented manually in a Buckner funnel which connected to a vacuum system ( FIG. 4 a ). A resin solution with 5-30% resin content was prepared by adding solvent to resin to circulate through the fibers. The said resin solution was spread all over the fibers and circulated for 0.3-15 minutes to impregnate the fibers with the solution ( FIG. 4 b ). In the last stage, vacuum pressure in the range of 50-1000 psi was applied to drain the excess solution ( FIG. 4 c ). Vacuum time can be varied ranging from 0.1-10 minutes depends on the required composition of the material. The initial weight of the said solution and the weight of solution in the filtrate were measured to calculate the amount of adsorbed solution to the fibers. After circulation of the resin solution, the wet mat was removed from Buckner and placed on a non-stick sheet and then kept in the oven at the temperature of 30-100° C. for 0.5-48 hours to remove all moisture content. The mat would be ready for compression molding process after drying.
[0030] Finally, to manufacture the composite the impregnated mat was cured at the temperature of 50-240° C. for 1-30 minutes using a hydraulic press in pressure of 10-50 tones. One or more layers of mats were combined together to reach to desirable finishing thickness. After heating cycle, the temperature of the composite was cooled down to a temperature less than 60° C. using water cooling system to prevent any blister formation due to any moisture content. The final composite was removed from the press and prepared for mechanical properties measurements.
[0000] Testing
[0031] Composite panels were cut into sections allowing for at least three tensile and flexural test specimens in each case. The tensile properties of the composites were measured following the ASTM standard method (D-638). The flexural properties were obtained according to the ASTM standard method (D-790). Also the ASTM D-256 was applied to measure the notched impact properties of samples.
EXAMPLES
[0000] Materials:
[0032] The fiber used in these experiments was hemp fibers in the form of non-woven loose fiber. The moisture content was in the range of 4 to 12% weight percentage. The polymer employed in these experiments was an environmentally friendly water-based acrylic thermoset polymer (viscosity at 23° C.=400-4000 mP·s).
[0033] The following examples are illustrative of some of the moldable non-woven cellulosic thermoset resin impregnated mat and composite products comprising lignocellulosic fibers and the method of making the same within the scope of the present invention.
Example 1
Processing of a Moldable Non-Woven Cellulosic Thermoset Mat by Vacuum Impregnation
[0034] Bast fibers, prefereably non-woven hemp with an average length of 2.5 centimeter and 9 centimeter were selected and 28 grams of fibers randomly oriented in a Buckner funnel with the inner diameter of 19 cm which connected to a vacuum system. A resin solution with 10 weight percentage of resin prepared by adding water as a solvent to an environmentally friendly acrylic resin to circulate through the fibers. The resin solution was circulated for 5 minutes to impregnate all the fibers with the solution. In the last stage, 2 minutes vacuum filtration was applied to remove the excess solution and keep almost 185 gram of the resin solution inside the fibers to have a composite with 40% resin content. After circulation of the resin solution, the wet mat was removed from Buckner and placed on the polyester sheet and then kept in the oven at 55° C. for 36 hrs to remove all moisture content. The mat would be ready for compression molding process after drying. Two layers of the dry impregnated mat were combined together and cured at 180° C. for 10 min using hydraulic press under 30 tones pressure to reach to almost 2.2 millimeter thickness. After heating cycle, the composite was cooled down under same pressure to around 50° C. using cold water system. The final composite was removed from the press and prepared for mechanical properties measurements.
Example 2
Compression Processing of a Moldable Non-Woven Cellulosic Resin Impregnated Mat Under Various Processing Condition
[0000] The vacuum resin impregnation processing of the non-woven cellulosic mats are the same as mentioned in example 1.
[0035] In one case, the moldable non-woven cellulosic resin impregnated mats were molded at different temperatures of 175, 180, 185 degree centigrade for 12 minutes
[0036] In the other case, the moldable non-woven cellulosic resin impregnated mats were molded at the temperature of 180 degree centigrade for two different times 10 and 12 minutes.
[0037] In the other case, the moldable non-woven cellulosic resin impregnated mat were manufactured for two different fiber lengths 2.5 and 9 centimeter and molded at the temperature of 180 degree centigrade for 10 minutes.
Example 3
Compression Processing a Moldable Non-Woven Cellulosic Resin Impregnated Mat Using a Prototype Mold
[0000] The vacuum resin impregnation processing of the non-woven cellulosic mats are the same as mentioned in example 1.
[0038] Having acceptable mechanical properties, a prototype mold was designed and built for an exterior mirror frame of automobile. The stainless steel mold contains two male and female parts was installed onto the platens of the hydraulic press. A moldable non-woven cellulosic resin impregnated mat obtained from example 1 was molded using the above mentioned mold at the temperature of 180 degree centigrade for 10 minutes under the pressure of 30 tones. Curvatures of the specimen clearly show a good formability of the composite especially at the corners.
RESULTS
[0039] Typical performance properties of the composite are shown in Table 1. The composite consists of 40% polymer and 60% fiber (9 cm) cured at 180° C. for 10 min under 30 tones pressure and cooling to less than 50° C.
TABLE 1 Mechanical properties of hemp fiber acrylic based composite Performance ASTM Average Maximum Minimum property Test Value Value Value SD Tensile Strength D-638 42.21 46.14 37.59 3.7 (MPa) Tensile Modulus D-638 5.1 5.15 4.7 0.25 (GPa) Flexural Strength D-790 93 110.16 82.31 10.9 (MPa) Flexural Modulus D-790 14.5 15.4 13.8 0.67 (GPa) Notch Izod (J/m) D-256 46 48.6 43.13 2.76
Influence of Cure Temperature
[0040] The effect of cure temperature on the performance of the composite was shown in FIGS. 5 and 6 . The mechanical properties of the composites consists of 40% polymer and 60% short fiber (2.5 cm) cured at different curing temperatures 175, 180, and 185° C. for 12 min were evaluated to obtain the optimum curing temperature. As it can be noticed, the composite cured at 180° C. has superior mechanical properties compare with others. That means at this temperature, strong adhesion between fiber and matrix due to higher crosslinking resulted in higher strength at the fiber/matrix interface.
[0000] Influence of Cure Time
[0041] The effect of cure time on the performance of the composite was shown in FIGS. 7 and 8 . The mechanical properties of the composites consists of 40 percentage of weight polymer and 60 percentage of weight long fiber (9 cm) cured at the curing temperature of 180 degree centigrade at two different curing times 10 and 12 min were evaluated to obtain the optimum curing time. As it can be noticed, the composite cured for 10 min has superior mechanical properties compare with another which can be due to decomposition of the resin in longer time.
[0000] Influence of Fiber Length
[0042] The mechanical properties of the cured pure polymer and the effect of fibers on the performance of the polymer were evaluated as shown in FIGS. 9 and 10 . As it can be noticed, adding 60 percentage of weight fiber to the pure resin has a pronounced effect on the mechanical properties of the polymer. When polymer resin stressed, random flaws in physical structure of the resin will cause the material to crack and fail. Introducing the fibers to the resin will overcome this problem and reinforce the material.
[0043] In order to investigate the effect of fiber length on the performance of the composite, two different fiber lengths (short and long) were selected (2.5 cm and 9 cm) and the composites were manufactured with two layers of impregnated mat at 180 degree centigrade for 10 min with 40 percentage of weight resin and 60 percentage of weight fiber. From the figures, for the same amount of fiber content, as the fiber length increases the number of stress concentrating fiber ends decreases which assist to transfer load from matrix to the fiber and thus contributes toward the entire composite and consequently improvement in mechanical properties.
[0000] Influence of Adhesion Promoter
[0044] Adhesion promoters such as styrene-maleimide and polysiloxane are used to treat the fiber. In a typical composition 0.2 to 3% of the adhesion promoters are used to treat the fibers. Treatment is carried out by spraying either on the bed in a non aqueous medium or they were dissolved in water and then spayed over the fiber bed. A maximum improvement of 15% of flexural strength was observed for composites made with thermosetting resins using the fiber treatment process as described above.
[0045] In yet another process liquid resin polyester, acrylic or vinyl ester is mixed with the strength promoters such as polysiloxanes including 3-aminopropyltriethoxysilane, Styrene maliec anhydride resins (SMA 1000, SMA 40001) before they are impregnated with fiber. This process resulted in improved flexural strength and moisture resistant properties of the composites.
[0000] For example, a 1% addition of 3-aminopropyltriethoxysilane directly in the polyester resin resulted in about 20% increase in the flexural strength and more than 50% improvement in the water resistance properties in relation to an untreated resin.
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The present invention relates to a process for the manufacture of non-woven short or long lignocellulosic fiber thermoset based composites, in which the process consists of forming natural fiber mats in a perforated screen, further impregnation of the lignocellulosic fibers by circulating the thermoset solution and applying vacuum pressure to drain the excess solution, further drying the prepreg mat at a temperature range of 30 to 100 degree centigrade for 0.5 to 48 hours, further compression molding under pressure of 10 to 50 tones and a temperature range of 50 to 240 degree centigrade for 1 to 30 minutes and cooling the mold to less than 60 degree centigrade under the same pressure into composite products. The said composites have a flexural strength of 94 MPa and a flexural modulus of 14 GPa. The invention also relates to the use of the said composites in cosmetic, semi-structural and structural applications.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a semiconductor storage device which is electrically rewritable.
2. Description of the Related Art
A nonvolatile memory, which is electrically writable and erasable, generally employs a structure which includes a recording transistor provided with a floating gate under a gate and a selecting transistor connected to the recording transistor. The floating gate has a structure in which electrically insulated electrodes are provided. In the structure, when a high voltage is applied to a drain and a gate, it is possible to store (write) an electron in the floating gate or to emit (erase) the electron stored in the floating gate.
A high voltage required in writing or erasing is generally about 20 V. As the high voltage, an optimum voltage is supplied such that a high voltage outputted by a booster circuit provided inside an IC is limited in a voltage by a limiter circuit so as not to be equal to or higher than a predetermined voltage to execute writing or erasing of data to the recording transistor.
Up to now, the limiter circuit outputs by one value a high voltage for executing writing or erasing of data to the recording transistor, and uses a surface breakdown voltage characteristic of a high withstand voltage MOS transistor.
A surface breakdown voltage of the high withstand voltage MOS transistor is generally about 20 V, and thus being most suitable for a voltage required for writing or erasing of data to the recording transistor.
For the purpose of measuring, for example, as an inspection before shipment of a product, electric characteristics of the recording transistor and the selecting transistor adapted to the recording transistor, a voltage is applied to the recording transistor and the selecting transistor. As the voltage required for this purpose, there is used a power supply voltage supplied from the outside of the IC or the limiter circuit output voltage for executing writing/erasing of data to the recording transistor.
Up to now, the limiter circuit is a circuit which supplies by one value a high voltage required for writing/erasing of data to the recording transistor. The high voltage supplied to the recording transistor and the selecting transistor adapted to the recording transistor uses an output of one value outputted in the limiter circuit in any purposes such as execution of writing/erasing of data to the recording transistor and execution of electric characteristic evaluation of the recording transistor and the selecting transistor.
The nonvolatile memory, which is electrically writable and erasable, is composed of the recording transistor provided with the floating gate under the gate and the selecting transistor adapted to the recording transistor. A gate of the selecting transistor is connected to a gate of the selecting transistor of a plurality of bits and is also used as a word line. In the word line, there is used polysilicon wiring in many cases. Below the polysilicon wiring, a poly-gate field transistor is formed and a source/drain of the poly-gate field transistor serves as a diffusion layer of the source/drain of the selecting transistor of the adjoining bit.
A reverse voltage of the poly-gate field transistor is designed so as to be higher than the high voltage supplied by the limiter circuit output, and therefore the poly-gate field transistor is not turned on.
However, semiconductor manufacturing process has progressed in miniaturization, so that it is difficult to increase a reverse voltage of the poly-gate field transistor.
The reverse voltage of the poly-gate field transistor is greatly influenced by a channel length of the poly-gate field transistor, that is, the distance from the diffusion layer of the source/drain of the adjoining selecting transistor. In recent miniaturizing process, this distance is shortened and the reverse voltage is further lowered. When the high voltage supplied by the limiter circuit output is higher than the reverse voltage of the poly-gate field transistor, the poly-gate field transistor is turned on. Therefore, there arises such a potential state that the bit line of the adjoining bit is short-circuited, resulting in a problem. To a gate of the poly-gate field transistor as the word line, at the time of writing/erasing of data to the recording transistor, a high voltage supplied by the limiter circuit output is applied, and then the transistor is turned on. However, since the source/drain of the adjoining selecting transistor as the source/drain both have the same potential or a high impedance, no current flows, resulting in no problem.
However, when the electric characteristics of the recording transistor and the selecting transistor are evaluated, the source/drain of the adjoining selecting transistor do not necessarily have the same potential, which causes a problem in that the electric characteristics can not be evaluated.
SUMMARY OF THE INVENTION
In order to solve the above-mentioned problems, the present invention has been made and has an object to provide a semiconductor storage device capable of outputting a high voltage supplied by a limiter circuit output as two values consisting of: a high voltage for executing writing/erasing of data to a recording transistor; and a high voltage for evaluating, as inspection before shipment of a product, for example, electric characteristics of the recording transistor and a selecting transistor, and of selectively outputting one voltage value out of the two values from the limiter circuit in synchronism with a signal generated by a timing circuit inside an IC or a signal given inside the IC via a terminal from the outside of the IC. In order to attain such object of the invention, the following measures are taken.
According to the present invention, there is provided a semiconductor storage device which is electrically writable and erasable, including: a booster circuit for boosting a power supply voltage supplied to an IC; and a limiter circuit having a function of performing voltage limitation of a high voltage which is a booster circuit output so as not to be boosted to a predetermined voltage or more, characterized in that the limiter circuit is capable of outputting two values of high voltage and the circuit is capable of selecting one voltage value out of the two values in synchronism with a signal generated by a timing circuit inside the IC or a signal given inside the IC via the terminal from the outside of the IC, to output the one of two voltage values.
According to the present invention, the high voltage which can be outputted from the limiter circuit is composed of two potentials having different voltage values, consisting of a high voltage for executing writing/erasing of data to the recording transistor and a high voltage for evaluating electric characteristics of the recording transistor and the selecting transistor.
The former high voltage for executing writing/erasing of data to the recording transistor is a voltage which is higher than a reverse voltage of a poly-gate field transistor formed on a word line, and which is required to move an electron to a floating gate provided in the recording transistor.
The latter high voltage for evaluating the electric characteristics of the recording transistor and the selecting transistor is a voltage which is lower than the reverse voltage of the poly-gate field transistor formed on the word line, and which does not turn on the poly-gate field transistor even if the high voltage is applied to the word line.
By switching those two high voltages according to the purpose thereof, it is possible to realize the proper function with respect to any operation of the IC.
According to the present invention, the limiter circuit that can output two kinds of high voltages, which are capable of being selectively switched, includes a high withstand voltage MOS transistor and a low withstand voltage MOS transistor, and which uses a difference between the withstand voltages of surface breakdown voltages of the respective MOS transistors.
The limiter circuit can output two values of the high voltages obtained by the two MOS transistor characteristics having different withstand voltages, and performs voltage limitation by connecting one of MOS transistors to an output of the booster circuit in synchronism with the signal generated by the timing circuit inside the IC or the signal given inside the IC via the terminal from the outside of the IC.
There is employed a circuit structure in which a switch adapted to the high withstand voltage MOS transistor can be eliminated. With this structure, it is possible to contribute to layout saving. The limiter circuit output voltage is determined by a surface breakdown characteristic of the high withstand MOS transistor by closing a switch of the low withstand voltage MOS transistor. On the contrary, when the switch is turned on, the output of the booster circuit is connected with the low withstand voltage MOS transistor and the high withstand voltage MOS transistor. However, since the limiter circuit output voltage is determined by the lower withstand voltage, it is determined by a surface breakdown characteristic of the low withstand MOS transistor.
There is also employed a circuit structure in which a switch adapted to the low withstand voltage MOS transistor can be eliminated. With this structure, it is possible to contribute to further layout saving. The high withstand voltage MOS transistor has a structure which also serves as the switch of the low withstand voltage MOS transistor. In the case where the high withstand voltage MOS transistor is opened, the limiter circuit output voltage is determined by the surface breakdown characteristic of the low withstand voltage MOS transistor. In the case where the high withstand voltage MOS transistor is closed, it is possible to perform voltage limitation thereof by the surface breakdown characteristic of the transistor itself.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
FIG. 1 is a diagram showing a structure of a limiter circuit and a circuit block which inputs and outputs a voltage to and from the limiter circuit in accordance with Embodiment 1 of the present invention;
FIG. 2 is a diagram showing a structure of a limiter circuit and a circuit block which inputs and outputs a voltage to and from the limiter circuit in accordance with Embodiment 2 of the present invention; and
FIG. 3 is a diagram showing a structure of a limiter circuit and a circuit block which inputs and outputs a voltage to and from the limiter circuit in accordance with Embodiment 3 of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Hereinafter, embodiments in accordance with the present invention will be described in detail with reference to the drawings.
FIG. 1 is a diagram showing a structure of a limiter circuit and a circuit block which inputs and-outputs a voltage to and from the limiter circuit in accordance with Embodiment 1 of the present invention.
A power supply voltage 11 inputted from the outside of an IC is boosted up to a voltage sufficiently high with respect to writing/erasing of data to a recording transistor constituted in a memory circuit block 14 by a booster circuit 12 provided inside the IC. A high voltage outputted by the booster circuit 12 is inputted to a limiter circuit 13 , where the voltage is limited in voltage so as not to be predetermined voltage or more. Then, the voltage is sent to the memory circuit block 14 . The memory circuit block 14 is a circuit block composed of the recording transistor described before and a selecting transistor connected to the recording transistor.
The limiter circuit 13 is comprised of a low withstand voltage MOS transistor 15 and a switch 17 connected to the low withstand voltage MOS transistor, and a high withstand voltage MOS transistor 16 and a switch 18 connected to the high withstand voltage MOS transistor. The switch 17 for the low withstand voltage MOS transistor and the switch 18 for the high withstand voltage MOS transistor are opened and closed based on whether it is a product use time or, for example, an inspection time before shipment of the product, by a signal generated by a timing circuit provided inside the IC or a timing signal inputted from the outside of the IC, and can connect either of the low withstand voltage MOS transistor 15 or the high withstand voltage MOS transistor 16 .
In the case where writing/erasing of data to the recording transistor is being executed, the switch 17 is turned off and the switch 18 is turned on. In this case, a high voltage output by the booster circuit 12 is connected to a drain of the high withstand voltage MOS transistor 16 , and is not connected to the low withstand voltage MOS transistor 15 . Since a gate of the high withstand voltage MOS transistor 16 is connected to ground, a surface breakdown characteristic of the high withstand MOS transistor is utilized to generate a voltage limit path in a path of a current path 20 . Thus, an output of the booster circuit 12 can be limited in voltage by a surface breakdown voltage of the high withstand voltage MOS transistor. The surface breakdown of the high withstand voltage MOS transistor is generally about 20 V and it is possible to execute writing/erasing of data to the recording transistor in the memory circuit block 14 .
In the case where electric characteristics of the recording transistor and the selecting transistor are being evaluated, the switch 17 is turned on and the switch 18 is turned off. In this case, a high voltage output by the booster circuit 12 is connected to a drain of the low withstand voltage MOS transistor 15 and is not connected to the high withstand voltage MOS transistor 16 . Since a gate of the low withstand voltage MOS transistor 15 is connected to ground, a surface breakdown characteristic of the low withstand voltage MOS transistor is utilized to generate a voltage limit path in a path of a current path 19 . Thus, an output of the booster circuit 12 can be limited in voltage by a surface breakdown voltage of the low withstand voltage MOS transistor. The surface breakdown of the low withstand voltage MOS transistor is generally about 10 V and it is possible to supply a high voltage lower than a reverse voltage of the poly-gate field transistor to the memory circuit block 14 .
By adopting a structure of the limiter circuit described in detail in Embodiment 1 of the present invention, it is possible to selectively supply the two values of high voltage to the memory circuit block.
Next, an explanation is made of Embodiment 2. FIG. 2 is a diagram showing a structure of a limiter circuit and a circuit block which inputs and outputs a voltage to and from the limiter circuit in accordance with Embodiment 2 of the present invention.
A power supply voltage 21 inputted from the outside of an IC is boosted up to a voltage sufficiently high with respect to writing/erasing of data to a recording transistor constituted in a memory circuit block 24 by a booster circuit 22 provided inside the IC. A high voltage outputted by the booster circuit 22 is inputted to a limiter circuit 23 , where the voltage limitation is performed so as not for the voltage boosted up to a predetermined voltage or more. Then, the voltage is sent to the memory circuit block 24 . The memory circuit block 24 is a circuit block composed of the recording transistor described before and a selecting transistor adapted to the recording transistor.
The limiter circuit 23 is constituted by a low withstand voltage MOS transistor 25 and a switch 27 adapted to the low withstand voltage MOS transistor, and a high withstand voltage MOS transistor 26 . The switch 27 for the low withstand voltage MOS transistor is opened and closed, based on whether it is a product use time or, for example, the inspection time before shipment of the product, by a signal generated by a timing circuit provided inside the IC or a timing signal inputted from the outside of the IC.
In the case where there is executed writing/erasing of data to the recording transistor, the switch 27 is turned off. In this case, a high voltage outputted by the booster circuit 22 is connected to a drain of the high withstand voltage MOS transistor 26 , and is not connected to the low withstand voltage MOS transistor 25 .
Here, since a gate of the high withstand voltage MOS transistor 26 is connected to a ground, a surface breakdown characteristic of the high withstand MOS transistor is utilized to generate a voltage limit path in a path of a current path 29 . Thus, an output of the booster circuit 22 can be limited in voltage by a surface breakdown voltage of the high withstand voltage MOS transistor. The surface breakdown of the high withstand voltage MOS transistor is generally about 20 V, and therefore the writing/erasing of data to the recording transistor in the memory circuit block 24 can be executed.
In the case where the electric characteristics of the recording transistor and the selecting transistor are evaluated, the switch 27 is turned on. In this case, a high voltage outputted by the booster circuit 22 is connected to a drain of the low withstand voltage MOS transistor 25 and the drain of the high withstand voltage MOS transistor 26 . Since a gate of the low withstand voltage MOS transistor 25 and a gate of the high withstand voltage MOS transistor 26 are connected to a ground, there is generated a double system voltage limit path in a path of a current path 28 where a surface breakdown characteristic of the low withstand voltage MOS transistor is utilized and the path of the current path 29 where the surface breakdown characteristic of the high withstand voltage MOS transistor is utilized. In this case, there is ultimately determined by the current path whose surface breakdown voltage is lower. Thus, an output of the booster circuit 22 can be limited in voltage by a surface breakdown voltage of the low withstand voltage MOS transistor. The surface breakdown of the low withstand voltage MOS transistor is generally about 10 V and therefore a high voltage lower than the reverse voltage of the poly-gate field transistor can be supplied to the memory circuit block 24 .
Note that, in this embodiment, there is provided one switch and a further simplified structure is taken in comparison with Embodiment 1.
Next, an explanation is made of Embodiment 3. FIG. 3 is a diagram showing a structure of a limiter circuit and a circuit block which inputs and outputs a voltage to and from the limiter circuit in accordance with Embodiment 3 of the present invention.
A power supply voltage 31 inputted from the outside of an IC is boosted up to a voltage sufficiently high with respect to writing/erasing of data to a recording transistor constituted in a memory circuit block 34 by a booster circuit 32 provided inside the IC. A high voltage outputted by the booster circuit 32 is inputted to a limiter circuit 33 , where the voltage limitation is performed so as not for the voltage to be boosted up to a predetermined voltage or more. Then, the voltage is sent to the memory circuit block 34 .
The memory circuit block 34 is a circuit block composed of the recording transistor described before and a selecting transistor adapted to the recording transistor.
The limiter circuit 33 is constituted by a low withstand voltage MOS transistor 35 and a high withstand voltage MOS transistor 36 .
To a gate of the high withstand voltage MOS transistor 36 , there is applied a signal generated by a timing circuit provided inside the IC or a timing signal inputted from the outside of the IC, based on whether it is the product use time or, for example, the inspection time before shipment of the product, to thereby open and close the transistor.
In the case where there is executed writing/erasing of data to the recording transistor, a ground is applied to the gate of the high withstand voltage MOS transistor 36 and the transistor is turned off. In this case, the high withstand voltage MOS transistor 36 is in the same state as those of the high withstand voltage MOS transistors 16 and 26 in Embodiments 1 and 2. Then, by a surface breakdown characteristic of the high withstand voltage MOS transistor 36 , there is generated a voltage limit path in a path of a current path 38 . Thus, an output of the booster circuit 32 can be limited in voltage by a surface breakdown voltage of the high withstand voltage MOS transistor. The surface breakdown of the high withstand voltage MOS transistor is generally about 20 V, and therefore writing/erasing of data can be executed to the recording transistor in the memory circuit block 24 .
In the case where electric characteristics of the recording transistor and the selecting transistor are evaluated, the high withstand voltage MOS transistor 36 is turned on. In this case, a high voltage outputted by the booster circuit 32 is connected to a drain of the low withstand voltage MOS transistor 35 . Since a gate of the low withstand voltage MOS transistor 35 is connected to a ground, there is generated a voltage limit path in a path of a current path 37 where a surface breakdown characteristic of the low withstand voltage MOS transistor is utilized. Thus, an output of the booster circuit 32 can be limited in voltage by a surface breakdown voltage of the low withstand voltage MOS transistor. The surface breakdown of the low withstand voltage MOS transistor is generally about 10 V, and therefore a high voltage lower than the reverse voltage of the poly-gate field transistor can be supplied to the memory circuit block 34 .
Note that, in this embodiment, there is provided one switch and a further simplified structure is taken in comparison with Embodiment 1.
As has been described, the present invention is a limiter circuit which uses a difference between surface breakdown characteristics of the high withstand voltage MOS transistor and the low withstand voltage MOS transistor, and can selectively output one value out of the two values of high voltage.
As the process in miniaturization has progressed recently, the reverse voltage of the poly-gate field transistor formed below the word line disposed within the memory cell becomes low. In such a process, by switching these two high voltages according to the purpose, it is possible to realize the proper function with respect to any operation of the IC.
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The semiconductor storage device includes: a booster circuit ( 12 ) for boosting a power supply voltage ( 11 ) supplied to the IC; and a limiter circuit ( 13 ) having a function of performing voltage limitation of a high voltage which is a booster circuit output. The limiter circuit 13 selects one voltage value from two values based on whether it is a data recording/erasing time or an evaluation time, to output the one to the memory circuit block 14.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an improved method of determining, while drilling in the earth with a drill bit, the positions of geologic formations in the earth. More particularly, it relates to a method for improving the quality of a reference signal.
[0003] 2. Description of the Related Art
[0004] Conventional reflection seismology utilizes surface sources and receivers to detect reflections from subsurface impedance contrasts. The obtained image often suffers in spatial accuracy, resolution and coherence due to the long travel paths between source, reflector, and receiver. In particular, due to the two way passage of seismic signals through a highly absorptive near surface weathered layer with a low, laterally varying velocity, subsurface images are poor quality. To overcome this difficulty, a technique commonly known as vertical seismic profiling (VSP) was developed to image the subsurface in the vicinity of a borehole. With VSP, a surface seismic source is used and signals are received at a single downhole receiver or an array of downhole receivers. This is repeated for different depths of the receiver (or receiver array). In offset VSP, a plurality of spaced apart sources are sequentially activated, enabling imaging of a larger range of distances than is possible with a single source
[0005] In reverse VSPs, the positions of the source and receivers are interchanged, i.e., a downhole source is used and recording is done at a surface receiver or array of receivers. A particular example of such a system is one developed by Western Atlas International Inc. and used with the service mark TOMEX®. In this, the drillbit itself is used as the seismic source. One of the problems with using a drillbit as a seismic source is that the source is not repeatable. As would be known to those versed in the art, analysis of VSP data preferably uses of a repeatable source so that any waveforms changes in the VSP data may be attributable to formation properties. With the drillbit as a seismic source, this is difficult. Hence it would be desirable to properly compensate for source variations prior to analysis of the VSP data.
[0006] A problem with proper compensation for source variations is that telemetry capability in a drilling environment is extremely limited, so that sending the characterizing information about the source wave let to the surface is not possible. U.S. Pat. No. 6,078,868 to Dubinsky, having the same assignee as the present application and the contents of which are fully incorporated herein by reference, teaches a method for making seismic while drilling (SWD) measurements in which a reference signal downhole near the drill bit is analyzed, and information about the signal is sent to the surface using a limited number of transmission bits. In one embodiment, a library of anticipated drill bit wavelets is stored in memory downhole and in memory at the surface. This library of anticipated drill bit wavelets is based on long term experience (several years) as well as theoretical considerations in collecting drill bit signals downhole and, in fact, could also be considered a data base of these collected drill bit signals. The best matching wavelet is identified by the processor downhole and then a code identifying the wavelet and a scaling factor are sent to the surface. At the surface, the best matching wavelet is retrieved based on the code received and then a reconstructed signal is created using the retrieved wavelet and the scaling factor. In another embodiment, key characteristics of the signal such as central frequency, frequency band, etc., are calculated downhole and transmitted to the surface. These key characteristics are then used to reconstruct the reference signal which is then used for correlation of surface detected signals. Once this correlation is done, the data are analyzed at the surface using known techniques.
[0007] The Dubinsky patent addresses the problem of telemetry of source wavelets to the surface in the context of a reverse VSP. The present invention is a modification of the apparatus and method of Dubinsky in the context of a conventional VSP, i.e., source at the surface and receiver downhole. There are other differences between the method and apparatus of the present invention and the teachings of Dubinsky. These are discussed below.
SUMMARY OF THE INVENTION
[0008] In a system and method of seismic surveying of an earth formation, a seismic wave is generated using a controllable source at a first location for propagating a seismic wave through said earth formation. A downhole receiver is used for receiving a first signal indicative of the propagating seismic wave. A second signal indicative of a character of the generated seismic wave is transmitted to the downhole location. The first signal is then processed using the second signal. The first location may be at or proximate to the surface of a body of water of land. Alternatively, the first location may be in a preexisting wellbore. The method received signal may be a direct signal or a reflected signal. Compressional or shear seismic signals may be generated.
[0009] The second signal may be a parameter of the control signal for the controllable source. Alternatively, the second signal is based at least in part on a signal measured by a reference detector proximate to the source location. The source may be a swept frequency source. Alternatively, the source may be an airgun array. Using measurements made at different depths, an attenuation factor may be derived from the direct arrival. When measurements are made at a plurality of depths, a vertical seismic profile (VSP) may be obtained.
[0010] In another embodiment of the invention, a seismic wave is generated at or near a surface location. Signals received by a receiver on a bottomhole assembly (BHA) at a shallow depth define a reference wavelet. This reference wavelet is then used for determining arrival times of direct signals at increasing depths of the BHA. The reference wavelet may be updated at each depth.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The present invention is best understood with reference to the accompanying figures in which like numerals refer to like elements, and in which:
[0012] FIG. 1 (Prior Art) shows a measurement-while-drilling device suitable for use with the present invention;
[0013] FIG. 2 illustrates the arrangement of source and sensors for the present invention;
[0014] FIG. 3 (Prior Art) shows an example of a vertical seismic profile;
[0015] FIG. 4 shows a flow chart of processing carried out with one embodiment of the present invention;
[0016] FIG. 5 shows an example of a frequency spectrum of the output of a swept frequency source;
[0017] FIG. 6 schematically illustrates the layout for a second embodiment of the present invention; and
[0018] FIG. 7 is a flow chart illustrating a second embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0019] FIG. 1 shows a schematic diagram of a drilling system 10 with a drillstring 20 carrying a drilling assembly 90 (also referred to as the bottom hole assembly, or “BHA”) conveyed in a “wellbore” or “borehole” 26 for drilling the wellbore. The drilling system 10 includes a conventional derrick 11 erected on a floor 12 which supports a rotary table 14 that is rotated by a prime mover such as an electric motor (not shown) at a desired rotational speed. The drillstring 20 includes a tubing such as a drill pipe 22 or a coiled-tubing extending downward from the surface into the borehole 26 . The drillstring 20 is pushed into the wellbore 26 when a drill pipe 22 is used as the tubing. For coiled-tubing applications, a tubing injector, such as an injector (not shown), however, is used to move the tubing from a source thereof, such as a reel (not shown), to the wellbore 26 . The drill bit 50 attached to the end of the drillstring breaks up the geological formations when it is rotated to drill the borehole 26 . If a drill pipe 22 is used, the drillstring 20 is coupled to a drawworks 30 via a kelly joint 21 , swivel 28 , and line 29 through a pulley 23 . During drilling operations, the drawworks 30 is operated to control the weight on bit, which is an important parameter that affects the rate of penetration. The operation of the drawworks is well known in the art and is thus not described in detail herein.
[0020] During drilling operations, a suitable drilling fluid 31 from a mud pit (source) 32 is circulated under pressure through a channel in the drillstring 20 by a mud pump 34 . The drilling fluid passes from the mud pump 34 into the drillstring 20 via a desurger (not shown), fluid line 28 and kelly joint 21 . The drilling fluid 31 is discharged at the borehole bottom 51 through an opening in the drill bit 50 . The drilling fluid 31 circulates uphole through the annular space 27 between the drillstring 20 and the borehole 26 and returns to the mud pit 32 via a return line 35 . The drilling fluid acts to lubricate the drill bit 50 and to carry borehole cutting or chips away from the drill bit 50 . A sensor S 1 placed in the line 38 can provide information about the fluid flow rate. A surface torque sensor S 2 and a sensor S 3 associated with the drillstring 20 respectively provide information about the torque and rotational speed of the drillstring. Additionally, a sensor (not shown) associated with line 29 is used to provide the hook load of the drillstring 20 .
[0021] In one embodiment of the invention, the drill bit 50 is rotated by only rotating the drill pipe 22 . In another embodiment of the invention, a downhole motor 55 (mud motor) is disposed in the drilling assembly 90 to rotate the drill bit 50 and the drill pipe 22 is rotated usually to supplement the rotational power, if required, and to effect changes in the drilling direction.
[0022] In one embodiment of FIG. 1 , the mud motor 55 is coupled to the drill bit 50 via a drive shaft (not shown) disposed in a bearing assembly 57 . The mud motor rotates the drill bit 50 when the drilling fluid 31 passes through the mud motor 55 under pressure. The bearing assembly 57 supports the radial and axial forces of the drill bit. A stabilizer 58 coupled to the bearing assembly 57 acts as a centralizer for the lowermost portion of the mud motor assembly.
[0023] In one embodiment of the invention, a drilling sensor module 59 is placed near the drill bit 50 . The drilling sensor module contains sensors, circuitry and processing software and algorithms relating to the dynamic drilling parameters. Such parameters can include bit bounce, stick-slip of the drilling assembly, backward rotation, torque, shocks, borehole and annulus pressure, acceleration measurements and other measurements of the drill bit condition. A suitable telemetry or communication sub 72 using, for example, two-way telemetry, is also provided as illustrated in the drilling assembly 90 . The drilling sensor module processes the sensor information and transmits it to the surface control unit 40 via the telemetry system 72 .
[0024] The communication sub 72 , a power unit 78 and an MWD tool 79 are all connected in tandem with the drillstring 20 . Flex subs, for example, are used in connecting the MWD tool 79 in the drilling assembly 90 . Such subs and tools form the bottom hole drilling assembly 90 between the drillstring 20 and the drill bit 50 . The drilling assembly 90 makes various measurements including the pulsed nuclear magnetic resonance measurements while the borehole 26 is being drilled. The communication sub 72 obtains the signals and measurements and transfers the signals, using two-way telemetry, for example, to be processed on the surface. Alternatively, the signals can be processed using a downhole processor at a suitable location (not shown) in the drilling assembly 90 .
[0025] The surface control unit or processor 40 also receives signals from other downhole sensors and devices and signals from sensors S 1 -S 3 and other sensors used in the system 10 and processes such signals according to programmed instructions provided to the surface control unit 40 . The surface control unit 40 displays desired drilling parameters and other information on a display/monitor 42 utilized by an operator to control the drilling operations. The surface control unit 40 can include a computer or a microprocessor-based processing system, memory for storing programs or models and data, a recorder for recording data, and other peripherals. The control unit 40 can be adapted to activate alarms 44 when certain unsafe or undesirable operating conditions occur.
[0026] The apparatus for use with the present invention also includes a downhole processor that may be positioned at any suitable location within or near the bottom hole assembly. The use of the processor is described below.
[0027] Turning now to FIG. 2 , an example is shown of source and receiver configurations for the method of the present invention. Shown is a drillbit 50 near the bottom of a borehole 26 ′. A surface seismic source is denoted by S and a reference receiver at the surface is denoted by R 1 . A downhole receiver is denoted by 53 , while 55 shows an exemplary raypath for seismic waves originating at the source S and received by the receiver 53 . The receiver 53 is usually in a fixed relation to the drillbit in the bottom hole assembly. Also shown in FIG. 2 is a raypath 55 ′ from the source S to another position 53 ′ near the bottom of the borehole. This other position 53 ′ could correspond to a second receiver in one embodiment of the invention wherein a plurality of seismic receivers are used downhole. In an alternate embodiment of the invention, the position 53 ′ corresponds to another position of the receiver 53 when the drillbit and the BHA are at a different depth.
[0028] Raypaths 55 and 55 ′ are shown as curved. This ray-bending commonly happens due to the fact that the velocity of propagation of seismic waves in the earth generally increases with depth. Also shown in FIG. 2 is a reflected ray 61 corresponding to seismic waves that have been produced by the source, reflected by an interface such as 63 , and received by the receiver at 53 .
[0029] An example of a VSP that would be recorded by such an arrangement is shown in FIG. 3 . The vertical axis 121 corresponds to depth while the horizontal axis 123 corresponds to time. The exemplary data in FIG. 3 was obtained using a wireline for deployment of the receivers. Measurements were made at a large number of depths, providing the large number of seismic traces shown in FIG. 3 .
[0030] Even to an untrained observer, several points are apparent in FIG. 3 . One point of interest is the direct compressional wave (P-wave) arrival denoted by 101 . This corresponds to energy that has generally propagated into the earth formation as a P-wave. Also apparent in FIG. 3 is a direct shear wave (S-wave) arrival denoted by 103 . Since S-waves have a lower velocity of propagation than P-waves, their arrival times are later than the arrival times of P-waves.
[0031] Both the compressional and shear wave direct arrivals are of interest since they are indicative of the type of rock through which the waves have propagated. To one skilled in the art, other visual information is seen in FIG. 3 . An example of this is denoted by 105 and corresponds to energy that is reflected from a deeper horizon, such as 63 in FIG. 2 and moves up the borehole. Consequently, the “moveout” of this is opposite too the moveout of the direct arrivals (P- or S-). Such reflections are an important part of the analysis of VSP data since they provide the ability to look ahead of the drillbit.
[0032] Turning now to FIG. 4 , a flow chart of an embodiment of the method of the present invention is shown. A surface signal is generated 203 . As in any VSP acquisition, there are a number of choices available for sources used in data acquisition. Broadly speaking, there are two types of sources: impulsive, and non-impulsive. In a marine environment, a commonly used impulsive source is an airgun or an airgun array. An airgun is a device with relatively low energy (in contrast to high energy explosive sources such as dynamite). Low energy sources such as airguns are used for several reasons, including reduced injury to marine life, and for safety issues. A single airgun produces an air bubble that produces continued pulsing and is hence not desirable for VSP data acquisition: the continued oscillations result in a fairly narrow spectral bandwidth that makes it difficult to accurately pick the arrival time of a seismic signal. For this reason, air gun arrays with a reasonably broad bandwidth are commonly used in marine data acquisition. With the use of air gun arrays comes the flexibility of spectrally tuning the air gun array to obtain a desirable bandwidth and to maximize the signal level at the receiver. An example of a tunable airgun array is given in U.S. Pat. No. 4,739,858 to Dragoset.
[0033] A non impulsive source that has been used for marine seismic data acquisition is a marine vibrator. Marine vibrators have a long history in seismic data acquisition. More recent developments, such as that disclosed in U.S. Pat. No. 4,918,668 to Sallas include the a tunable array of marine vibrators. In vibratory surveys, the source sends out a low power swept-frequency signal with a duration of the order of ten to twenty seconds. The received signal is cross-correlated with the the sweep signal (or a signal related to the sweep signal) to recover the impulse response of the earth. Processing of marine vibratory data in conventional surface seismic data acquisition requires a Doppler compensation for the motion of the source. This is not a problem with VSP data acquisition carried out at a fixed source location. However, if an offset-VSP survey is carried out with a moving source, Doppler correction is necessary. Doppler compensation methods have been discussed, for example, in U.S. Pat. No. 4,809,235 to Dragoset et. al.
[0034] Use of vibrators as a seismic source for land seismic surveys has an equally long history. U.S. Pat. No. 3,701,968 to Broding and U.S. Pat. No. 3,727,717 to Miller disclose the use of vibrators with vertical motion suitable for use as compressional wave sources. U.S. Pat. No. 3,159,232 to Fair discloses the use of a horizontal vibrator for generation of shear wave energy.
[0035] A common characteristic of the sources described above is that the output signal is controllable in terms of directionality and, particularly, the frequency spectrum. In this sense, the seismic sources are controllable. The ability to control the spectral characteristics is used in one embodiment of the invention discussed below.
[0036] The downhole detectors used in the present invention typically include one or more of hydrophones, geophones, or accelerometers. Hydrophones are sensitive to pressure variations and as such, do not require coupling to the earth formation. The performance of the other sensors (geophones and accelerometers) is improved if there is good coupling with the earth formation. When these sensors are on the BHA, coupling may be difficult to achieve. In one embodiment of the invention, the downhole detectors are mounted on a non-rotating sleeve that may be clamped to the borehole wall. Such a non-rotating sleeve is disclosed in U.S. Pat. No. 6,247,542 to Kruspe et. al., having the same assignee as the present invention and the contents of which are fully incorporated herein by reference. When used for shear-wave VSPs, it is particularly important to have sensors that are responsive to horizontal motion, i.e., x- and y-component geophones or accelerometers (in a vertical borehole) since a vertically propagating shear wave has little or no vertical motion. When a P-wave VSP is being conducted, it is not necessary to have the sensors in a fixed position. Hydrophones are omnidirectional in their sensitivity and can be used on a rotating sensor for receiving P-wave signals downhole.
[0037] Another consideration is that with swept frequency sources, the response of the downhole x- and y-sensors to an arriving a shear wave signal will depend upon the orientation of the sensors. If the sensors are rotating with the BHA, it is necessary to know the orientation of the sensors during the data acquisition. This can be done using magnetometers and/or accelerometers. The received signals must be corrected (using a straightforward rotation of coordinates) for the orientation prior to further processing and this capability is part of the downhole processor. On the other hand, if the sensors are on a non-rotating sleeve, this continuous correction is not needed.
[0038] It should be noted that with a source at the surface and downhole detectors, the number of parameters needed to characterize the source wavelet (and the possible suite of possible wavelet shapes) is less than for the problem addressed by Dubinsky. In Dubinsky, the drillbit itself acts as a seismic source, and even in the simplest situations, the output seismic signals are dependent upon many parameters such as the earth formations being drilled, the weight on bit, the torque applied at the drill string. The source wavelet would be further dependent upon the drilling mode (possible whirl, sticking of the drillbit, etc.). On the other hand, the receiver for the present invention is in a much more noisy environment due to its proximity to the drillbit. In one embodiment of the present invention, an attenuator is used for attenuating noise
[0039] Returning to FIG. 2 , activation of the source results in propagation of a seismic waves into the earth formation (as depicted by the rays 55 , 55 ′, and 61 ). The resulting data are received by the downhole detector(s) and may be stored on a suitable memory device downhole. A reference detector R 1 may be used to measure the downgoing signal, and key characteristics of the generated signal are transmitted downhole 205 . This telemetry may be accomplished, for example, by using mud pulse telemetry such as that disclosed in U.S. Pat. No. 5,963,138 to Gruenhagen. When a reference detector is used in land VSP surveys, it could be a buried detector (geophone, hydrophone or accelerometer). When a reference detector is used in marine VSP surveys, it could be a hydrophone within the water layer, or it could be a detector buried in the sub-bottom.
[0040] With a swept frequency source, the most commonly used sweep is a linear sweep in which the instantaneous frequency is given by an expression of the form:
ω=ω 0 +At (1)
where ω 0 is the initial angular frequency, ω is the frequency at time t, and A is the rate of change of the angular frequency with time. The amplitude of the sweep typically includes a middle portion where the amplitude is uniform, and an earlier and later taper to zero amplitude. This is illustrated schematically in FIG. 5 .
[0041] When a linear frequency sweep is used, the key characteristics of the source signal that are transmitted downhole are the initial frequency ω 0 , the sweep rate A and the duration of the sweep. Those versed in the art would recognize that essentially the same information could be conveyed by the total time of the sweep, and the initial and ending frequencies. Other equivalent formulations may also be used. In addition, the key characteristics would include information pertaining to the amplitude taper rate from FIG. 5 . The point to note is that the source signal can be characterized by a limited number of characteristics, so that transmitting the information downhole is feasible within the limited telemetry capabilities of the telemetry system.
[0042] Once this key information about the source characteristics has been transmitted downhole, the downhole processor can reconstruct the source signal. Another piece of information that is transmitted downhole is the start time of the signal. In one embodiment of the invention, a rubidium clock is used for maintaining synchronization between the surface seismic source and the downhole processor. Such a rubidium clock is disclosed in a U.S. patent application filed under Attorney Docket No. 584-34604 on Sep. 18, 2003 of DiFoggio et al. having the same assignee as the present invention and the contents of which are fully incorporated herein by reference.
[0043] Those versed in the art would recognize that the earth is a dissipative medium that selectively absorbs higher frequencies. A commonly used model characterizes the earth by a quality factor Q. The quality factor may be a slowly varying function of depth depending upon the formation lithology and fluid content. With such a model, the propagation wave number of a seismic wave propagating in the z- direction can be written as:
k 2 = ( ω V + i α ) ( 2 )
where k z is the wave number, ω is the angular frequency, V is the phase velocity, and α is the attenuation factor. The attenuation factor α is related to the quality factor Q by
α = ω 2 QV . ( 3 )
A commonly used approximation relates the velocity V to a reference velocity V r at angular frequency ω r by a relation of the form:
V r V = 1 - 1 π Q ln ( ω ω r ) ( 4 )
Using eqns (2)-(4) and the key characteristics of the source signal transmitted downhole, the waveform of the seismic signal can be reconstructed. The time of source activation is used to define the window for analysis 211 of the data downhole. The reconstructed waveform may be used as a filter for processing the the recorded data 209 for further analysis 213 using known methods for processing the VSP data.
[0044] Using the concepts discussed above, an exemplary use of the invention is discussed next with reference to FIG. 6 . In a VSP-type measurement, a seismic signal generated by a reproducible standard surface seismic source 301 like an air gun or a vibrator is recorded while drilling by means of multiple downhole acoustic sensitive sensors (geophones, accelerometers, hydrophones). The source wavelet is registered on the surface by means of a near-source receiver 303 . In FIG. 6 , the receiver 305 is shown on the surface of the earth, but it could be buried (in land), in the water or in the sub-bottom (for marine recording).
[0045] Starting at an initial depth such as 305 while drilling ahead, the seismic signal generated by the source may be recorded. This may be done at a shallow depth and within an acoustic “silent” environment so that the wavelet is a fair representation of the outgoing signal from the source. From the known source wavelet (either predetermined, or telemetered downhole) an attenuation factor α for the raypath 351 may be determined.
[0046] At the next depth level 307 , a second measurement cycle is performed. Due to the greater depth and the increased noise level caused by the drilling process, the signal is much more attenuated and distorted at this level than when the receiver is at 305 . Now the previously identified wavelet from depth 305 nay be used to determine the first arrival time of the new measurement cycle by means of cross-correlation or similar techniques. The wavelet is then identified within the seismic trace of the actual measurement based on the received signal following the first arrival time. In one embodiment of the invention, an attenuation factor a is determined from a comparison of the wavelet derived at 305 and the wavelet at depth 307 . The attenuation factor may be considered to be a parameter characteristic of the earth formation.
[0047] The process described above is then repeated at other depths such as 309 . . . 311 so that first arrival times and attenuation factors can be obtained using wavelets measured at shallower depths
[0048] The process of determining first arrival times is schematically illustrated in FIG. 7 . As shown in FIG. 7 , at the initial depth 401 , the reference wavelet (signal) is determined 411 . An initial value of a may also be determined at this point. This reference wavelet is then used, at the next depth 403 , to determine a first arrival time 405 . Once the arrival time at depth 403 is established, by proper windowing an updated wavelet 407 is obtained. If the drilling of the well is continued 409 , the process is repeated starting at 403 with the updated wavelet 407 serving as the new reference wavelet 411 . An attenuation factor a may also be determined 413 . As would be known to those versed in the art, in most cases of practical interest, the direct arrival occurs within ten seconds of activation of a seismic source at the surface.
[0049] In an alternate embodiment of the invention, an average value of α may be determined at each depth using telemetered information from the surface about the source signal. Using such telemetered information for determining an average value of α avoids problems that may occur when noisy wavelets at successive depths are used for determining an incremental value of α.
[0050] The present invention has been described in the context of VSP data acquisition in which a seismic source is at or near a surface location. However, the invention could also be used when the seismic source is located in a preexisting wellbore. With such an arrangement, crosswell measurements could be made during the process of drilling a wellbore. Based on these crosswell measurements, the position of the wellbore being drilled from a preexisting wellbore can be determined and, based on the determined distance, the drilling direction of the wellbore can be controlled.
[0051] While the foregoing disclosure is directed to the preferred embodiments of the invention, various modifications will be apparent to those skilled in the art. It is intended that all such variations within the scope and spirit of the appended claims be embraced by the foregoing disclosure.
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A controllable seismic source is used in a seismic-while-drilling system for obtaining VSP data. Coded information is sent downhole about the signal generated by said controllable source. The information about the seismic source is used for reconstructing the source waveform and processing the VSP data. Optionally, a reference signal measured at one depth of the BHA is used for processing of signals at subsequent depths
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RELATED APPLICATIONS
[0001] This application is a continuation of application Ser. No. 10/395,608, filed on Mar. 24, 2003, entitled “Mortarless Wall Structure,” and published as US Publication No. 2003/0188497 on Oct. 9, 2003 which is a continuation in part of application Ser. No. 10/015,052, filed Dec. 11, 2001, entitled “Mortarless Wall Structure,” and issued as U.S. Pat. No. 6,691,471 on Feb. 17, 2004, which is a continuation in part of application Ser. No. 09/547,206, filed Apr. 12, 2000, entitled “Skirting Wall System,” and issued as U.S. Pat. No. 6,374,552 on Apr. 23, 2002. This application is also a continuation in part of application Ser. No. 10/363,999, filed Apr. 12, 2001, entitled “Mortarless Wall Structure,” and published as US Publication No. 2004/0006945 on Jan. 15, 2004, which is a continuation in part of application Ser. No. 09/547,206, filed Apr. 12, 2000, entitled “Skirting Wall System,” and issued as U.S. Pat. No. 6,374,552 on Apr. 23, 2002. This application also claims priority to PCT application Ser. No. PCT/US01/11957 filed on Apr. 12, 2001, entitled “Wall Structure,” and PCT application Ser. No. PCT/US00/25791 filed on Sep. 20, 2000, entitled “Wall Structure,” and all of which are hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to decorative and structural blocks designed to be installed as exterior and interior walls for buildings. More particularly, the present invention relates to a system that uses specifically designed and manufactured masonry blocks that are used in conjunction with specifically designed support beams and/or brackets to provide durable, attractive, easy to assemble surfaces to a wide variety of buildings, structures, and structural elements.
BACKGROUND OF THE INVENTION
[0003] Transportable structures such as mobile homes, trailer homes, modular homes and recreational vehicles, by their very nature, are usually not intended to be built upon a conventional foundation. Rather, they are brought or driven to a location where they may remain for indeterminate periods of time. Often, over an extended period at a particular site, such structures may start to settle differentially onto or in the ground due to factors such as deflating tires or local variations in soil bearing capacities.
[0004] Additionally, factors such as erosion and freeze-thaw cycles may also cause such structures to shift and/or tilt. In order to prevent such unwanted movement and ensure that a structure is level regardless of the ground's topography, the structures are often placed on stilts that extend from the structure or upon piles that extend from the ground, or even on isolated footings that distribute the weight of a structure over a relatively large surface area. While this solves the aforementioned problem of shifting/or sinking it often results in an unsightly visible gap in the area between the ground and the bottom of the structure.
[0005] Various attempts to cover the unsightly gap have included the use of plants, natural material such as rocks and wood and manmade products such as cement, masonry and plastics. These attempts have proven to be either prohibitively expensive, difficult to install and/or disassemble, or unattractive and unable to withstand sustained exposure to nature's elements. Attempts that tend to be prohibitively expensive or difficult to install include, for example, wall structures constructed of large, custom-made, cement slabs having decorative faces, and standard masonry blocks held together with mortar. Attempts that fall into the latter category include such relatively fragile and easily breakable products as wooden or plastic lattices, and synthetic panels designed to simulate stones or bricks.
[0006] Consequently, there is a need for an easy to assemble and/or dissemble, lightweight and sturdy, inexpensive wall structure for covering the gap between the ground and an elevated structure such as a mobile home.
[0007] In other applications, where brick, stone, or concrete is used as veneer or fascia, for fencing, and as load-bearing and non load-bearing walls, etc., these structures are constructed with an eye towards permanence. That is, the structures are not meant to be easily dismantled. This means that the component parts are often able to interconnect with each other and/or with a support framework in some fashion. This usually entails the use of robust connections such as mechanical fasteners, adhesives, cement, or the like. For example, many types of veneers are typically coated with adhesive or cementitious material to enable them to be securely and directly bonded to a structure. Or, as another example, walls may be constructed in a conventional manner with blocks and mortar.
[0008] Alternatively, wall structures may comprise heavy, interlocking blocks that rely on size and weight to achieve some measure of permanence. As one may well imagine, each of the aforementioned structures would be difficult and time consuming to reconfigure, remove, or repair should the need arise. And while the construction of some of these structures typically requires specialized knowledge, skills, and tools to achieve, it will be appreciated that disassembly may require other, additional specialized knowledge, skills, and tools to achieve. In light of these shortcomings, there is an additional need for a wall structure that may be easily assembled, disassembled and rebuilt or reconfigured by an unskilled user without damage to the constituent parts of the wall structure and which may be used as a veneer, fascia, cladding, fence, or as a load-bearing or non load-bearing wall.
[0009] The present invention provides a solution to these needs and other problems, and offers other advantages over the prior art.
SUMMARY OF THE INVENTION
[0010] Generally, the present invention provides a system by which structures may be provided with durable, easy to assemble externally facing surfaces, which are generally vertical and which may be used in a wide variety of applications. The system utilizes a series of particularly configured blocks that may be operatively connected to the structures by beams and/or brackets. One embodiment of the present invention provides a block wall system for use in skirting elevated structures. The blocks are shaped to be stacked in vertically independent, self-supporting columns, strengthened and linked together by specially shaped, lightweight, lateral support beams positioned between adjacent columns, and which may be stabilized by one or more inverted u-shaped brackets which are attached at or near the bottom of an elevated structure. In an alternative embodiment, a u-shaped bracket is provided with an arm that is rotatably attached thereto and which is movable into a position that facilitates attachment to a generally vertical surface. In another embodiment, the blocks are configured so that lateral support beams may be positioned not only between adjacent columns but also at intermediate positions along the block as well. In another embodiment, the lateral support beam is configured so that it can be movably coupled to a bracket, which may be attached to an existing structure.
[0011] One embodiment of the block comprises a front face, a rear face, top and bottom surfaces, and side surfaces, and each side surface includes an outwardly opening, vertically oriented groove for receiving a portion of a support beam. The top and bottom surfaces are configured to facilitate a stacking relationship between adjacent courses of blocks such that they are generally coplanar. This relationship is most easily achieved by making the top and bottom surfaces substantially collateral, planar and relatively perpendicular to rear and/or front faces. Another embodiment of the block includes the provision of externally formed channels that are configured and arranged to prevent moisture from forming and collecting at the rear face of the block. Another embodiment of the block includes at least one through hole or aperture that is substantially aligned with outwardly opening, vertically oriented grooves in the side surfaces of a block. As will be explained later, the through holes or apertures facilitate use with support beams in a variety of applications. Another embodiment of the block has viewable surfaces or facings that are angled with respect to each other and which facilitate the formation of closed structures.
[0012] One purpose of the beams is to keep vertically stacked, self-supporting columns of blocks from buckling when subjected to a force normal to the plane of the column. This strengthening is accomplished providing the beams with lateral extensions or ribs that are configured to be received in aligned grooves at the sides of the vertically stacked blocks. Another purpose of the beams is to link adjacent columns of blocks together in a colonnade-like arrangement to form a wall structure. This is also achieved with the aforementioned lateral extensions and grooves. As may be expected, the beams provide very little, if any, support in a vertical direction. The columns so constructed are considered independent because, unlike conventionally constructed masonry or stone walls, the joints between adjacent blocks are in alignment with each other rather than being offset as in a running bond. This enables the columns of blocks to move up and down relative to each other, without appreciably altering the inherent continuity of a wall structure. As will be appreciated, the rigidity of the blocks provides enough support to prevent a column from failing in the vertical direction. When a more robust wall structure is desired, blocks that have appropriately configured apertures and rearwardly facing slots may be stacked in a running bond arrangement and strengthened and linked together by support beams. Although the beams can be fabricated form a variety of materials such as metals and plastics, extruded aluminum, nylon, and polyvinyl chloride (PVC) are preferred.
[0013] It will be appreciated that the use of the lateral support beams also eliminates and/or substantially reduces the need for mortar to stabilize and unify the blocks. This wall structure system is advantageous over traditional brick and mortar walls for obvious reasons. First, fewer materials are required to build a wall. Second, the materials are easier to handle and manipulate, and no special tools or skills are required. Third, a wall can be constructed under conditions that would not be possible using traditional brick and mortar construction and a person need not be concerned about time constraints imposed by drying mortar. Fourth, the joints formed between adjacent blocks allow the wall to appear monolithic or seamless at a surprisingly close distance. Moreover, by providing blocks that have had their marginal areas modified, it is also possible to create walls that have the appearance of conventional block and mortar construction. Fifth, the block wall system can be constructed on a variety of surfaces, including sand, gravel, dirt, or building elements such as H-beams, flooring, base blocks, etc. It is not necessary to pour a foundation.
[0014] The lateral support beams also allow the blocks to be substantially thinner than conventional masonry blocks. These thin, lightweight blocks are not only easier to handle and ship, but require less material and time to fabricate. The blocks are generally about 1 to 4 inches (2.5-10 cm.) thick, about 6 to 12 inches (15-30 cm.) in height and about 6 to 24 inches (15-60 cm.) in width, and preferably have a thickness on the order of around 2½ inches (6.0 cm.). As one may appreciate, the combination of the thin blocks and the support beams facilitates construction of masonry wall structures in locations and configurations that were heretofore not possible using thin blocks alone. The resulting wall structure of this system is surprisingly strong and it may even be used to provide support to an elevated structure. When a wall structure is installed about an elevated structure, such as a portable home, the elevated structure may be lowered onto the blocks of the wall. Alternatively, the block wall system may serve as a skirt, which improves the aesthetics of the structure and keeps animals, litter, snow, etc. from intruding or being otherwise introduced beneath the structure. Or, the block wall system may be used with existing structures such as elevated decks and retaining walls. With these embodiments, it is not necessary that the blocks make actual contact with the structure.
[0015] The block wall system also allows the wall to be easily disassembled and reassembled. This not only gives flexibility during initial construction, but also allows later renovations to be made quickly and inexpensively. For instance, it may be desirable or required to vent elevated structures having skirting walls, to prevent the buildup of moisture or condensation between the ground and the elevated structure. Such vents can be easily installed into an existing wall, especially if they are of similar dimensions and configurations as the blocks. The blocks of a given column are simply removed and reinstalled, replacing one of the blocks with the vent. Other auxiliary items, such as an access door or lights, could be installed in a similar manner.
[0016] The wall block system of the present invention is not confined to linear structures. As will be appreciated, the system also allows walls to intersect to form angled or closed structures. In one embodiment, two intersecting walls are simply aligned to form a butt joint and fasteners such as pegs, or screws, and plastic inserts are used to fasten one wall to the other. Alternatively, construction mastic, or a similar type of adhesive, may be applied instead of or in combination with the above mentioned fasteners. In another embodiment, blocks are preformed as angled intersecting wall units that have been provided with outwardly opening, vertically oriented side grooves configured to receive portions of support beams, which may be further linked to other wall blocks as described above. As will be appreciated, such blocks may be combined together to form hollow columnar structures, or may be used to clad an existing structure such as a support post. Again, ease of installation is greatly improved by the block wall system of the present invention.
[0017] Another embodiment of the wall structure uses a differently configured bracket than the aforementioned u-shaped bracket. It, too, is used to operatively connect the wall structure to a support. The bracket of this embodiment, however, attaches in a slightly different manner than the u-shaped bracket. Instead of straddling the upper portion of a top-most block as with the u-shaped bracket of the aforementioned embodiment, this bracket has one end that is configured to be positioned within space defined by opposing vertical grooves of adjacent blocks. That is, the bracket is designed to be installed at or near the sides of a column. The other end of the bracket is configured to be attached at or near the bottom of a structure. An advantage with this bracket it that it is able to provide support for the wall structure in two directions, while allowing movement of wall components relative thereto in a third direction. As will be appreciated, this bracket may be easily installed and removed without the need for special training or tools. Preferably, the bracket of this embodiment is L-shaped, although it is envisioned that other shapes are possible. For example, the bracket may be linear, or it may be linear and have an axial twist in it. Or, the structure-engaging portion may be provided with a u-shape or even its own integral fastener.
[0018] An assembly of blocks may be operatively connected to a support using yet another embodiment of the wall skirting system. With this embodiment, the support beam is configured to be movably coupled to one or more brackets that, in turn, may be attached to the support. This allows the beam to move relative to the bracket(s) without sacrificing the strength of the assembled blocks, and also allows the beams to be connected to the structure at different locations along its length. For example, at the top, at the bottom, or anywhere in between. As will be understood, in order for the support beam and bracket to operate in such a constrained manner the bracket(s) need to be configured so that they are able to slidingly retain the beam. Thus, differently configured beams may require specially configured brackets.
[0019] In another embodiment of the block wall system, blocks are operatively connected to a structure with one or more brackets, which are configured to be able to engage the side grooves of adjacent blocks, and which may be directly attached to the structure. As will be appreciated, the brackets of this embodiment will permit the blocks to move relative thereto, but not to the degree that is available with the aforementioned support beam and bracket combination. As with the aforementioned support beams, the brackets can be fabricated form a variety of materials such as metals and plastics. However, steel, extruded aluminum, nylon, and polyvinyl chloride (PVC) are preferred.
[0020] It will be appreciated that wall structures other than linear structures are possible. For example, support beams and blocks may be used to construct circular, or sinuous structures by providing curved blocks or blocks with one curved viewable surface (when viewed cross-sectionally from a point above the top surface of the block) that are operatively connected to support beams that are similarly arranged. Alternatively, a wall structure may be constructed in a zigzag or erose form with the support beams collaterally arranged relative to each other in a zigzag manner. To reduce vertical gaps between forwardly facing viewable surfaces of adjacent blocks in such a wall structure, it would be a matter of providing support beams with ribs that are angled with respect to the web and mitering or beveling the opposing sides of the blocks, or using a combination of both angling and mitering the ribs and sides, respectively. A similarly configured wall may also be constructed using support beams arranged in a coplanar or staggered fashion relative to each other and blocks having a predetermined, angular viewable surface (when viewed cross-sectionally from a point above the top surface of the blocks). For example, a “V”, “L”, or a “W”. Such blocks may have parallel front and rear faces, if desired. With such a construction, neither the support beams nor the opposing fingers need to be modified. In a related construction, it is envisioned that blocks be constructed having angles of ninety degrees so that they may be used as inner or outer corners. With such blocks, the opposing sides and their fingers would be perpendicular to each other.
[0021] In one method of constructing a freestanding, low wall structure of the present invention, a person would prepare or otherwise select an appropriate location in which to construct a wall. The construction would begin by placing a first block having opposing side grooves in a desired position and orientation. Then, a second, similar block would be placed directly on top of the first block so that the opposing side grooves of the first and second blocks are in vertical alignment with each other and the first and second blocks form a column. Next, the first and second blocks would be operatively connected to each other along their respective sides by inserting at least one rib of first and second support beams into the aligned grooves of the respective sides of the first and second blocks and seating them securely. A second column comprising similarly configured third and a fourth blocks may now be constructed. The operation is much the same, except now the third block is positioned so that one of its sides is adjacent to one of the sides of the first block and its groove engages at least one other rib of one of the already positioned support beams. The fourth block is then positioned on top of the third block in a similar manner. That is, the fourth block is positioned so that one of its sides is adjacent to one of the sides of the second block and its groove engages at least one other rib of one of the already positioned support beam. After the second column is erected, the third and fourth blocks would be operatively connected to each other along their respective free side by inserting at least one rib of a third support beam into their aligned vertical groove of the respective sides of the first and second blocks and seating them securely. And so on.
[0022] Another, alternative method of constructing a wall structure of the present invention according to the present invention would be as follows. A person would prepare or otherwise select an appropriate substructure on which to construct a wall structure. The construction would begin by operatively connecting a first elongated support beam to the substructure. Then using the first support beam as a reference, a series of additional support beams would be operatively connected to the substructure, with all of the support beams in vertical and collateral alignment, and with the distance between adjacent support beams sufficient to enable the ribs of adjacent beams to engage opposing side grooves of a block. Once the dimensions of the wall structure have been established, the blocks with opposing side grooves may be positioned by sliding the blocks along the length of and between adjacent support beams. This may be done course by course, column by column, or in a mixture of both columns and courses, as desired.
[0023] In a variation of the aforementioned methods of construction, a person would begin by operatively connecting a first elongated support beam to the substructure in a vertical orientation. Then a first block having opposing side grooves would be placed in a desired position and orientation against the first elongate support beam so that at least one of the ribs of the first beam is seated within one of the side grooves of the block. Then, a second, similar block would be placed directly on top of the first block so that the at least one rib of the first beam is also seated within one of the side grooves of the second block so that the opposing side grooves of the first and second blocks are in vertical alignment with each other and the first and second blocks form a column. Next, the first and second blocks are operatively connected to each other along their other respective sides by aligning the grooves of the respective sides of the first and second blocks, and inserting at least one rib of a second support beam into the aligned grooves and seating it securely therein. After the second support beam is seated, it is attached to the substructure. A second column comprising similarly configured third and a fourth blocks may now be constructed. The operation is the same, with the third block positioned so that one of its sides is adjacent to one of the sides of the first block and its groove engages another rib of the already positioned second support beam. The fourth block is then positioned on top of the third block in a similar manner. That is, the fourth block is positioned so that one of its sides is adjacent to one of the sides of the second block and its groove engages another rib of the already positioned second support beam. After the second column is erected, the third and fourth blocks would be operatively connected to each other along their respective free side by aligning the grooves of the respective sides of the third and fourth blocks, and inserting at least one rib of a third support beam into the aligned grooves and seating it securely therein. After the third support beam is seated, it is attached to the substructure. And so on.
[0024] Additional advantages and features of the invention will be set forth in part in the description which follows, and in part, will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] FIG. 1 is a partial, perspective view of two embodiments of the block wall system, with one preferred embodiment of blocks arranged below an elevated first (upper level) deck structure and another embodiment of blocks arranged about the perimeter of an adjacent, elevated second (lower level) deck structure;
[0026] FIG. 2 is a partial, exploded, perspective view of the block arrangement below the elevated first (upper level) deck structure of FIG. 1 ;
[0027] FIG. 2 a is a top plan view of the block arrangement of FIG. 1 , taken generally along lines 2 a - 2 a;
[0028] FIG. 3 is a side elevational, cross-sectional view of the block arrangement about the perimeter of the elevated second (lower level) deck structure of FIG. 1 taken generally along lines 3 - 3 ;
[0029] FIG. 3 a is a partial, side elevational, cross-sectional view of an alternative support for the block arrangement of FIG. 3 ;
[0030] FIG. 4 is a perspective view of an elevated structure skirted with an embodiment of the blocks of the present invention arranged in a wall structure;
[0031] FIG. 5 is a side elevational view the wall structure of FIG. 4 taken generally along lines 5 - 5 ;
[0032] FIG. 6 is a partial, perspective view of an embodiment of blocks arranged to provide a facia wall for a retaining wall;
[0033] FIG. 6 a is a partial, side elevational, cross-sectional view of the block arrangement of FIG. 6 taken generally along lines 6 a - 6 a;
[0034] FIG. 7 is a perspective view of another embodiment of a block of the present invention;
[0035] FIG. 7 a is a perspective view of another embodiment of a block of the present invention;
[0036] FIG. 7 b is a bottom plan view of the block of FIG. 7 a;
[0037] FIG. 8 is a partial, cross-sectional, plan view of an embodiment of a corner construction of a wall structure of the present invention;
[0038] FIG. 9 is a perspective view of another embodiment of a block of the present invention;
[0039] FIG. 10 is a bottom plan view of the block of FIG. 9 ;
[0040] FIG. 11 is a partial, perspective view of an embodiment of a support beam of the present invention;
[0041] FIG. 11 a is a partial, perspective view of an alternative embodiment of a support beam of the present invention;
[0042] FIG. 12 is a partial, perspective view of an alternative embodiment of a support beam;
[0043] FIG. 13 is a partial, perspective view of an alternative embodiment of a support beam;
[0044] FIG. 14 is a plan view of an alternative embodiment of a block engagement portion of a vertical support beam similar to that of FIG. 11 a , with the remainder of the support beam shown in phantom;
[0045] FIG. 15 is a plan view of an alternative embodiment of a block engagement portion of a support beam similar to that of FIG. 11 a , with the remainder of the support beam shown in phantom;
[0046] FIG. 16 is a partial, perspective view of an embodiment of a support beam of the present invention;
[0047] FIG. 17 is a partial, perspective view of another embodiment of a support beam in conjunction with a bracket, with the bracket configured to be attached to a sub structure;
[0048] FIG. 18 is a partial, perspective view of another embodiment of a support beam in conjunction with another embodiment of a bracket, with the bracket configured to be attached to a sub structure;
[0049] FIG. 19 is a partial, perspective view of another embodiment of a support beam in conjunction with another embodiment of a bracket with the bracket configured to be attached to a substructure;
[0050] FIG. 20 is a partial, perspective view of an embodiment of a support beam having an integrally formed aperture and an integrally formed bracket, with the support beam able to be used with the support beam of FIG. 19 to construct/form a double sided wall structure;
[0051] FIG. 21 a partial, perspective view of another embodiment of a support beam;
[0052] FIG. 22 is a partial, top plan view, taken generally along lines 22 - 22 of FIG. 4 , of showing adjacent blocks of the present invention in conjunction with a support beam;
[0053] FIG. 23 is a partial, top plan view of the two blocks abutted with a support beam of FIG. 22 , but with the support beam arranged in an alternative configuration;
[0054] FIG. 23 a is a partial, top plan view of the blocks of FIG. 23 as they may be assembled into a wall structure, or as a wall structure is disassembled;
[0055] FIG. 24 is a partial, top plan view of two blocks, a support beam, and a support bracket that have been assembled into a wall structure;
[0056] FIG. 24 a is a partial, top plan view of a portion of the blocks, support beam, and bracket of FIG. 24 , as they may be assembled into a wall structure, or as a wall structure is disassembled;
[0057] FIG. 25 is a partial, top plan view of two blocks of the present invention in conjunction with an alternative embodiment of a support beam;
[0058] FIG. 26 is a partial, top plan view of two blocks of the present invention in conjunction with another alternative embodiment of a support beam;
[0059] FIG. 27 is a partial, top plan view of the support beams shown in FIGS. 12 and 13 in conjunction with blocks of the present invention;
[0060] FIG. 28 is a partial, top plan view of two blocks of FIG. 7 a that are operatively connected to the support beam of FIG. 11 a;
[0061] FIG. 29 is a partial, top plan view of the support beam of FIG. 16 as it may be used to operatively connect blocks of the present invention to a substructure;
[0062] FIG. 30 is a perspective view of a wall structure construction using another preferred embodiment of support beams and blocks of the present invention;
[0063] FIG. 31 is a partial, top plan view of the support beam and bracket of FIG. 17 as they may be used to operatively connect blocks to a substructure;
[0064] FIG. 32 is a partial, top plan view of the support beam and bracket of FIG. 18 as they may be used to operatively connect blocks to a substructure;
[0065] FIG. 33 is a partial, top plan view of the support beam and bracket of FIG. 19 as they may be used to operatively connect blocks to a substructure;
[0066] FIG. 34 is a partial, top plan view of an alternative embodiment of the support beam of FIG. 21 as it may be used to operatively connect blocks to a substructure;
[0067] FIG. 35 is a partial, top plan view of the support beam of FIG. 21 as it may be used to operatively connect blocks to a substructure;
[0068] FIG. 36 is a partial, top plan view of the support beam of FIG. 20 and the support beam of FIG. 19 as they may be used to operatively connect differently sized blocks together in a dual-sided wall structure;
[0069] FIG. 37 is a partial, top plan view of the blocks of FIG. 7 in conjunction with another embodiment of a support beam, with the support beam operatively connecting the blocks to an existing structure;
[0070] FIG. 37 a is a partial, top plan view of the blocks of FIG. 7 in conjunction with another alternative embodiment of a support beam with the support beam operatively connecting the blocks to an existing structure;
[0071] FIG. 37 b is a partial, top plan view of blocks of FIG. 7 in conjunction with another alternative embodiment of a support beam with the support beam operatively connecting the blocks to an existing structure;
[0072] FIG. 38 is a partial, top plan view of a free standing dual wall structure wherein the respective walls of the wall structure are connected to each other in a spaced relation by an alternative embodiment of a support beam;
[0073] FIG. 39 is a partial, top plan view of blocks of FIG. 7 in conjunction with an alternative embodiment of the support beam of FIG. 20 , wherein the aperture is configured to received a post;
[0074] FIG. 40 is a partial, perspective view of an embodiment of a wall structure of the present invention and a preferred attachment bracket;
[0075] FIG. 41 is a perspective view of the attachment bracket of FIG. 40 ;
[0076] FIG. 42 is a side elevational view of the bracket of FIG. 41 attached to a lower surface of a structure, and as it may be attached to an upper surface of the structure (shown in phantom);
[0077] FIG. 43 is a perspective view if the attachment bracket of FIG. 41 as it may be used in conjunction with the support beam of FIG. 11 ;
[0078] FIG. 44 is an exploded, perspective view of an attachment bracket and the support beam of FIG. 11 a;
[0079] FIG. 45 is a rear perspective view of the attachment bracket and support beam of FIG. 44 after they have been operatively connected to each other;
[0080] FIG. 46 is a perspective view of an alternative embodiment of an attachment bracket suitable for use with a support beam as depicted in FIG. 11 a;
[0081] FIG. 47 is a plan view of the attachment bracket of FIG. 46 as it may be operatively connected to a support beam as depicted in FIG. 11 a;
[0082] FIG. 48 is a perspective view of an alternative embodiment of an attachment bracket having an arm that is rotatably connected thereto, and which is in a first position;
[0083] FIG. 49 is a perspective view of the attachment bracket of FIG. 48 in which the arm has been rotated to a second position;
[0084] FIG. 50 is a perspective view of an embodiment of an attachment bracket;
[0085] FIG. 51 is a partial, perspective view of a wall structure in which blocks of the present invention are operatively connected to a substructure by the vertically oriented support beams and brackets of FIGS. 2 and 2 a;
[0086] FIG. 52 is another partial perspective view of a wall structure in which blocks of the present invention are operatively connected to a substructure by horizontally oriented support beams and brackets of FIGS. 2 and 2 a;
[0087] FIG. 53 is a side elevation view of a block wall structure that is operatively connected to a structure;
[0088] FIG. 54 is an edge view of a sealing element that is used in the construction of the wall structure of FIG. 53 ;
[0089] FIG. 55 is a perspective view of the sealing element of FIG. 54 ;
[0090] FIG. 56 is an enlarged view of a portion of FIG. 53 , which depicts the sealing element of FIGS. 54 and 55 as it resides between structural elements;
[0091] FIG. 57 is a perspective view of an alternative embodiment of an attachment bracket for use in conjunction with blocks of the present invention;
[0092] FIG. 58 is a perspective view of an alternative embodiment of an attachment bracket for use in conjunction with blocks of the present invention;
[0093] FIG. 59 is a perspective view of an alternative embodiment of an attachment bracket for use in conjunction with blocks of the present invention; and,
[0094] FIG. 60 is a plan view of the brackets of FIGS. 57 and 59 operatively connecting blocks of the present invention to a substructure.
DETAILED DESCRIPTION
[0095] FIG. 1 illustrates several embodiments of the wall block system of present invention, as practiced with an elevated first (upper level) deck d 1 and an adjacent, elevated second (lower level) deck structure d 2 . The first embodiment is an elevated upper level deck structure d 1 , which is supported by a plurality of vertical posts that have been provided with an external sheathing of blocks that are operatively connected to the posts by support beams and brackets.
[0096] As depicted, the blocks used to sheath the post are angled blocks, such as depicted in FIGS. 2 and 2 a . The blocks, which are provided with grooves at their side edges, are configured to be operatively connected to a post by one or more support beams 716 , which will be discussed later in greater detail. As depicted, the support beams may be directly attached to the post. Alternatively, the blocks may also be operatively connected to the post by a support beam and a bracket 354 (see, for example, FIG. 2 a , which will be discussed later in greater detail), or by brackets alone (see FIGS. 57, 58 , 59 and 60 ). While it will be understood that a post sheathing will be relatively robust, it may be desirable to create a more permanent structure. This can be achieved, for example, by providing the horizontal and/or vertical edge surfaces of the blocks with a suitable adhesive 58 (vertical edge surfaces shown in phantom). Alternatively, the blocks may be secured by one or more circumferential bands of material (not shown).
[0097] Referring again to FIGS. 1, 2 and 2 a , it will be apparent that gaps may exist between the blocks and the post, and that moisture and debris may infiltrate the gaps from above, and/or between the joints between adjacent blocks. As will be understood, such infiltration may be substantially reduced by providing the sheathed post with cap stones, flashing gaskets or other construction elements that serve to effectively close the gaps from above. Infiltration reduction may also be achieved by providing the horizontal and vertical edge surfaces with caulking material.
[0098] The second embodiment of the block wall system of FIG. 1 depicts another application of the present invention, where blocks are used to skirt an elevated, lower level, second deck structure d 2 . In this application, the wall structure comprises several block embodiments. Starting from the left corner, the upper and lowermost courses comprise blocks that are similar to the corner blocks of FIGS. 2 and 2 a . The middle course, while it could comprise a block of FIGS. 2 and 2 a , is constructed using two linear blocks that are connected to each other by fastening element such as pins and/or adhesive material (see, for example, FIG. 8 ). Continuing towards the right, the next block embodiments, which will be discussed later in greater detail, are generally linear and as will be discussed later, configured to be operatively connected to the deck frame. Continuing on to the right corner, the arrangement of the blocks is similar to the arrangement of the blocks depicted at the left corner. The right corner differs, however, in that the corners formed by the blocks are not ninety degrees. Instead, the corner formed by the intersection of two walls is obtuse.
[0099] As will be discussed later in greater detail, the skirting structure blocks may be operatively connected to the deck frame in a manner similar to the previously discussed post sheathing. That is, through the use of support beams, support beams and bracket, or brackets. The wall structure depicted in FIG. 5 uses a support beam that is attached directly to the deck frame. As will be discussed later, the support beam serves to maintain and align a plurality of blocks. As depicted, the blocks of FIG. 5 are supported by a longitudinal L-shaped support bar that is also attached to the deck frame. With this operative connection, the blocks are not subject to external forces such as frost heave, and are generally static.
[0100] In the partial depiction wall structure of FIG. 5 a , the support beam is indirectly connected to the deck frame by one or more brackets. In this instance, the beam and bracket combination is similar to the beam and bracket combination of FIG. 2 a . This combination allows the beam (and blocks), which rest on a footing, to move in response to external forces such as frost heave. In this regard, the operative connection can be considered dynamic.
[0101] FIG. 3 is a perspective view of an elevated structure “S” skirted with a wall system 10 of the present invention. Generally, the wall structure 10 comprises of a plurality of blocks 12 forming columns 14 (see also, FIG. 4 ) partially spaced apart and held in place by vertically oriented, lateral support beams (see, for example, FIGS. 5, 11 , 22 , and 23 ). Downward opening brackets 18 (see FIGS. 5 and 22 ) that are attached to the bottom of the structure “S” being skirted, are configured to engaged the top block 12 of selected columns 14 to help prevent the wall structure 10 from tipping rearwardly or forwardly. As used herein, the term “forward” means away from the center of the elevated structure “S” and the term “rearward” means toward the center of the elevated structure “S”.
[0102] FIGS. 4 and 7 show an arrangement of blocks 12 that form a plurality of columns 14 . Referring particularly to FIG. 7 , each block 12 is generally panel-shaped and includes a front face 20 , a rear face 22 , a top surface 24 , a bottom surface 26 and pairs of side surfaces 28 a , 29 a and 28 b , 29 b , respectively. The side surface pairs 28 a , 29 a and 28 b , 29 b , respectively, are preferably somewhat perpendicular to the rear face 22 and/or the front face 20 . Side surface 28 a is spaced from side surface 28 b by a distance (taken along a “x” direction in a three-dimensional coordinate system relative to the blocks 12 ) to define a width 33 of the block 12 . Additionally, each pair of side surfaces 28 a and 29 a , 28 b and 29 b , include a substantially vertical groove 34 therebetween, which is configured to receive a portion of a lateral support beam 16 (See, for example, FIG. 11 ).
[0103] Note that while the top and bottom surfaces 24 , 26 of adjacent blocks 12 are configured to contact each other without thick layers of mortar or binding material therebetween, it is envisioned that the use of thin layers of intermediate materials, which may serve to strengthen and/or provide resistance to moisture may be practiced without departing from the spirit and scope of the invention. Moreover, it will be apparent that thin or no intermediate layers will minimize the spacing between blocks and allow the marginal areas 23 c , 23 d of adjacent blocks 12 to combine and simulate horizontally oriented splitting recesses.
[0104] As will be understood, the brackets 18 (see FIGS. 4 and 22 ) prevent rearward or forward movement of the column 14 and also work in conjunction with the beam 16 to prevent columns 14 not in direct contact with the bracket 18 from tipping over rearwardly or forwardly. It is envisioned that the beams 16 may be directly attached to the wall structure 10 (similar to FIG. 29 ) or alternatively, the bracket 18 may be solely responsible for preventing the wall structure 10 from tipping over. While it will be understood that the bracket 18 can be of any suitable material, synthetic, more preferably poly-vinyl chloride (PVC) or other durable plastic is preferred.
[0105] The bracket 18 comprises a front wall 44 , a rear wall 46 spaced apart from front wall 44 and a top wall 48 joining the front wall 44 to the rear wall 46 in a generally inverted “U”-shape. The front wall 44 and the rear wall 46 define an opening 50 , which is configured and arranged to receive an uppermost portion of the top block 12 of a column 14 . In practice, the bracket 18 is attached at or near the underside of a structure “S” to be skirted so that the opening 50 can receive the upper portion of the top block 12 of a column 14 . Preferably, the bracket 18 is positioned such that it may straddle the central region of an uppermost block 12 . It may be desired to make rear wall 46 of a greater vertical dimension than the front wall 44 to provide additional support. It may also be desired to provide a bracket 18 with a rear wall 46 , width that extends in a lateral direction further than the front wall 44 width. Furthermore, it is envisioned that the bracket 18 can be formed into a variety of lengths. For instance, the bracket 18 can be as short as one inch or as long as the entire skirted structure “S”.
[0106] While the top wall 48 of the bracket 18 is depicted in FIG. 4 as being in contact with the top surface 24 of the uppermost block 12 of the column 14 , it should be understood that this need not always be the case. In situations where the wall structure 10 is not a load bearing wall, or where the terrain shifts or changes due to climate, settling, animals, roots, etc., it may be desirable to provide a gap between the top wall 48 and the top surface of the wall structure 10 . Thus, individual columns 14 will be able to move vertically in small increments without destroying the integrity of the wall structure 10 or the skirted structure (not shown). In that regard, it should be appreciated that the beams 16 slidingly grip portions of the blocks 12 . That is to say, the beams 16 do not grip the blocks 12 with so much force as to preclude relative movement of the blocks 12 therealong in a longitudinal direction.
[0107] FIGS. 6 and 6 a show an embodiment of another application of the present invention, where blocks are used to provide a facia wall in front of an existing retaining wall. The facia wall is formed using support beams and brackets similar to the beams and brackets depicted in FIGS. 2 and 2 a . That is, the support beam 716 , as shown, comprises an elongated spine or web 718 and plurality of ribs 720 and 722 , 724 and 726 , which are arranged in a substantially coplanar and collateral relation so that the first pair of ribs 720 , 722 , which are substantially coplanar and extend away from each other. The first pair of ribs 720 , 722 are designed to engage the grooves of one or more blocks of a structure (see, for example, FIG. 6 a ).
[0108] In addition, the web 718 also includes a second pair of ribs 724 , 726 , which are also substantially coplanar and which extend away from each other. Note that the pairs of ribs 724 and 726 are in substantially collateral or parallel relation with respect to each other and are spaced apart from each other by a distance defined by the web 718 . As better shown in FIGS. 51 and 52 , he support beam 716 also includes a pair of pair of leg structures 730 having leg portions 732 a , 732 b that they extend rearwardly away from ribs 724 , 726 and which form a generally U-shaped channel therewith. One of the leg portions 732 b includes a foot 734 . that extends laterally away from the leg portion 732 b and is generally parallel with ribs 724 , 726 . As with the embodiment of FIGS. 2 and 2 a , the foot may be connected directly or indirectly to a support structure. However, as depicted, the beams of FIGS. 6 and 6 a are operatively connected to a structure by a plurality of brackets 354 , which are attached to blocks of the retaining wall. With such an arrangement the beams, which are slidingly constrained by the brackets, permit blocks to move without destroying the integrity of the structure.
[0109] The brackets 354 used to operatively connect the beams 718 to the retaining wall blocks generally comprise a structure engaging portion, a web, and a support beam engaging portion. As shown in FIG. 50 , the structure engaging portion 356 of bracket 354 comprises a single or first member 357 that is provided with an aperture 360 , which is used to facilitate attachment to the retaining wall with fastening elements such as nails, threaded fasteners, or anchor bolts. It will be appreciated, however, that an aperture or apertures need not be present in order to attach the bracket to a structure. The fastening element(s) may be driven through the first member, if desired. Additionally, it will also be appreciated that attachment may also be achieved with suitable adhesives, in lieu of, or in addition to, fastening elements. The support beam engaging portion 358 comprises a web 362 and a pair of legs 364 , 366 , which are angled with respect to the web to form a generally “L”-shape. The web 362 includes an aperture 368 that is accessible through a slot 370 defined by edges 372 and 374 of legs 366 and 364 , respectively. The aperture 368 and slot 370 are configured to slidingly receive a leg portion 732 b and foot 734 of a support beam (see also, FIGS. 50, 51 and 52 ).
[0110] Attention is now directed to the individual components of a wall structure 10 . FIG. 7 depicts a preferred embodiment of a block 12 . It can be seen that the block 12 is generally panel-shaped and includes a front face 20 , a rear face 22 , a top surface 24 , a bottom surface 26 and pairs of side surfaces 28 a , 29 a and 28 b , 29 b , respectively. The block 12 is preferably made of a composite masonry material in a dry-cast molding operation. Though the general shape of the blocks 12 is more important than the material used in order to practice the present invention, composite masonry material provides the most desirable combination of strength, appearance, economy, and ease of manufacturing. It is envisioned, however, that other materials can be used, such as concrete, fiberglass, ceramics, hard plastics, dense foam, or even wood.
[0111] The front face 20 is spaced from the rear face 22 by a predetermined distance herein defining the thickness or depth 30 (generally about 1 to 4 inches (2.5 to 10.0 cm)) of the block 12 . As shown in FIG. 7 , the front face 20 is formed to have a roughened or rustic surface. Such surfaces commonly result during block fabrication, where a mold is cast and the casting is later split or fractured into two blocks along a predetermined plane, with the plane of separation between the two blocks defining a pair of opposing front faces. Splitting is not necessary to carry out the spirit of the invention, however, and the block 12 may be formed by other known methods. Moreover, the front face 20 can be dressed, modified, or otherwise worked in any desired manner.
[0112] A vertically oriented splitting recess 21 may be provided on the front face 20 of the block 12 to enable the block 12 to be fashioned into predetermined shapes. In FIG. 7 , the splitting recess 21 is depicted as bisecting the block 12 . However, it is understood that the splitting recess can be located and oriented elsewhere on the block. That is, the splitting recess can be off-center, horizontal, diagonal, etc. Moreover, it is also understood that the block can be provided with more than one splitting recess, if desired.
[0113] The front face 20 includes marginal areas 23 a , 23 b , 23 c , and 23 d . As may be expected, the number of marginal areas corresponds to the number of edges of the front face 20 . These marginal areas may be worked or modified, if desired, to produce different visual effects. Here, the desired effect is for the marginal areas 23 a , 23 b , 23 c , and 23 d to simulate splitting recesses 21 . Thus, the marginal areas 23 a , 23 b , 23 c , and 23 d are formed so that when blocks 12 are positioned in contact with each other in a wall structure 10 , the cross-sectional profiles of their marginal areas 23 a , 23 b , 23 c , and 23 d , when combined, simulate splitting recesses 21 . As depicted the splitting recesses 21 have a cross-sectional profile that is somewhat circular, and the marginal areas 23 a , 23 b , 23 c , and 23 d have cross-sectional areas that are fluted or arced. As can be appreciated, the splitting recesses 21 and marginal areas 23 a , 23 b , 23 c , and 23 d may be configured with other cross-sectional profiles, if desired. For example, a “V”-shaped cross-sectional profile.
[0114] As mentioned above, tight or thin joints 31 (See FIG. 3 ) between adjacent blocks 12 enables a wall structure to appear monolithic or seamless. This feature may be used in combination with splitting recesses 21 and marginal areas 23 a - d of the blocks 12 to create different visual effects. For example, it is envisioned that a wall structure may simulate running bonds by having the blocks of each column alternate between a block with no splitting recess and worked marginal areas and a block having a splitting recess and worked horizontal marginal areas (see, for example, FIG. 40 ). Or, it is envisioned that the splitting recesses and marginal areas be selected to enable the wall structure to simulate an ashlar block wall (not shown).
[0115] Referring again to FIG. 7 , the top surface 24 is spaced from the bottom surface 26 by a distance (taken along a “y” direction in a three-dimensional coordinate system relative to the block 12 ) to define the height 32 (about 6 to 12 inches (15 to 30 cm)) of the block 12 . When blocks 12 are arranged vertically to form a column 14 (see FIG. 4 ), the bottom surface 26 of any block 12 other than the bottom block of a column 14 (not shown) rests on the top surface 24 of the block therebelow. It is therefore preferred that the top surface 24 and the bottom surface 26 be configured to facilitate a stacking relationship between two blocks 12 . A stacking relationship is most easily achieved by making the top and bottom surfaces 24 , 26 substantially collateral, planar, and relatively perpendicular to the rear face 22 and/or the front face 20 , as best shown in FIGS. 4 and 5 . Alternatively, it is envisioned that top and bottom surfaces 24 , 26 may be complementarily shaped, and not perpendicular to the rear face and/or the front face, but which permit upper and lower blocks to be stacked in a vertical relationship (not shown). For example, the surfaces could be non-planar and/or irregular. Alternatively, the surfaces can have compound curves or even interlocking segments (not shown).
[0116] The side surface pairs 28 a , 29 a and 28 b , 29 b , respectively, are preferably somewhat perpendicular to the rear face 22 and/or the front face 20 . Side surface 28 a is spaced from side surface 28 b by a distance (taken along a “x” direction in a three-dimensional coordinate system relative to a block 12 ) to define the width 33 (6 to 24 inches (15 to 60 cm)) of block 12 . Additionally, each pair of side surfaces 28 a and 29 a , 28 b and 29 b , include a substantially vertical groove 34 therebetween that is configured to receive a portion of a lateral support beam 16 (see, for example, FIG. 11 ). While a pair of side grooves for each block is preferred, it is envisioned that one side surface be provided with a groove and the other side surface have a tongue configured to mate with the groove, thereby obviating the need for beams 16 . However, in order to maintain the vertically independent characteristics of columns 14 , the use of beams 16 is preferred.
[0117] Referring now to FIGS. 7 a and 7 b , another embodiment of the block of the present invention is depicted. The block 112 is generally panel-shaped and includes a front face 120 , a rear face 122 , a top surface 124 , a bottom surface 126 and pairs of side surfaces 128 a , 129 a , and 128 b , 129 b , respectively.
[0118] The front face 120 is spaced from the rear face 122 by a predetermined distance defining the thickness or depth 130 (generally about 1 to 4 inches (2.5 to 10.0 cm)) of the block 112 . As shown in FIG. 7 a , the front face 120 is formed to having a roughened or weathered surface. However, it is understood that the front face 120 could, be dressed, modified, or otherwise worked in any desired manner.
[0119] Vertically oriented splitting recesses may be provided on the front face of the block to enable the block to be fashioned into predetermined shapes. Here, the splitting recesses 121 are depicted as quartering the block 112 and forming front face segments 125 a , 125 b , 125 c , and 125 d . However, it is understood that the splitting recesses 121 may be located and oriented elsewhere on the block 112 . That is, the splitting recesses 121 could be off center, horizontal, diagonal, etc. Moreover, it is also understood that a block splitting recesses 121 may be omitted, if desired.
[0120] The front face 120 includes marginal areas 123 a , 123 b , 123 c , and 123 d . As may be expected, the number of marginal areas corresponds to the number of edges of the front face 120 . The marginal areas 123 a - d may be worked or modified, if desired, to produce different visual effects. In FIG. 7 a , the desired visual effect is for the marginal areas to simulate splitting recesses. Thus, the marginal areas 123 a - d are formed so that when blocks 112 are positioned in contact with each other in a wall structure 10 (See FIG. 3 , for example), the cross-sectional profiles of their marginal areas 123 a - d , when combined, simulate splitting recesses at the joints formed by the block. As depicted, the splitting recesses 121 have a cross-sectional profile that is somewhat circular, and the marginal areas 123 a - d have cross-sectional areas that are fluted or arced. As can be appreciated, the splitting recesses and marginal areas 123 a - d may be configured with other cross-sectional profiles, if desired. For example, a “V”-shaped cross-sectional profile.
[0121] Referring again to FIG. 7 a , the top surface 124 is spaced from the bottom surface 126 by a distance (taken along a “y” direction in a three-dimensional coordinate system relative to the block 112 ) to define the height 132 (about 6 to 12 inches (15 to 30 cm)) of the block 112 . When the blocks 112 are arranged vertically to form a column 14 (see, for example, FIGS. 4 and 5 ), the bottom surface 126 (not shown) of any block 112 other than the bottom block of a column 14 (See FIG. 5 ) rests on the top surface 124 of the block 112 therebelow. It is therefore preferred that the top surface 124 and the bottom surface 126 be configured to facilitate a stacking relationship between two blocks 112 . A stacking relationship is most easily achieved by making the top and bottom surfaces 124 , 126 substantially collateral, planar and relatively perpendicular to the rear face 122 and/or the front face 120 , as shown in FIGS. 4 and 5 . Alternatively, it is envisioned that the top surface 124 and the bottom surface 126 (see FIG. 7 b ) may be complementarily shaped, and not perpendicular to the rear face 122 and/or the front face 120 , as long as the upper and lower blocks 112 can be stacked in a vertical relationship. For example, the surfaces 124 , 126 (not shown) can be non-planar and/or irregular. Or, the surfaces 124 , 126 (not shown) can have compound curves or interlocking segments (not shown).
[0122] Referring to FIG. 7 b , the side surface pairs 128 a , 129 a and 128 b , 129 b , respectively, are preferably somewhat perpendicular to the rear face 122 and/or the front face 120 . The side surface 128 a is spaced from the side surface 128 b by a distance (taken along the “x” direction in a three-dimensional coordinate system relative to the block 112 ) to define the width 133 (6 to 24 inches (15 to 60 cm)) of the block 112 . Additionally, each pair of side surfaces 128 a , 129 a , 128 b and 129 b , include a substantially vertical groove 134 located therebetween that is configured to receive a portion of a lateral support beam (see, for example, the lateral support beam depicted in FIGS. 11 , and 23 - 36 ).
[0123] The block 112 is that it is additionally provided with one or more substantially vertical apertures or through holes 150 a , 150 b , and 150 c . As can be seen, apertures 150 a , 150 b , and 150 c , which are in substantial alignment with the grooves 134 located on either side of the block 112 . This enables for use with support beams 270 such as those shown in (See FIG. 12 ), to be used, if desired. The vertical apertures 150 a - c also allow a plurality of blocks 112 to be positioned in a running bond (again using support beams 270 such as those shown in FIG. 12 , for example). The aperture 150 b may be provided with a slot 152 , which that provides an opening to the rear face 122 . In addition, the block 112 may now be split into smaller predetermined sizes, with each smaller block (not shown) having a set of side grooves 134 . Although not depicted, it will be understood that apertures 150 a and 150 c may also be provided with slots (as with aperture 150 b ), if desired.
[0124] Another feature of block 112 is the provision of recesses 127 a and 127 b on the rear surface 122 adjacent the side surfaces 129 a and 129 b . The recesses come into play during, and aid in, the manufacturing of the block. After a large block (not shown) is molded and split into two smaller blocks and the smaller blocks are removed from the conveyor on which they rest by a pusher bar (not shown) that impacts the rear surfaces of the blocks and moves them in a desired direction. This works if the blocks are substantially parallel to the pusher bar. However, if the blocks are not substantially parallel to the pusher bar, the bar has a tendency to chip and break the side segments. The recesses provide clearance so that if the block is somewhat askew relative to the pusher bar, the bar will not contact the side segments and thereby reducing chipping and breakage.
[0125] FIG. 8 shows a preferred corner configuration using the blocks 12 of the present invention. The design of the block 12 lends itself to the formation of corners without the need for mortar, corner braces, or other supports. Two blocks 12 a and 12 b are simply aligned to form a corner butt joint 51 . Preferably, block 12 b is broken along its splitting recess to form a new split face, which roughly matches split front face of block 12 a . Holes 54 are drilled through the blocks 12 a and 12 b so that a fastener 56 may be inserted therein. Generally, the fastener may be any suitable fastener, and preferably, an appropriately sized pin, peg, or screw, and the like. Alternatively, glue, preferably construction mastic, may be applied instead of or, more preferably, in combination with fasteners to secure the blocks to each other.
[0126] Referring now to FIGS. 9 and 10 , another embodiment of a block 156 of the present invention is depicted. The block 156 is generally angularly-shaped and includes a front face 158 , a rear face 160 , a top surface 164 , a bottom surface 166 and pairs of side surfaces 168 a , 169 a , and 168 b , 169 b , respectively. As with the previously described blocks 112 , the side surfaces 168 a , 169 a , and 168 b , 169 b are provided with grooves 170 a and 170 b that are configured to receive portions of lateral support beams, and will not be discussed here in detail. An alternate embodiment of the block 156 ′ is illustrated in FIGS. 1-2 a . As shown in FIGS. 9-10 , front face 158 is formed with a roughened or weathered surface or facing segments 159 a - b and is provided with marginal areas 163 a - d . These features are not necessary to carry out the spirit of the invention, however. The front face 158 may be dressed, modified, or otherwise worked in any desired manner. The block 156 may also be provided with recesses 167 a and 167 b , located on the rear face segments 161 a and 161 b , adjacent the side surfaces 169 a and 169 b . As discussed previously, the recesses 167 a - b prevent and/or reduce chipping during the manufacturing process.
[0127] As depicted, the block 156 is configured so that the front face segments 159 a and 159 b , and the rear face segments 161 a and 161 b are oriented so that they intersect each other at a predetermined angle 172 . The angle of intersection 172 can vary from about 15 degrees to about 165 degrees. Preferably, though, the angle of intersection is about 90 degrees so that the block may be used to construct rectilinear structures. In that regard, it will be appreciated that the blocks 156 may be used with or without linearly shaped blocks to form columnar structures of varying shapes and sizes (see, for example FIG. 1 ). Moreover, it is envisioned that the blocks may be formed with more than two front and rear face segments 159 a - b , 161 a - b , and/or that the block could be formed in a generally arcuate shape.
[0128] Referring now to FIG. 11 , an embodiment of a beam of the present invention generally comprises an elongated spine or web and at least one rib, which is substantially coextensive therewith. More specifically, a preferred embodiment of beam 16 , as shown, includes a plurality of ribs that are arranged in a substantially coplanar and collateral relation. That is, there is a first pair of ribs 38 a , which are substantially coplanar and extend away from each other. And, there is a second pair of ribs 38 b , which are also substantially coplanar and extend away from each other. Note that the pairs of ribs 38 a and 38 b are in substantial collateral relation with each other and are spaced apart from each other by a distance defined by the web 36 . This configuration of two pairs of ribs 38 a and 38 b attached to each other by web 36 forms somewhat of an I-beam configuration. It is preferred that at least one set of ribs 38 a be resiliently deformable and, even more preferred, that they converge slightly towards and then diverge slightly away from the other ribs 38 b in a somewhat “V”-shaped configuration towards the ends of the ribs 38 . A “V”-shaped configuration is preferred because it allows a segment 35 of a block 12 to be gripped between the ribs 38 a - b (see, for example, FIGS. 23 and 24 ). As will be appreciated, in order for the desired amount of gripping force to occur, the distance or span 42 between a rib 38 b and the apex of the “V” of an unflexed rib 38 a should be slightly less than the thickness of segment 35 (see FIG. 24 ). It will also be appreciated that the distance or span 43 between the leading edge of flange 40 of the unflexed rib 38 a and the rib 38 b should be slightly greater than the thickness of segment 35 (See, again FIG. 24 ). Thus, when a beam 16 is attached to a block 12 the rib 38 a is deflected from its unstressed state to a stressed state and a segment 35 of a block may be gripped between ribs 38 a and 38 b . As depicted in FIG. 23 the ribs 38 a and 38 b are preferred because they prevent unwanted movement and misalignment between blocks 12 of a given column 14 and they are able to compensate for variations in dimensions that sometimes occur during manufacture of the blocks.
[0129] Beam 16 may be attached at its upper ends to a structure being skirted (see, for example, FIG. 1 ) if desired, preferably at or near the lowermost edge or bottom of the structure, and using conventional fastening techniques and technologies. Such attachments may be used in conjunction with or without a bracket 18 to provide support and stability to the independent columns 14 (see FIG. 5 ) by preventing them from leaning or falling forwardly or rearwardly. The beams aligns the blocks 12 of a given column), by preventing lateral movement therebetween (that is, movement along the “x” direction in a three-dimensional coordinate system relative to the blocks 12 ).
[0130] Another embodiment of a lateral support beam 116 is depicted in FIG. 1 a . Here, the beam 116 generally comprises a body having block-engaging portion and a bracket-engaging portion. More specifically, the beam 116 comprises a first web 180 and a second web 181 that are generally aligned with each other. Projecting from the webs 180 , 181 are pairs of ribs 182 a , 182 b , and 182 c . The first pair of ribs 182 a , which form the block-engaging portion, extend away from each other in a generally coplanar relation. The second pair of ribs 182 b is generally collaterally aligned with the first pair of ribs 182 a and is separated therefrom by a predetermined span 188 . The third pair of ribs 182 c is generally collaterally aligned with the second pair of ribs 182 b and is separated therefrom by a predetermined span 190 . The outer ends of ribs 182 a are provided with resilient flanges 184 that are configured and arranged such that the ribs 182 a are able to be received by the vertical grooves on the blocks. With this beam embodiment, segments of the sides of a block are not gripped between adjacent pairs of ribs. Rather, engagement with blocks is achieved through the first set of ribs 182 a that substantially span the depth of the vertical grooves of the blocks, where depth is taken along the “z” axis in the three dimensional coordinate system (see, for example, FIG. 7 a ). It will be appreciated that the block engaging portion, i.e., the first pair of ribs 182 a , need not be restricted to a flange configuration. A frictional engagement, for example, can be achieved with other configurations.
[0131] Alternative embodiments of support beams 270 , 287 and blocks 312 are illustrated in FIGS. 12, 13 and 27 . With regard to the support beam 270 depicted in FIG. 12 , support beam 270 comprises a pair of webs 272 , 274 , which are generally parallel to each other and that terminate in opposing ribs. A third web 276 extends from the surface formed by opposing ribs in general alignment with webs 272 , 274 and terminates in opposing ribs 278 c . The ends of opposing ribs 278 a and 278 b may be provided with flanges and coupling elements 280 , 282 , respectively. As will be appreciated, two webs 272 , 274 (versus a single web) increases the overall strength of the beam 270 so that the beam resists bending and warping more than beams that have only single webs that connect their opposing ribs.
[0132] The support beam 287 of FIG. 13 is similar to the support beam 270 of FIG. 12 . Instead of having opposed ribs that engage a block, however, the block engagement section 288 of the beam is configured so that it is able to substantially span the depths of the grooves of two opposing blocks, or the depth of the aperture 350 in the interior section of a block 312 (see FIG. 27 ) (where depth is taken along the “z” axis in the three dimensional coordinate system as shown in FIG. 7 a ). As depicted, the engagement section 288 of the support beam 287 is generally “T”-shaped and substantially spans the depth of the aperture 350 (i.e. see FIG. 27 ) where depth is taken along the “z” axis in the three dimensional coordinate system as shown in FIG. 7 a (see FIG. 45 , for example), and generally spans the width of the slot 352 of a block (see, FIG. 27 ). As shown, the engagement section 288 is hollow, however, it is understood that the engagement section 288 may be solid, if desired. The base of the “T”-shaped engagement section 288 is provided with a web 276 and a pair of opposing ribs 278 c to enable the support beam 287 to be connected to a bracket such as those depicted in FIGS. 44-45 . With regard to FIG. 27 , it will be appreciated that the depiction of the support beams 270 and 287 relative to the blocks 312 are for illustrative purposes only, and that they may be interchanged if desired.
[0133] A frictional engagement may be desired and this could be achieved with other configurations. For example, in FIG. 14 the block-engaging section 288 may take the form of generally planar opposing planar sections 192 each having resilient spurs 194 projecting therefrom. Or, as seen in FIG. 15 , the block-engaging section 288 may take the form of a preformed resilient body 196 having an aperture 198 . Note that in FIGS. 14 and 15 , the bracket-engaging portions 290 are shown in phantom.
[0134] With reference to FIG. 16 , the support beam 116 is similar to the support beam of prior embodiments in that it includes a web 510 from which a plurality of ribs 503 , 504 , 505 and 506 extend. In a departure from previous embodiments, the support beam 116 of this embodiment includes an extension 508 that terminates with an attachment member 512 . Preferably, the extension 508 is aligned with, and extends from the web 510 so as to position the attachment member 512 a predetermined distance from the plurality of ribs 503 , 504 , 505 and 506 . This arrangement serves several purposes. As explained above, not only does the extension 508 create spaces between a wall structure and a substructure that may be used as plenums, conduits, or for retaining insulative, fire-retardant or other building materials, but it also facilitates attachment of the support beam 116 to a substructure. Preferably, the attachment member 512 comprises feet 516 and 518 that extend laterally in opposite directions from the extension 508 to provide a point or points of connection which may be used with adhesive or fastening elements, such as nails or screws, in attaching a support beam to a substructure (see also, FIG. 29 ).
[0135] Referring now to FIG. 17 , the support beam 116 , again, has an extension 508 , which terminates in an attachment member 512 having feet 516 , 518 . However, in this embodiment, the extension 508 and the feet 516 , 518 are foreshortened. Note that the support beam 116 is not directly connected to a substructure but is operatively connected to a bracket 534 that is, in turn, operatively connected to a substructure. The bracket 534 includes a substructure engaging portion 536 , a span 538 and an attachment member with a support beam engaging portion 542 . The support beam engaging portion 542 is sized to be snuggly received and frictionally retained within a channel 530 or 532 formed by a rib and a foot 505 , 516 ; 506 , 518 , respectively, of the beam 116 . Note that the support beam 116 need not extend along the length of the bracket 534 , and more particularly, the support beam 116 need not be coextensive with the side of a block 112 (see FIG. 7 a ) to which it may be operatively connected. The reason for this is that a block need not be retained along its entire length of its grooves to be adequately retained as part of a wall structure. Instead, it is only necessary for a block to retained at several points. Thus, the support beams 116 may take the form of clips that attach to the bracket 534 , and a block 112 can be retained at a plurality of predetermined locations (i.e. such as upper and lower ends). It will be appreciated that such support beam clips may be used to operatively connect a pair of blocks to a support bracket by positioning the clips so that they span the interface between two adjacent blocks. It will also be appreciated that the support beam clip may be longer than a side of a block to which it is operatively connected so that it may operatively connect more than two blocks to a bracket.
[0136] The span 538 of the bracket 534 serves to position the support beam 116 a predetermined distance from a substructure while the substructure engaging portion 536 serves to attach the bracket 534 to a substructure. As with the aforementioned embodiment, the bracket 534 may be operatively connected to a substructure using a variety of fastening elements. It will be appreciated that both channels 530 , 532 of the support beam 116 of this embodiment may be used with oppositely facing brackets, if desired, to form a more robust connection between the wall structure and a substructure.
[0137] Referring now to FIG. 18 , the support beam 116 terminates at an attachment member 512 that includes two spaced apart resilient walls 550 , 552 having confronting arms 554 , 556 , which define a slot 558 and channel 560 , which are sized to admit and retain a second attachment member.
[0138] With this embodiment, the support beam 116 is not directly connected to a substructure but is operatively connected to a bracket 562 that is, in turn, operatively connected to a substructure (see, for example, FIG. 32 ). The bracket 562 includes substructure engaging portions 564 , 566 , a span 538 and a first attachment member 570 . Preferably, the first attachment member 570 is a dart-shaped head 572 having shoulders 574 , 576 that are configured to engage arms 554 , 556 of the support beam 116 in a constrained relation. That is, the attachment member 512 of the support beam is sized to slidingly receive the head 572 within a slot 558 and a channel 560 formed by the resilient walls 550 , 552 and their confronting arms 554 , 556 . Thus, the support beam 116 may be connected to a bracket 562 in a constrained manner. It will be appreciated that the support beam 116 can be operatively connected to the bracket 562 in several ways. For example, by positioning the bottom of the channel 560 and the slot 558 over the top of the dart shaped head 572 and the span 568 of bracket 562 and then sliding the support beam 116 down along the bracket 562 and interconnecting with an already positioned block, or sliding the support beam down along the bracket 562 and later interconnecting with a block, which is slid into position in a similar manner. Alternatively, a support beam 116 may be operatively connected to a bracket 562 by aligning the slot 558 of the attachment member 512 opposite the apex of the dart shaped head 572 and then pushing the support beam 116 towards the dart shaped head 572 until the arms 554 , 556 of the attachment member 512 engage the shoulders 574 , 576 of the dart shaped head 572 .
[0139] As will be appreciated, the support beam 116 of FIG. 18 need not extend along the length of the bracket 562 and, more particularly, the support beam need not be co-extensive with the side of a block to which it is operatively connected. The span 538 of bracket 562 serves to position the support beam 116 a predetermined distance from a substructure and the substructure engaging portion 564 , 566 serves to attach the bracket 562 onto a substructure. Bracket 562 may be operatively connected to a substructure using a variety of fastening elements 578 (see also, FIG. 32 ).
[0140] Referring now to FIG. 19 , the operative connection is reversed from that shown in FIG. 18 . That is, support beam 116 includes an extension that terminates in a first attachment member 570 having a head 594 with shoulders 596 , 598 . The bracket 580 now includes two spaced-apart resilient walls 582 , 584 having confronting arms 586 , 588 , which define a slot 590 and a channel 592 , which are sized to admit and retain the attachment member 594 in a constrained relation, as discussed above. As with the aforementioned embodiments, the support beam 116 need not extend along the length of the bracket 580 . The bracket may be operatively connected to a substructure using a variety of fastening elements.
[0141] Referring now to FIG. 20 , another preferred embodiment depicts a post 600 which has been provided with a plurality of connectors to enable the post 600 to support a plurality of wall structures. In this embodiment, the post 600 includes front and rear surfaces 602 , 604 and opposing sides, with a web 606 that extends from the front surface 602 , and an attachment bracket 612 that extends from the rear surface 604 . A pair of ribs 608 , 610 extend laterally in opposite directions from the web 606 in the same manner as the ribs 38 of support beam 16 in FIG. 11 , while the attachment bracket 612 includes a slot 614 and channel structure 616 similar to the slot 558 , 590 and channel 560 , 592 structures described and shown in FIGS. 18 and 19 , respectively. Thus, with this embodiment, blocks may be directly connected to the post 600 at side 602 or connected indirectly at side 604 via an appropriately configured support beam (such as beam 116 of FIG. 19 ).
[0142] Although not shown, other combinations of operative connections may also be used. For example, the post 600 may be provided with two direct connectors (webs with laterally extending ribs) or the post may be provided with two indirect connectors (attachment members, such as channels). As will be appreciated, the post 600 may be operatively connected to a substructure such as a footing or foundation, or be set into the ground using known techniques and technologies. While the post 600 is depicted as having a hollow cross-section, it is understood that the post may also be a solid in cross section or may have a reinforcing structure such as a pipe or a rod received therein.
[0143] With reference to FIG. 21 , the support beam 116 is similar to the support beam of prior embodiments, in that it includes a web 510 from which a plurality of ribs 503 , 504 , 505 and 506 extend. The support beam 116 includes an extension 508 that terminates with an attachment member 512 . Preferably, the extension 508 is aligned with, and extends from the web 510 so as to position the attachment member 512 a predetermined distance from the plurality of ribs 503 , 504 , 505 and 506 . In FIG. 21 , the attachment member 512 is depicted as feet 516 and 518 , however it is understood that the attachment member may take other forms. Note that ribs 503 , 504 , 505 and 506 are reversed relative to each other so that the pair of opposing ribs 505 and 506 are now forward, relative to the opposing pair of ribs 503 and 504 (similar to the rib arrangement as depicted in FIGS. 23 and 24 ). Note also,. that the pair of forwardly facing opposing ribs 505 and 506 are somewhat thicker than the pair of opposing ribs 503 and 504 . This feature allows the support beam 116 to have a viewable surface 507 , which may form part of an observed wall structure (see FIG. 35 ).
[0144] Referring now to FIG. 22 , a partial horizontal section of the wall structure 10 of FIG. 4 is depicted. As shown, a beam 16 operatively connects two adjacent blocks 12 of adjacent columns 14 to each other. Here, the “V”-shaped ribs 38 a are positioned within grooves 34 of adjacent blocks 12 and ribs 38 b are positioned against the rear faces 22 of adjacent blocks 12 . In this configuration, the beam 16 remains hidden from view and provides support along several axes (taken along the “z” and “x” directions in a three-dimensional coordinate system relative to a block 12 ). With the beam 16 of this embodiment, the grooves 34 may be considerably larger than the thickness of the ribs 38 a , without affecting the gripping ability of the beam 16 . Thus, there may be quite a large space in front of the ribs 38 a . Note that the distance between side surfaces 29 a and 29 b of block 12 is less than the distance between side surfaces 28 a and 28 b of block 12 to allow the side surfaces 28 a , 28 b of adjacent blocks 12 to be brought into intimate contact with each other while providing enough space to accommodate the web 36 of the beam 16 (see FIGS. 24 and 24 a ). Note that a bracket 18 is shown (in dashed lines) as it would be positioned relative to an uppermost block 12 of a column 14 .
[0145] FIGS. 23 and 24 show a preferred beam arrangement in which the beam 16 shown in FIGS. 11 and 22 is reversed with respect to blocks 12 to which the beam is connected. That is, the ribs 38 b are positioned within opposing grooves 34 and ribs 38 a are positioned against the rear faces 22 of blocks 12 . This arrangement does not significantly change the function and gripping ability of the beam 16 as discussed above.
[0146] As with to the embodiment depicted in FIG. 22 , the distance between side surfaces 29 a and 29 b of the blocks is less than the distance between side surfaces 28 a and 28 b to allow side surfaces 28 a , 28 b of adjacent blocks 12 to be brought into intimate contact with each other while providing enough space to accommodate the web 36 of the beam 16 . Note that when two adjacent blocks 12 are brought into contact with each other, their corresponding margins 23 a and 23 b combine to form a profile that is substantially the same as the profile of a splitting recess 21 (as shown in FIGS. 22 and 24 ). It will be appreciated that the splitting recess 21 and may have other profiles, such as a “V”-shape and that the corresponding margins would be more beveled or chamfered.
[0147] Referring now to FIGS. 23, 23 a , 24 and 24 a , operatively connecting blocks together to form a wall structure 10 begins with connecting a block 12 to a beam 16 . As depicted in FIGS. 23 a and 24 a , the leading edge of flange 40 allows the rib 38 a to be displaced as it encounters the block segment 35 . As the beam 16 is connected to the block 12 , block segment 35 is gripped by ribs 38 a and 38 b .
[0148] In a preferred method to operatively connect a wall to a structure using the aforementioned bracket, a person would prepare or otherwise select an appropriate location in which to construct a wall. The construction would begin by placing a first block having opposing side grooves in a desired position and orientation. Then, a second, similar block would be placed directly on top of the first block so that the opposing side grooves of the first and second blocks are in vertical alignment with each other and the first and second blocks form a column. Next, the first and second blocks would be operatively connected to each other along one of their respective sides by inserting a rib of first support beam into the aligned grooves and seating it securely.
[0149] Next, a bracket is positioned so that its wall engaging portion is collaterally aligned and in contact with the support beam such that it extends therewith along the groove in the block. The structure engaging portion of the bracket is then brought into position for attachment to a structure by sliding or otherwise manipulating the bracket in a direction towards the point of attachment on the structure (this is generally above and co-planar with the wall). The bracket is than attached to the structure using conventional techniques and technologies. The rib of a second support beam is then inserted into the aligned grooves of the opposite sides of the blocks, and a second bracket is used to operatively connect this portion of the wall to a structure using the aforementioned steps.
[0150] A second column comprising similarly configured third and a fourth blocks may now be constructed. The operation is much the same, except now the third block is positioned so that one of its sides is adjacent to one of the sides of the first block and its groove engages at least one other rib of one of the already positioned support beams. The fourth block is then positioned on top of the third block in a similar manner. That is, the fourth block is positioned so that one of its sides is adjacent to one of the sides of the second block and its groove engages at least one other rib of one of the already positioned support beam and the wall engaging portion of the already installed bracket.
[0151] After the second column is erected, the third and fourth blocks would be operatively connected to each other along their respective free side by inserting at least one rib of a third support beam into their aligned vertical groove of the respective sides of the first and second blocks and seating them securely, and that support beam would be operatively connected to a support by yet another bracket. And so on. It will be appreciated that other methods of constructing a wall structure using the aforementioned components are possible.
[0152] FIG. 25 illustrates an alternative embodiment of a beam 16 having two ribs 38 a , 38 b but only one resiliently deformable rib 38 a . FIG. 26 shows yet another embodiment of a beam 16 comprising one pair of opposed ribs 38 b such that the support beam 16 is essentially an elongate spline. It should be understood that for purposes of clarity, the ribs 38 b as depicted in FIGS. 25 and 26 are substantially thinner than the grooves 34 in which they are positioned, and that in actuality ribs 38 a - b and grooves 34 would be configured to effectively maintain blocks 12 in a coplanar relation with little or no play.
[0153] Alternative embodiments of support beams and blocks are shown in FIG. 27 . As depicted in FIG. 27 , a support beam 270 may be operatively connected to one or more blocks 312 , at grooves 334 a and 334 b . Note that the blocks 312 include a front face 320 , a rear face 322 , a top surface 324 , a bottom surface (not shown), and side surfaces 328 a and 329 a , and 328 b and 329 b . The blocks 312 also include marginal areas 323 and notches 327 , which will not be discussed here in detail. As can be seen, the side surfaces 329 a and 329 b are foreshortened to accommodate the increased width of the support beam 270 . The support beam 270 may be operatively connected to a block 312 when the ribs 278 a and 278 b grip side segments 335 a , 335 b . The support beam 287 can be operatively connected to a block 312 by sliding a block engagement section 288 into the aperture 350 .
[0154] Another embodiment of a lateral support beam is depicted in FIG. 28 . Here, the beam 116 generally comprises a body having block-engaging portion and a bracket-engaging portion. More specifically, the beam 116 comprises a first web 180 and a second web 181 that are generally aligned with each other. Projecting from the webs 180 , 181 are pairs of ribs 182 a , 182 b , and 182 c . The first pair of ribs 182 a form block-engaging portions, which extend away from each other in a generally coplanar relation. The second pair of ribs 182 b is generally collaterally aligned with the first pair of ribs 182 a and is separated therefrom by a predetermined span 188 . The third pair of ribs 182 c is generally collaterally aligned with the second pair of ribs 182 b and is separated therefrom by a predetermined span 190 . The outer ends of ribs 182 a are provided with resilient flanges 184 that are configured and arranged such that the ribs 182 a are able to be received by the vertical grooves on the blocks of the present invention. With this embodiment, segments of the sides of a blocks re not gripped between adjacent pairs of ribs.
[0155] Now referring to FIG. 29 , a support beam 116 , similar to the support beam of prior embodiments, includes a web 500 from which a plurality of ribs 503 , 504 , 505 and 506 extend. The support beam 116 of this embodiment includes an extension 508 that terminates with an attachment member 512 . Preferably, the extension 508 is aligned with, and extends from the web 500 so as to position the attachment member 512 a predetermined distance from the plurality of ribs 503 , 504 , 505 , and 506 . The extension 508 not only creates spaces between a wall structure and a substructure that may be used as plenums, conduits, or for retaining insulative, fire-retardant or other building materials, and also facilitates attachment of the support beam 116 to a substructure “S” (partially shown). Preferably, the attachment member 512 comprises feet 516 , 518 that extend laterally in opposite directions from the extension 508 to provide a point or points of connection which may be used with adhesive or mechanical fastening elements, such as nails or screws 522 , in attaching a support beam to a substructure “S”.
[0156] FIG. 30 illustrates a partially assembled wall structure 410 comprising a plurality of blocks 412 retained in place by a plurality of vertically oriented, elongated support beams 416 that are operatively connected to a substructure “S” (shown in dashed lines). The support beams 416 allow the blocks 412 of adjacent horizontal courses to be substantially superposed one above the other and not laterally offset from each other in a bond pattern, as one may expect of such a wall structure. Thus, the wall structure 410 is comprised of a plurality of adjacent columns 414 a - d that may be operatively connected to each other in a serial fashion. Each block 412 of the wall structure 410 includes a front face 420 , a rear face 422 , a top surface 424 , a bottom surface 426 and opposing sides 427 a , 427 b . Each opposing side 427 a , 427 b includes opposing grooves 434 , 436 defined by plurality of outwardly extending fingers 428 a , 428 c and 428 b , 428 d , with outwardly facing surfaces 430 a , 430 c and 430 b , 430 d.
[0157] Preferably, the blocks 412 are symmetrically formed, so that either the front or rear face 420 , 422 , respectively, may face forwardly. This feature allows a block which has been damaged or had its surface otherwise altered to be easily removed and reinstalled by merely turning the block around (or over) so that other good or undamaged sides now being the viewable surface of the block. In other words, the blocks are reversible. The front and rear faces need not have the same surface treatment. That is, a block 412 may have a smooth front face and a roughened rear face 422 . Or, a block 412 may have roughened front face and a decorated or non-planar rear face. For example, in FIG. 30 , the lower most blocks 412 of column 414 c and column 414 d , respectively, have forwardly facing rear faces 422 while the remaining blocks in the partially assembled wall structure 410 have forwardly facing front faces. As depicted, the viewable front faces 420 of the blocks 412 of the wall structure 410 are smooth and the viewable rear faces 422 of the blocks of the wall structure 410 are roughened or otherwise decorated. Note that the leftmost beam 416 may be used to form the base and a cap of a horizontally oriented wall structure.
[0158] Referring now to FIG. 31 , a support beam 116 , has an extension 508 , which terminates in an attachment member 512 -with feet 516 , 518 . However, in this embodiment the extension 508 and the feet 516 , 518 are foreshortened. Note that the support beam 116 is not directly connected to a substructure “S” but is operatively connected to a bracket 534 that is, in turn, operatively connected to a substructure “S” (shown in dashed lines). The bracket 534 includes a substructure engaging portion 536 , a span 538 and an attachment member with a support beam engaging portion 542 . The support beam engagement portion 542 is sized to be snuggly received and frictionally retained within a channel 530 or 532 formed by a rib and a foot ( 505 , 516 ; 506 , 518 , respectively) of the beam 116 . Note that the support beam 116 need not extend along the length of the bracket 534 , and more particularly the support beam need not be coextensive with the side of a block to which it is operatively connected. The reason for this is that a block 112 need not be retained along its entire length of its grooves to be adequately retained as part of a wall structure. Instead, it is only necessary for a block to retained at several points. Thus, the support beams 116 may take the form of clips that attach to the bracket 534 , and a block 112 may be retained at a plurality of predetermined locations such as its upper and lower ends. It will be appreciated that such support beam clips may be used to operatively connect a pair of blocks to a support bracket 534 by positioning the clips so that they span the interface between two adjacent blocks. It will also be appreciated that the support beam clip may be longer than a side of a block to which it is operatively connected so that it may operatively connect more than two blocks to a bracket.
[0159] The span 538 of the bracket 534 serves to position the support beam 116 a predetermined distance from a substructure “S” while the substructure engaging portion 536 serves to attach the bracket 534 onto a substructure “S”. As with the aforementioned embodiment, the bracket 534 may be operatively connected to a substructure “S” using a variety of fastening elements. It will be appreciated that the support beam 116 of this embodiment may be used with oppositely facing brackets, if desired, to form a more robust connection between the wall structure and a substructure “S”.
[0160] Referring now to FIGS. 32 and 18 , the support beam 116 does not have an extension. Rather, as best shown in FIG. 18 , the beam 116 terminates at a first attachment member 512 that includes two spaced apart resilient walls 550 , 552 having confronting arms 554 , 556 , which define a slot 558 and channel 560 that are sized to admit and retain a second attachment member 570 .
[0161] With this embodiment, the support beam 116 is not directly connected to a substructure “S” but is operatively connected to a bracket 562 that is, in turn, operatively connected to a substructure “S” (shown in dashed lines). The bracket 562 includes substructure engaging portions 564 , 566 , a span 538 and an attachment member 570 . As best shown in FIG. 18 , the attachment member 570 is dart-shaped head 572 having shoulders 574 , 576 , which are configured to engage confronting arms 554 , 556 in a constrained relation. That is, the attachment member 570 of the support beam is sized to slidingly receive the dart shaped head 572 within a slot 558 and channel 560 formed by the resilient walls 550 , 552 and their confronting arms 554 , 556 . Thus, the support beam 116 may be connected to the bracket 562 in a constrained manner. It will be appreciated that the support beam 116 may be operatively connected to a bracket 562 in several ways. For example, by positioning the bottom of the channel 560 and the slot 558 over the dart shaped head 572 of the bracket 562 , the support beam 116 may be slid down along the bracket 562 to interconnect with an already positioned block 112 . Alternatively, the beam 116 may be slid down along the bracket 562 and later interconnecting with a block 112 , which is slid into position in a similar manner. Alternatively, a support beam 116 may be operatively connected to a bracket 562 by aligning the slot 558 of the attachment member 512 opposite the apex of the dart shaped head 572 and then pushing the support beam 116 towards the dart shaped head 572 until the confronting arms 554 , 556 of the attachment member 512 engage the shoulders 574 , 576 of the dart shaped head 572 .
[0162] The support beam 116 need not extend along the length of the bracket 562 , and, more particularly, the support beam need not be co-extensive with the side of a block to which it is operatively connected. The reasons for this have been discussed in conjunction with the description of FIG. 31 , and for purposes of brevity will not be repeated. The span 538 of the bracket 562 serves to position the support beam 116 . a predetermined distance from a substructure “S” and the substructure engaging portion 564 , 566 serves to attach the bracket 562 to a substructure “S”.
[0163] Referring now to FIGS. 33 and 19 , the operative connection is reversed from FIG. 32 . That is, the support beam 116 includes an extension 508 that terminates in an attachment member 570 having a dart-shaped head 594 with shoulders 596 , 598 . The bracket 580 includes two spaced-apart resilient walls 582 , 584 having confronting arms 586 , 588 , which define a slot 590 and channel 592 that are sized to admit and retain the dart-shaped attachment member 594 in a constrained relation, as discussed above. As with the aforementioned embodiments, the support beam 116 need not extend along the length of the bracket 562 , and the bracket 562 may be operatively connected to a substructure “S” using a variety of fastening elements.
[0164] With reference to FIGS. 34 and 35 , support beam 116 depicted is similar to the support beam of prior embodiments in that it includes a web 510 from which a plurality of ribs 503 , 504 , 505 and 506 extend. In a departure from this previous embodiment, the support beam 116 includes an extension 500 that terminates with an attachment member 512 . Preferably, the extension 500 is aligned with, and extends from the web 510 so as to position the attachment member 512 is a predetermined distance from the plurality of ribs. Note that the ribs 503 , 504 , 505 and 506 are reversed relative to each other so that the pair of opposing ribs 505 and 506 are now forward relative to the opposing pair of ribs 503 and 504 . In FIG. 34 , the attachment member 512 is depicted as having feet 516 and 518 , however it is understood that the attachment member may take other forms such as those depicted in FIGS. 18-20 . Note also, that the pair of forwardly facing opposing ribs 505 , 506 are somewhat thicker than the pair of opposing ribs 503 , 504 . This feature allows the support beam 116 to have a viewable surface 507 , which may form part of an observed wall. As depicted in FIGS. 34 and 35 , ribs 505 and 506 may be coplanar or collateral relative to the viewable faces 320 , 322 of blocks in a wall structure.
[0165] Referring again to FIGS. 34 and 35 , the blocks 312 that are used with the aforementioned beam 116 are similar to the blocks 112 depicted in the wall construction 110 of FIG. 30 . That is, each block 312 has a front face 320 , a rear face 322 , a top surface, a bottom surface and opposing sides.
[0166] Each block 312 differs from the block 112 depicted in FIG. 30 in several respects. First, block 312 has only one pair of opposing fingers 328 a ′, 328 b ′ instead of the pair of opposing fingers depicted in FIG. 33 . Thus, each block 312 does not have a groove that obscures a support beam rib. Instead of a groove, each block 312 has opposing ledges 334 , 336 defined by pairs of side surfaces 330 a , 330 b , 330 c , 330 d and fingers 328 a ′, 328 b ′, respectively. Preferably, the thickness of the ledges 336 , 338 will be substantially the same as the thickness of opposing ribs 505 , 506 to enable the viewable surface of a wall structure to be substantially contiguous. However, it is understood that the thicknesses of the ledges 336 , 338 and/or opposing ribs 505 , 506 need not be substantially the same. For example, the thickness of the ribs 505 , 506 may be greater than the thickness of the ledges 336 , 338 of the blocks so that the viewable surface 507 of a support beam projects outwardly with respect to the viewable surface of the blocks of the wall structure (as in FIG. 35 ), or the thickness of the ribs 505 , 506 may be less than the thickness of the ledges 336 , 338 of the blocks so that the viewable surface 507 of the support beam is recessed with respect to the viewable surface.
[0167] Another difference between block 312 and block 112 is that the opposing laterally extending, aligned fingers 328 a ′, 328 b ′ are offset from the center plane of the block 312 . As seen in FIGS. 34 and 35 this allows blocks to be operatively connected to a support beam in several configurations. In FIG. 34 , for example, blocks 312 are operatively connected to a support beam so that front face 320 (left side) and rear face 322 (right side) are substantially flush with the viewable surface 507 of the support beam 116 . As with the aforementioned blocks of FIG. 30 , the front and rear faces may have the same surface or different surfaces. Here, the front face 320 on the left side of FIG. 34 is depicted as being smooth, while the rear face 322 on the left side of FIG. 34 is depicted as being roughened. The viewable surfaces on the right side of FIG. 34 are reversed. In FIG. 35 , the blocks 312 have been rotated so that when they are operatively connected to the support beam 116 they are set back from the viewable surface 507 . It will be appreciated that the blocks 312 need not be all coplanar or set back with respect to the viewable surface 507 of the support beam 116 . Combinations of setback blocks and coplanar blocks are possible to create a myriad of wall surfaces. It is contemplated that such combinations may be arranged into identifiable forms or patterns and may also be arranged to display alphanumeric characters and the like. Note that the viewable surface 507 may be provided with a textured or otherwise decorated surface, which matches the surfaces of adjacent blocks. Alternatively, as depicted in FIG. 34 , the forward facing surface of the support beam can be provided with a cap or strip 145 of material with a viewable surface 147 , which may be textured or otherwise decorated as desired and which may be affixed or attached to the viewable surface 147 in a conventional manner.
[0168] Referring now to FIG. 36 , another preferred embodiment depicts a post 600 , which has been provided with a plurality of connectors to enable the post to support a plurality of wall structures. In this embodiment, the post 600 includes opposing sides 602 , 604 from which extend a web 606 and a bracket 612 , respectively. A pair of ribs 608 , 610 extend laterally in opposite directions from the web 606 , while the bracket 612 includes the slot 614 and channel structure 616 similar to the slot and channel structures described and shown in FIG. 18 , respectively. Thus, with this embodiment, blocks may be directly connected to the post 600 at side 602 or connected indirectly at side 604 via an appropriately configured support beam.
[0169] Other combinations of operative connections may also be used. For example, the post 600 . may be provided with two direct connectors (webs with laterally extending ribs) or the post may be provided with two indirect connectors (attachment members, such as channels). As will be appreciated, the post 600 may be operatively connected to a substructure such as a footing or foundation, or be set into the ground using known techniques and technologies. While the post 600 is depicted as having a hollow cross-section, it is understood that the post may also be a solid in cross-section or may have a reinforcing structure such as a pipe or a rod received therein (see, for example, FIG. 39 ).
[0170] FIGS. 37-37 b illustrate additional embodiments of the present invention. FIG. 37 shows a support beam 16 having a pair of leg structures 654 that are constructed and arranged to secure a wall comprising columns 14 of blocks 12 to an existing support structure 658 . The support structure 658 may be a building or any other type of structure that may support a wall structure 10 according to the present invention. Legs or leg portions 656 of the leg structures 654 extend rearwardly from the support beam 16 and are preferably secured to ribs 38 b thereof. The leg structures 654 may also be formed as part of the web 36 of the support beam 16 . The leg portions 656 have a foot 660 , which extends laterally therefrom to provide a point of connection for the support beam 16 to the existing support structure 658 . Nails, screws, or other appropriate fasteners 662 may be driven through the feet 660 of the support beam 16 and into the sheathing 664 of the typical wall of the wall of the existing structure 658 . The sheathing 664 is typically supported by a plurality of horizontal girts 666 . Once the support beam 16 has been secured to the existing structure 658 , blocks 12 are stacked between respective support beams 16 as illustrated in FIG. 37 such that ribs 38 a of the support beam 16 reside in grooves 34 in the sides of the blocks 12 .
[0171] In order to prevent the inflow of water into the wall structure 10 , it may be desirable to apply a bead of a waterproof material 670 , such as mastic or caulk, along the horizontal surfaces of the blocks 12 . The bead of waterproof material 670 forms a seal between the upper surface 24 of the lower block 12 upon which the waterproof material 670 has been applied and the lower surface 26 of the block 12 immediately above the lower block 12 . It will be appreciated that mastic or caulk may also be applied to the vertical side surfaces of the blocks (not shown).
[0172] Legs or leg portions 656 of support beam 16 preferably extend rearwardly from the ribs 38 b in a perpendicular relationship thereto. Similarly, it is preferred that the feet 660 of the support beam 16 extend laterally perpendicular to the leg portions 656 . The perpendicular relationship of the feet and legs to the remainder of the support beam 16 is the preferred embodiment thereof since the purpose of the leg portions 656 and the feet 660 to provide an offset for the wall structure from the existing structure 658 . This offset allows a wall structure 10 to be secured over uneven surfaces such as corrugated steel siding 668 , as illustrated in FIG. 37 . As can be seen, legs or leg portions 656 of support beam 16 are sufficiently long such that the support beam 16 clears ridge 673 of the steel siding 668 . As can be appreciated, steel siding 668 typically presents a plurality of vertically flat attachment surfaces. Where a wall structure 10 is to be applied to a wall of an existing structure 658 that is not vertically smooth, furring strips or blocking may be fastened to the wall of exterior of the existing structure 658 as needed. As support beams 16 provide no vertical support for the blocks 12 , the blocks must be provided with some sort of foundation. Examples of suitable foundation include, but are not limited to, a concrete pad or footing that is sunk into the ground, and a cantilever ledge or bracket which is securely affixed to the wall of the existing structure.
[0173] FIG. 37 a illustrates a support beam 16 having two pairs of ribs 38 a and 38 b separated by a web 36 and only a single leg structure 654 comprising a leg portion 656 and a foot 660 . The embodiment of FIG. 37 a is particularly useful when an obstruction, such as ridge 673 of steel siding 668 would prevent one of the leg structures 654 illustrated in FIG. 37 from securely contacting the wall of the structure 658 . Fasteners 662 are sufficient to provide the requisite lateral support for the wall structure 10 . The support beam 16 having only a single leg structure 654 may be rotated end-for-end depending on the offset location of an obstruction such as ridge 673 .
[0174] Preferably, the support beams of the present invention will be extruded or molded from a material such as a plastic, a fiber reinforced resin, or a metal such as aluminum. In addition to forming embodiments of support beams 16 having the respective profiles of the support beams illustrated in FIG. 37 a , it is possible that one leg structure 654 could be removed from a support beam 16 such as the support beam 16 of FIG. 37 having two leg structures 654 , thereby resulting in the support beam 16 embodiment illustrated in FIG. 37 a . However, where a single leg structure 654 would be sufficient to provide the needed lateral support for a wall structure 10 , it would be more economical to manufacture support 16 having only a single leg structure 654 . As used herein, the term “forward” means away from the center of the elevated structure (and along the “z” direction in a three-dimensional coordinate system relative to a block) and the term “rearward” means toward the center of the elevated structure (also along the “z” direction in a three-dimensional coordinate system relative to a block).
[0175] FIG. 37 b illustrates a support beam 16 that is constructed and arranged to provide lateral support to a wall structure 10 as described in conjunction with FIGS. 37 and 37 a . The main difference here being that the support beam 16 of FIG. 37 b has a pair of ribs 38 a and only a single rib 38 b extending from the web 36 . A leg structure 654 extends rearwardly from the rib 38 b preferably in a perpendicular relation thereto. While it is preferred that the leg or leg portion 656 and foot 660 be arranged at right angles to each other and to the ribs 38 b of the support beam 16 , these structures may be arranged at any angle to one another provided, of course, that there is a sufficient offset from the wall of the existing structure 658 to allow installation of the blocks 12 of the wall structure 10 and that the foot 660 of leg structure 654 may be securely fastened to an supporting structure 658 .
[0176] FIG. 38 illustrates a double-ended support beam 80 b , which is useful for constructing a dual wall structure 10 having a front face 74 and a rear face 76 . The space between the front and rear faces 74 , 76 of the wall structure 10 may remain hollow or may be filled. Each end of the double-ended support beam 80 b comprises a support beam or block engagement structure having a cross-sectional profile similar to the support beam illustrated in FIG. 11 arranged back-to-back in a spaced apart relation and connected by a spacer web 82 b . Spacer web 82 b is connected to the base pair of ribs 38 b of each of the support beam portions in a perpendicular fashion. In this manner, support beam 80 b couples dual walls of the wall structure 10 to provide mutual lateral support. Further support can be had by backfilling the space between the front and rear sides of the dual wall structure 10 with gravel, earth, sand, concrete or insulative material 79 . Preferably, it will be appreciated that a cap 81 , such may be placed over the top of the dual wall structure 10 to prevent the ingress of water, debris, or nuisance animals. It will also be appreciated that such a cap 81 may be secured to the dual wall structure by known technologies and techniques, if desired. See, for example, the use of adhesive material depicted in FIG. 37 .
[0177] FIG. 39 illustrates a single-sided wall structure 10 comprising columns 14 of blocks 12 supported by a post-like support beam 84 . Support beam 84 comprises a post 85 having extending therefrom a web 36 . A pair of ribs 38 a extend laterally from the web 36 in the same manner as the ribs 38 a of support beams 16 described in conjunction with FIG. 11 . As installed, post 85 is preferably rigidly seated in a footing or foundation set into the ground below the wall structure 10 . As can be appreciated, blocks 12 are stacked between respective post support beams 84 as described above. The post 85 preferably has a hollow cross-section. However, post 85 may also be solid in cross-section or be provided with a reinforcing structure such as a pipe or a rod received therein. An alternate embodiment for the post or support beam 84 involves securely seating a plurality of rods or members in footings or a foundation beneath the wall structure 10 and sliding the post or beam 84 of the type illustrated in FIG. 39 thereover. Blocks 12 would then disposed between respective pairs of post support beams 84 as described above.
[0178] Now turning to FIG. 40 , a wall structure 10 is depicted as it may be used in conjunction with an elevated structure “S.” As with the wall structure generally depicted in FIGS. 4 and 22 , this wall structure 10 is comprised of a plurality of blocks 12 arranged in columns 14 , having the columns 14 held in place by vertically oriented, lateral support beams 16 , and with each beam 16 operably connecting adjacent columns 14 together. The brackets 19 used in this embodiment, however, differ from the “U”-shaped brackets 18 of the previously described embodiment in several respects. First, the brackets 19 are shaped differently than the bracket 18 of FIGS. 4 and 22 . Instead of having an inverted “U”-shaped configuration as with bracket 18 , the bracket 19 of this embodiment has a single, downwardly extending portion. Another difference is that rather than positioning a portion of a block 12 within an opening 50 defined by a pair of walls 44 , 46 , the bracket 19 of the embodiment has a wall engaging portion 62 that extends downwardly into vertical grooves 34 at the sides of blocks 12 . Another difference between brackets 18 and 19 is that bracket 18 connects to a column 14 in a generally central location, whereas the brackets 19 of this embodiment connect at the sides of column 14 . As with the previously described brackets 18 , brackets 19 help to stabilize and prevent the wall structure 10 from tipping rearwardly or forwardly. The brackets 19 also prevent the structure from shifting from side to side.
[0179] For purposes of illustration, the size of the wall structure 10 of this embodiment has been limited three columns 14 and four courses, with the two uppermost blocks of the left column 14 removed to reveal the juxtaposition between the brackets 19 , beams 16 and blocks 12 . Note that the wall structure 10 depicted in this embodiment also includes a plurality of footings or support pads 80 a that are positioned beneath the columns 14 at the junction where they connect to the beams 16 . Preferably, each footing or support pad 80 a may be provided with a setting channel 82 a that is configured and arranged to receive the bottom edges of one or more columns of blocks in a constrained relation. Note that the footing or support pad 80 a for the middle and right columns 14 has been removed and replaced with an “L”-shaped support base or angle iron (see, for example, the support base in FIGS. 3 and 53 ) that spans the bottom of the middle and right columns 14 . This construction can be used when the use of individual, regularly spaced footings 80 a is not possible or desirable. Also note that the wall structure 10 is depicted as having a running bond on its three lowermost courses. As can be seen, the bottom and third courses of blocks do not have splitting recesses. They do, however, have their perimeter marginal areas 23 a - d worked. The second course of blocks, on the other hand, have splitting recesses 21 and have only their horizontal marginal areas worked. Thus, each column 14 will have blocks with alternating front faces. When the columns of blocks are positioned adjacent each other in the normal assembly procedure some of the blocks 12 will form tight joints 31 and some of the blocks will form joints that appear substantially thicker. Thus, from a distance, the wall structure 10 will give the impression that it was constructed of blocks and mortar in a conventional manner. It will be appreciated that the externally viewable surface of the wall structure depicted in FIG. 40 is merely one example of an externally viewable surface, and that many other externally viewable surfaces are possible.
[0180] Turning now to FIGS. 41-43 , a preferred embodiment of bracket 19 depicted in FIG. 40 will now be discussed. As can be seen in FIGS. 41 and 42 , the bracket 19 comprises a structure engaging portion 60 and a wall engaging portion 62 . The wall engaging portion 62 of the bracket 19 includes opposing surfaces 64 , 66 , which are arranged and configured to contact a portion of a beam 16 and a portion of a block, respectively. If desired, the wall engaging portion 62 may be provided with strengthening creases 67 . As will be appreciated, the wall engaging portion 62 of the bracket 19 has a width 77 and a length 78 whose dimensions correspond to the particular blocks that are being used to construct a wall, and will be discussed only in general terms. Thus, the width 77 may range from a distance roughly equivalent to the depth of a single groove 34 in one block, to a distance roughly equivalent to the depth of two grooves 34 of opposing blocks. The width may also be roughly equivalent to the width of the web 36 of the beam 16 so that the wall engaging portion of the bracket may be oriented transversely to the wall structure. The length 78 may also vary depending upon the requirements of the wall structure (not shown). A typical width and length for a wall engaging portion 62 may be on the order of about two inches by about four inches, and a typical width and length for a structure engaging portion 60 may be on the order of about two inches by about one-and-a-half inches. It will be appreciated that the bracket 19 may be formed from material that may be modified or otherwise altered to fit a particular application. Thus, for example, the width and/or length of the wall engaging portion may be cut-to-length length or otherwise tailored at a jobsite without appreciably delaying or hindering construction.
[0181] The structure engaging portion 60 of the bracket 19 also includes opposing surfaces 68 , 70 . However, in this embodiment, only opposing surface 68 is configured to contact a portion of a structure (See, FIGS. 40 and 42 ). As depicted, the structure engaging portion 60 is attached to a lower surface of a structure “S” by an upwardly extending fastener or fastening element 73 . It is understood, however, that the attachment surface of the structure can be an upper surface, in which case the opposing surface 70 would contact the surface of the structure “S” and the fastener would extend downwardly from surface 68 (shown in dashed lines). As shown in FIG. 42 , the structure engaging portion 60 and the wall engaging portion 62 are planar and substantially orthogonal with respect to each other. It is understood, however, that the wall engaging portion 62 and the structure engaging portion 60 need not be orthogonal to each other. They may be linearly aligned, for example. It is also envisioned that the wall and structure engaging portions may be formed in other configurations. For instance, either portion 60 , 62 may be formed with U-shaped profiles that enable the portions 60 , 62 to straddle sections of the structure and/or wall. That is the structure engaging portion may be formed so that it may straddle the bottom and side edges of a structure and the wall engaging portion may be formed to engage a wall structure at its front and/or rear surfaces. The structure engaging portion 60 is provided with an aperture 72 that may be used with a conventional fastener 73 . For purposes of this application, the term “fastening element” or “fastener” may include mechanical fasteners such as screws, nails, bolts, rivets, or their equivalents, and/or adhesives, weldments, or the like. Alternatively, the structure engaging portion 60 may be provided with an integral fastening element so that the portion 60 may be driven into or otherwise attached to a support.
[0182] Another embodiment of a bracket is depicted in FIGS. 44 and 45 . As can be seen, the bracket 200 generally comprises a structure engaging portion 202 and a support beam engaging portion 203 . More specifically, the structure engaging portion 202 comprises a first member 204 and a second member 206 , which are angled with respect to each other to form a generally “L”-shaped form. The first and second members may be provided with apertures 208 that permit attachment to a structure with fastening elements such as nail and threaded fasteners. It will be appreciated, though, that attachment may also be achieved with suitable adhesives used in lieu of or in addition to fastening elements. The support beam engaging portion 203 comprises a web 210 and a pair of legs 212 , 214 , which are angled with respect to the web 210 to form a generally “L”-shaped form. The web 210 includes an aperture 220 that is accessible through a slot 222 defined by edges 216 and 218 of legs 212 and 214 , respectively. The aperture 220 and slot 222 are configured to slidingly receive a pair of ribs and a portion of a web of a support beam. As depicted in FIGS. 44 , and 45 , when a support beam is attached to the bracket, the support beam is able to move in a constrained manner relative thereto. This feature allows, the bracket to be attached at different points along a structure as well as different points along a beam. Moreover, it allows a wall construction to be self-adjusting. An application of bracket 200 , a support beam 116 , and a plurality of brackets 112 as can be seen in FIG. 53 .
[0183] Another embodiment of a bracket is depicted in FIGS. 46 and 47 . The bracket 230 of this embodiment comprises a structure engaging portion 232 , a connecting web 234 , and a support beam engaging portion 235 that comprises a rib 236 and a coupling element 238 . The bracket 230 is configured and arranged to operatively connect a support beam (such as the support beams depicted in FIGS. 11 a , 28 , 44 , and 45 ) to a support. As with the previously described bracket embodiment ( 200 ), the structure engaging portion 232 may be provided with apertures 240 that permit the bracket to be attached to a structure with conventional fastening elements. Alternatively, the bracket may be attached to a support using other known technologies and techniques. When the bracket 230 is used to operatively connect a beam to a support, the coupling element 238 of the beam engaging portion 235 is slidingly retained between one of the coupling elements 186 and one of the pairs of ribs 182 a . Thus configured, a support beam is able to move in a constrained or sliding manner relative thereto. This feature allows the bracket to be attached at different points along a structure as well as along different points along a beam. The bracket also permits a wall structure to be self-adjusting.
[0184] Referring now to FIGS. 48 and 49 , an alternative embodiment of an attachment bracket 90 is depicted. Here, the bracket 90 is similar to earlier discussed bracket 18 (see FIGS. 4 and 22 ) in that it has opposing walls 92 , 94 that are connected to each other by a top wall or span 96 , and which retain a portion of a block in a constrained relation. However, in this embodiment, the shorter of the two walls 94 is provided with an arm 98 that is movably attached thereto by a connector 100 , such as a rivet. As depicted in FIG. 48 , the arm 98 is in a first position where it extends towards a block (not shown). In this position, the bracket 90 resembles bracket 18 (see FIG. 4 ) and may be attached at or near the underside of a structure in the usual manner, via the span 96 .
[0185] In situations where it is not possible to easily attach the bracket 90 to the underside of a structure, a user of the bracket 90 need only rotate the arm 98 to a second position so that it extends away from a block (not shown) as depicted in FIG. 49 . In this position, the bracket may be attached to a vertical surface via the arm by a conventional fastener, such as a nail or screw, which extends through an aperture 102 . Alternatively, the bracket may be secured to a vertical surface by a suitable adhesive. As will be appreciated, the bracket 90 may be oriented so that either one of the walls 92 , 94 may be in confronting relation with the front or rear face of a block.
[0186] FIGS. 50-52 illustrate brackets and beams as shown in FIGS. 2 and 2 a as they may be used in conjunction with blocks to form alternative structures. Starting with FIG. 50 , bracket 354 is depicted. The bracket 354 is similar to previously described bracket 200 shown in FIGS. 44 and 45 in that it generally comprises a structure engaging portion and a support beam engaging portion. However, there are differences. Instead of having a structure engaging portion that comprises a first member and a second member, structure engaging portion 356 of bracket 354 comprises a single or first member 357 . As depicted, the first member 357 is provided with an aperture 360 that facilitates attachment to a structure with fastening elements such as nails, threaded fasteners, or rivets. It will be appreciated, however, that an aperture or apertures need not be present in order to attach the bracket to a structure. The fastening element(s) may be driven through the first member, if desired. Additionally, it will also be appreciated that attachment may also be achieved with suitable adhesives, in lieu of, or in addition to, fastening elements. Continuing on, the support beam engaging portion 358 comprises a web 362 and a pair of legs 364 , 366 , which are angled with respect to the web to form a generally “L”-shaped form. The web 362 includes an aperture 368 that is accessible through a slot 370 defined by edges 372 and 374 of legs 366 and 364 , respectively. The aperture 368 and slot 370 are configured to slidingly receive a leg portion 732 b and foot 734 of a support beam 716 of FIGS. 51 and 52 .
[0187] Generally, the bracket of FIG. 50 may be used with beams and blocks as shown in FIGS. 51 and 52 to form wall structures similar to wall structures previously discussed. More specifically, support beam 716 , as shown, comprises an elongated spine or web 718 and plurality of ribs 720 and 722 , 724 and 726 , which are arranged in a substantially coplanar and collateral relation so that the first pair of ribs 720 , 722 , which are substantially coplanar, extend away from each other in a manner similar to other embodiments already described. As shown, a first pair of ribs 720 , 722 are designed to engage the grooves 728 of one or more blocks of a structure. As shown in FIG. 51 , the support beams 716 may be oriented in a generally vertical direction, or as in FIG. 52 , a generally horizontal direction. Note that in either orientation, the blocks would essentially be self-supporting.
[0188] In addition, the web also includes a second pair of ribs 724 , 726 which are also substantially coplanar and which extend away from each other. Note that the pairs of ribs 720 , 722 and 724 , 726 are in substantially collateral or parallel relation with respect to each other and are spaced apart from each other by a distance defined by the web 718 . The support beam 716 also includes a pair of pair of leg structures 730 having leg portions 732 a - b that are similar to the leg structures of FIG. 37 in that they extend rearwardly away from ribs 724 , 726 and which form a generally U-shaped channel therewith. The support beam differs, however, in that only one of the leg portions 732 b includes a foot 734 . As depicted, the foot 734 extends laterally away from the leg portion 732 b and is generally parallel with ribs 720 , 722 . As with the embodiment of FIGS. 2 and 2 a , the foot may be connected directly or indirectly to a support structure. However, as depicted, the beams of FIGS. 51 and 52 are operatively connected to a structure by a plurality of brackets 354 , which are attached to suitable structural members. With such an arrangement the beams, which are slidingly constrained by the brackets, permit blocks to move without destroying the integrity of the structure.
[0189] As shown in FIG. 53 , a bracket 200 is used as part of a wall system to operatively connect a support beam 116 to a structure “S”. Note that the lowermost course of blocks is supported by a horizontally oriented, elongated base, preferably in the form of an angle iron 83 , which can be used with one or more support pads or footings 80 a , if desired. The angle iron 83 includes an upper surface 86 , that is configured to receive one or more blocks thereon and a sidewall 88 that prevents the block(s) from being shifted backwards. Optionally, the upper surface and/or the sidewall of the angle iron 83 may be provided with adhesive material to enable the block(s) to be secured thereto, which increases the strength and stability of the wall structure. Often, a completed wall structure will terminate in an upper course of blocks that is offset from the structure “S”. In these situations, one or more capstones or sills 113 may be used to provide a finished look, with the sills being positioned upon the upper course of blocks. As will be understood, the sills may be attached to the upper course of blocks using known technologies and techniques, such as adhesives. Sometimes, there is a gap between a capstone or sill 113 and the structure “S”, through which moisture, debris, insects, etc. may pass. This gap can be effectively closed using a sealing element 250 as depicted in FIGS. 54 and 55 .
[0190] The sealing element 250 of the present invention generally comprises a body having a plurality of flexible, resilient strips that provide an effective seal between the sills or finish moldings and the structure. More specifically the sealing element 250 comprises a sealing panel 251 that is formed by first and second strips 252 and 254 and an attachment portion 255 that is formed by third and fourth strips 256 and 258 . The attachment portion 255 is operatively connected to the panel 251 such that the third and fourth strips extend therefrom in a generally radial relation. As can be seen in FIGS. 54 and 55 , the sealing element is in an unflexed state and the third and fourth strips 256 and 258 define an angle 262 , which can range from about 15 degrees to about 165 degrees. The preferred range of the angle however is in the range of about 45 degrees to about 75 degrees. The third and fourth strips 256 and 258 may include beads or wales 260 that enable the sealing element to anchor itself into position. In use, the third and fourth strips 256 and 258 of the attachment portion 255 are pinched together and inserted into the gap between the wall and a structure, as shown in FIGS. 53 and 56 . As the attachment portion 255 is seated, the first and second strips 252 , 254 of the panel 251 contact the surfaces of the sill 113 and the structure “S” and exert normal forces there against. Thus, effectively seals the gap. As will be appreciated, the sealing element is maintained in position by the beads 260 that, due to the resilient nature of the strips, tend to catch against irregularities in the surfaces of the sill and the structure “S” and resist movement. As will be appreciated, the sealing element 250 may be oriented so that the first and third strips 252 , 256 contact the sill 113 and the second and fourth strips 254 , 258 contact the structure “S”, if desired.
[0191] There may be times when it is not possible, practical, or desirable to use beams or the combination of beams and brackets, as previously described to operatively connect blocks to a structure. In such cases, blocks may be attached to a structure using only brackets. Generally, as shown in FIGS. 57-59 , each bracket comprises a structure engagement portion and a block engagement portion that are spaced from each other by a web. In one preferred embodiment, shown in FIG. 57 , the bracket 754 comprises a structure engagement portion 756 that is similar to previously described structure engagement portions in that it is configured and arranged to act as a point of attachment to a structure, and comprises a member 766 having an aperture 768 , with the aperture configured to be used in conjunction with a fastening element such as a nail, screw or rivet. The bracket also comprises a web 762 and a panel 760 , which collectively serve to connect the structure engagement portion 756 to a block engagement portion 758 , and which serve to position a block a predetermined distance from a structure to which it may be attached. While the structure engagement portion 756 and the web 762 form a generally 90 degree angle therebetween, it will be understood that the angle may be modified depending upon the configuration of the structure to which it is attached. Thus, for example, the angle could be acute or obtuse. The block engagement portion 758 , which is connected to the web, comprises a plurality of generally planar sections 759 a , 759 b , 759 c , 759 d , and which are configured to cooperatively engage portions of one or more blocks such that forward and rearward movement of the blocks relative to the structure, is limited. This is achieved by forming some sections so that they are substantially coplanar with each other and forming some sections so that they are substantially parallel to each other (when viewing the bracket on edge). Note that those sections that are coplanar with each other extend away from the web in opposite directions, while those sections that are parallel to each other and spaced from each other by a panel, need not be so restricted. Note also, that the sections are configured and arranged so that when viewed from front, the sections do not overlap or superimpose upon each other. As will be appreciated, this permits to bracket to be manufactured from material such as metal and formed into the desired configuration with a series of cuts and bends. It will be understood, however, that the bracket may be manufactured from different materials (eg. plastics) and formed using different techniques (eg. molding) without departing from the spirit and scope of the invention. In use, as shown in FIG. 60 (right side), the bracket 754 operatively connects two blocks to a structure “S”.
[0192] Alternative embodiments of bracket 754 are depicted in FIGS. 58 and 59 . As with the previously described bracket, these brackets 754 ′ and 754 ″, respectively, comprise a structure engagement portion, a web, and a block engagement portion. The structure engagement portions are similar to the structure engagement portion of FIG. 57 in that they are configured and arranged to act as a point of attachment to a structure, and comprises a member 766 ′, 766 ″ having an aperture 768 ′, 768 ″ respectively, with the aperture configured to be used in conjunction with a fastening element such as a nail, screw or rivet. Likewise, the brackets also comprise a web 762 ′, 762 ″ which serve to connect the structure engagement portion 756 ′, 756 ″ to a block engagement portion 758 ′, 758 ″, respectively, and which serve to position a block a predetermined distance from a structure to which it may be attached. In a departure from the web structure of FIG. 57 , the webs of FIGS. 58 and 59 include an additional aperture 764 ′, 764 ″ that is configured and arranged to act as a point of attachment to a structure (see, for example, the left side of FIG. 60 ). As with the previously describe embodiment of FIG. 57 , the angle formed by the structure engagement portion and the web (shown generally as 90 degrees) may be modified depending upon the configuration of the structure to which it is attached. The block engagement portions 758 ′, 758 ″, which are connected to respective webs, each comprise a plurality of sections 759 a ′and 759 b ′, 759 a ″ and 759 b ″, which are configured to cooperatively engage portions of one or more blocks such that forward and rearward movement of the blocks relative to the structure, is limited. This is achieved by forming the sections so that they are generally coplanar to each other (when viewing the bracket on edge) and able to engage opposing surfaces in one or more blocks. A feature common to each of the sections 758 a ′and 758 b ′, 758 a ″ and 758 b ″ is that they have a thickness 776 ′, 776 ″ that effectively spans the distance between the opposing surfaces into which they are positioned, such that forward and rearward movement of the blocks relative to the structure, is limited. In particular, the effective thickness of each section 776 ′, 776 ″ of bracket 754 ′, 754 ″ is achieved by forming creases 772 in each section to form darts 770 , whose ends define the extent of the effective thickness 776 ′. A strengthening rib 774 may be provided for each section, if desired. The effective thickness 776 ′ of the sections 770 of bracket 754 ′ is achieved by forming the sections so that they have high and low block contacting areas, preferably by curving the sections and more preferably by forming the sections into the shape of arcs. FIG. 60 is a plan view of the brackets of FIGS. 57 and 59 operatively connecting blocks of the present invention to a substructure.
[0193] It is to be understood that even though numerous characteristics and advantages of various embodiments of the present invention have been set forth in the foregoing description, together with details of the structure and function of various embodiments of the invention, this disclosure is illustrative only, and changes may be made in detail, especially in matters of structure and arrangement of parts within the principles of the present invention to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed.
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The present invention relates to decorative and structural blocks designed to be installed as skirting structures for buildings, elevated structures and structural elements such as posts. More particularly, the present invention relates to a system that uses specifically designed and manufactured masonry blocks that are used in conjunction with specifically designed support beams and/or brackets to provide durable, attractive, easy to assemble surfaces or skirting structures. The blocks are shaped to be stacked in vertically independent, self-supporting columns, strengthened and linked together by specially shaped, lightweight, lateral support beams positioned between adjacent columns, and which may be attached directly or indirectly to a sub-structure.
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PRIORITY CLAIM
The present application claims priority from U.S. Provisional Application No. 60/810,538, filed on Jun. 2, 2006, by Robotham et al., titled “Transformer for Impedance-Matching Power Output of RF Amplifier to Gas-Laser Discharge.” U.S. Provisional Application No. 60/810,538 is hereby incorporated herein by reference in its entirety.
TECHNICAL FIELD OF THE INVENTION
The present invention relates in general to radio-frequency (RF) gas-discharge lasers and, in particular, to a transformer for matching the output of an RF amplifier to the gas discharge in such a laser.
DISCUSSION OF BACKGROUND ART
The cost of solid-state RF power supplies used for CO 2 lasers is approximately equal to the cost of the laser head. It is well known to those skilled in the art that, as the RF laser excitation frequency of the power supply is increased, the amount of RF power that can be coupled into the laser's gas discharge can be increased to a higher value without developing arcs within the discharge volume. Arcs within the discharge are detrimental to CO 2 laser performance. It is also well known that, as the RF frequency is increased, the discharge can be operated at higher pressures while still maintaining a uniform discharge. Both of these higher frequency benefits enable higher laser output power to be obtained from a given-size laser head.
Unfortunately, as the RF frequency of the solid-state power supply is increased, the design, assembly and cost of the power supply increases. Laser manufacturers are forced to make compromises between benefits in decreased laser size for a given laser power output, versus the disadvantages associated with design, assembly and higher cost associated with the use of higher-frequency solid-state power supplies.
Typically, frequencies in the VHF band (e.g. 30 to 300 MHz) are utilized in sealed-off, RF excited, diffusion cooled CO 2 lasers, with the frequencies between 30 MHz and 100 MHz being most common.
RF power supplies for the above-discussed lasers usually include a master oscillator and at least one stage of amplification. One of the more challenging tasks in designing RF power supplies for CO 2 lasers is the matching between the final RF amplifier and the laser discharge. The final RF amplifier may require impedances as low as 5-10 Ohms, while the transmission line carrying RF power to the discharge has an impedance that is typically 50 Ohms. The laser discharge impedance is in the order of 50 Ohms after ignition for laser power of 100 W. The power drops for higher power CO 2 lasers. This match must be efficient such that minimum RF power is lost within the impedance transformation. In addition, the impedance of the un-lit discharge is much higher than for the lit discharge. Consequently, there is a large mismatch prior to the discharge being lit. Additionally, the match must be able to withstand the possible high voltages generated during the process of igniting the discharge. Since to light the discharge requires a higher voltage than to keep it running after ignition, the ignition is usually performed with a high voltage pulse or a series of fast pulses. Transmission line transformers are inherently broadband so that they can deliver the high voltage “spikes” and they are also very efficient under continuous wave (CW) operation. Consequently, they are presently the preferred choice for this application. As discussed in detail below, the present invention provides a transformer design that maintains these characteristics and provides additional benefits.
Another challenging task is matching the relatively high output impedance (i.e. typically 50 ohms) of the electronic oscillator circuitry feeding into the relatively low input impedance (i.e. typically several ohms) of the input to the first stage of the RF power amplifier chain. The present invention can also be used to address this challenge.
The most mature RF impedance matching transformer technology is the use of wire wound on ferrite cores. This technology dates back to the middle 1950's and is commonly used at lower RF frequencies (i.e. below 80 MHz) as ferrite transformers tend to be lossey at higher RF frequencies (i.e. above 80 MHz). At high RF power levels (say, above 300 W) and for frequencies above 80 MHz, the loss within the ferrite creates a thermal problem and, therefore, adds further design complexity and cost to the RF supply. Many users of CO 2 lasers having up to approximately 100 W of output power usually desire to have the laser's RF power supply mounted directly on the laser head. The totally self-contained laser and power supply allows the user to avoid dealing with a co-axial cable connecting the laser head to a remotely located RF power supply. This desire is especially strong in applications that require the laser to be mounted on a robotic arm.
Cooling the ferrite transformers within RF power supplies mounted directly on laser heads is especially difficult when air cooling is desired. In addition to the loss at higher RF frequencies, ferrite transformers tend to have larger height, width and depth dimensions than other components on the printed circuit board (PCB).
The electrical characteristics of ferrite transformers vary from unit to unit so as to require special sorting before being used in a PCB assembly. The sorting results in special tuning steps required during power supply assembly. The sorting, assembly tuning and thermal management raise the final cost of the laser and are major disadvantages of this technology.
FIG. 1A schematically shows a co-axial cable 100 that includes an outer conductor 102 and an inner conductor 104 with a dielectric 106 separating the two conductors. FIG. 1B is a schematic illustration of a 1-to-4 step-up co-axial transformer frequently used in RF power supplies to drive sealed-off, diffusion cooled CO 2 laser discharges. Such transformers are presently used in commercially available 100 MHz power supplies driving 20 W to 100 W CO 2 wave-guide laser discharges. FIG. 1C shows a schematic of the physical electrical connections between two co-axial cables of equal length L to form the 1-to-4 step-up transformers shown in FIG. 1B .
The advantages of the co-axial transformers over the ferrite transformer approach are lower cost, lower RF losses and the capability of higher frequency operation. Unfortunately, the co-axial transformer technology shares some of the same disadvantages associated with ferrite transformer technology. These disadvantages are: the need to mount, restrain, and connect the transformer onto the PCB; the completed transformer has a relatively large height dimension when compared to the other components on the PCB; and its electrical characteristics are strongly related to position and manner of connection to the PCB. The last issue is the one of most concern.
SUMMARY OF THE INVENTION
The present invention enables the use of a combination of buried micro-strip and coupled micro-strip technology to achieve high RF frequency step-up or step-down transformers. The disclosed technology overcomes most of the disadvantages of the well-established ferrite and semi-rigid co-axial transmission line transformers technology with reduced over-all cost, increased repeatability, and increased reliability.
A transformer in accordance with one embodiment of the present invention comprises first and second dielectric plates each having an upper surface and a lower surface. The lower surface of the first dielectric plate is non-conductively bonded to the upper surface of the second dielectric plate. A primary transformer winding in the form of an electrically conductive strip is embedded in the upper surface of the second dielectric plate. A secondary transformer winding in the form of an electrically conductive strip is formed on the upper surface of the first dielectric plate. A ground plane electrode is formed on the lower surface of the second dielectric plate. An electrical connector connects the secondary transformer winding to the ground plane electrode via a via-hole extending through the first and second dielectric plates.
In one example of the inventive transformer for providing an about one-to-two impedance matching ratio (e.g., a step-up ratio), the primary transformer winding has one, generally U-shaped turn, and has a first strip-width. The secondary transformer winding has about two, coplanar turns, and has a second strip-width that is less than one-half of the first strip-width. The primary and secondary windings are arranged face-to-face with the secondary transformer winding overlapping the primary transformer winding. The terms “about one turn” and “about two turns” as used above mean that the number of turns need not be complete turns or that the strip length may be more than needed to form the stated number of turns. In this example, a higher step-up ratio may be achieved using more than about two turns cooperative with the U-shaped primary winding. By way of example, a secondary winding having about two secondary turns may be used to achieve a step-up ratio of about one-to-four. The strip width of the secondary winding in this case would be less than one-quarter of the primary strip-width.
The features and advantages of the various aspects of the present invention will be more fully understood and appreciated upon consideration of the following detailed description of the invention and the accompanying drawings, which set forth illustrative embodiments in which the concepts of the invention are utilized.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A shows a conventional co-axial transmission line cable.
FIG. 1B is a schematic drawing illustrating an impedance transformer for use with a co-axial cable transmission line.
FIG. 1C is a schematic drawing illustrating the physical electrical connections for 1 1-to-4 steep-up co-axial transformer.
FIGS. 2 and 2A are cross section drawings illustrating an embodiment of an impedance matching transformer in accordance with the present invention.
FIG. 3 is a top view drawing illustrating the FIGS. 2 / 2 A transformer.
FIG. 4 provides a 3-dimensional illustration of the transformer of FIGS. 2 / 2 A and 3 .
FIG. 5 is a schematic drawing illustrating a co-axial cable transmission line equivalent circuit for the 1-to-4 step-up transformer shown in FIGS, 2 , 2 A, 3 and 4 .
DETAILED DESCRIPTION OF THE INVENTION
FIGS. 2 and 2A schematically illustrate in cross-section an embodiment of a buried micro-strip/coupled micro-strip impedance matching transformer 200 in accordance with the present invention for driving a CO 2 laser discharge. The transformer 200 includes an electrical conductor 202 , such as copper, deposited on the bottom of a high thermal conductivity, low RF loss dielectric, printed circuit board (PCB) material 204 , such as, for example, R04350B manufactured by Rogers Corporation. The copper 202 serves as an electrical ground plane and for making good thermal contact to a chill plate (not shown) to conduct heat away from the transformer 200 . The dielectric material 204 upon which the metal electrical ground plane 202 is deposited has a thickness “A”.
A second dielectric layer 206 of thickness “B” is copper plated on both sides and etched on both sides to obtain patterns of thin metal layers that form both the primary winding 208 and the secondary winding 210 of the transformer 200 . This second dielectric layer 206 is thin so as to provide good inductive coupling between the primary 208 and secondary 210 tracks. The primary 208 is formed in the shape of a wide horse-shoe or U-shape, while the secondary 210 overlays the primary 208 on the opposite side of the dielectric 206 and consists of the desired number of overlapping traces. The number of secondary traces determines the turns ratio and, therefore, the impedance transformation. The actual number of secondary turns is only limited by the width of the primary 208 such that suitable coupling may be established between the two metal patterns separated by the thin dielectric 206 of thickness B. This dielectric layer 206 , with the finished metal traces forming the primary circuit 208 and the secondary circuit 210 is then laminated onto the first dielectric layer 204 of thickness A. Rogers Corporation supplies the required printed circuit dielectrics, RO4350B and RO4450, and the adhesives used to laminate these two dielectric layers together. The Rogers material is used as an example in this disclosure, but those skilled in the art will appreciate that other high performance dielectric manufacturers material's may be substituted.
As shown in FIG. 2 , the lamination of the two dielectric layers 204 , 206 results in a PCB structure of height “C” including the thickness of the interlayer binding material 212 . At the back end of the primary pattern, a connector is provided for connecting a dc power supply voltage, normally 48 volts dc.
The “A” and “B” dimensions of the dielectric 204 an 206 , respectively, and the configurations of the primary 208 and secondary 210 , such as length, width and thickness, are determined with the use of RF circuit design software tools to obtain the desired impedances and the overall impedance transformation for a desired application. As shown in FIGS. 2 and 2A , a via hole 214 from one end of the secondary coil 210 down to the ground plane 202 is provided to obtain an electrical connection between the two electrical conductors. The other end 210 a of the secondary coil 210 serves as the RF output to drive the CO 2 laser discharge.
FIG. 3 provides a top down view of the 1-to-4 step-up, high frequency, RF impedance matching transformer 200 shown in cross-section in FIGS. 2 and 2A . The secondary 210 (shown in white), a 2-turn coil in this case, is clearly seen with the output end 210 a of the coil 210 (i.e. to the right in FIG. 3 ) serving as the output connector feeding the CO 2 laser's discharge. The opposite end 210 b of the 2-turn coil secondary 210 is located near the center of FIG. 3 (with legend “Via to Ground”) and is connected to the ground plane 202 by a via-hole connector, as discussed above and shown in FIGS. 2 and 2A . Underneath the secondary coil 210 is the top surface of the high thermal conductivity, low RF loss upper dielectric 206 of thickness B through which the via hole 214 is formed. The via-hole 214 also goes through the lower dielectric of thickness A.
The wide U-shape, single turn, primary 208 that is deposited on top of the lower dielectric 204 of thickness A is also shown in FIG. 3 (cross-hatched). The tab 208 a protruding from the primary 208 at the top of FIG. 3 is the connector to the DC power supply for the power transistors. This voltage is normally 48V dc. At the bottom of FIG. 3 are the two contacts 208 b , 208 c for connecting the transformer primary to the drains/collectors of two RF power transistors (not shown), which may be operated in a push-pull configuration and in class-C operation for maximum efficiency, as is well know to those skilled in the art. Those skilled in the art will also appreciate that other circuit topologies and class of RF power amplifiers (PA) operation may be used depending on specific design requirements. Two additional tabs 208 d and 208 e are shown near the drain/collector connections for connection to a reactive element (not shown) for optional fine tuning. It is noted that the drawing of FIG. 3 is approximately 2× scale (i.e. approximately 2¼″ long by 1¼″ wide) and was designed for a 100 MHz, 1-to-4 step-up transformer 200 delivering approximately 350 W of CW output power into a discharge. This power is sufficient to drive approximately a 35 W CO 2 laser. The use of this approach with four transistors to double the delivered power would require two of these transformers, etc.
FIG. 4 presents a 3-D illustration of the 1-to-4 step-up buried micro-strip/coupled micro-strip line transformer 200 of FIGS. 2 , 2 A and 3 . For a 4-to-1 step-down version for impedance matching, the high output-impedance of digital semiconductor circuitry to the low input-impedance of a typical power transistors, the connections are reversed. In other words, the 2-turn coil coupled micro-strip 210 becomes the primary and the wide, U-shape buried micro-strip 208 becomes the secondary of the transformer. Consequently for this step down case, the digital signal is fed to the connector that serves as the output to the discharge in the step-up case of FIG. 4 . For the step-down case, the inputs to the push/pull transistors are provided to the two connectors previously used to connect to the drains/collectors of the transistors.
A proof of principle 100 MHz, 1-to-4 step-up model was designed, constructed and tested. The DC power into the RF PA stage was 450 W. The RF PA plus the invented transformer transmitted 370 W into a 50 ohm load yielding an efficiency of 82%. The hottest spot on the secondary was found to be 75 C with a chill plate temperature of 20 C. Thermal images (not included herein) of each of the transistors showed no visible signs of drain load unbalance. In achieving this performance, the A and B dimensions of the R04450 material were 0.040 inches and 0.10 inches, respectfully. The thickness of the pre-pregnated layers of R4450B material used to bind the top and bottom dielectric together was 0.012 inches.
FIG. 5 illustrates a co-axial cable transmission line equivalent circuit for the 1-to-4 step-up transformer 200 illustrated in FIGS. 2 , 2 A, 3 and 4 .
It should be understood that the particular embodiments of the invention described above have been provided by way of example and that other modifications may occur to a person skilled in the art without departing from the spirit and scope of the invention as expressed in the appended claims and their equivalents.
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An RF impedance-matching transformer for matching the output impedance of an RF amplifier to the discharge of a gas-discharge laser includes upper and lower dielectric plates arranged face-to-face and bonded together. A primary U-shaped strip winding is embedded in the bonded surface of one of the dielectric plates. A secondary strip-winding is formed on an exposed surface of the upper dielectric plates. A ground-plane electrode formed on an exposed surface of the lower dielectric plate. An electrical connector connects one end of the secondary strip-winding to the ground-plane electrode via a via-hole extending through the dielectric plates. The other end of the secondary strip-winding can be connected to the laser.
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TECHNICAL FIELD
The present invention relates in general to a method for affixing individual fibrils to a film, and in particular but not by way of limitation, to a method for affixing individual fibrils to a three-dimensional formed and apertured film by causing a low melt point web to intermingle with and/or captivate individual fibrils of essentially non-melting material, wherein the fibrils become partially embedded and/or entangled in the low melting point web to form a composite temporary web of both a low melt point polymer and the affixed fibrils, and subsequently introducing the composite temporary web into a second molten web of higher melt temperature, thereby causing the temporary web to melt into the contacting face of the second molten web and subsequently in preferred embodiments aperturing and forming the permanent film.
BACKGROUND OF THE INVENTION
Absorbent articles such as sanitary napkins, incontinent devices, diapers, wound dressings and other products are well known. These articles absorb liquid and retain the liquid within a core. The interior or topsheet of the absorbent article is made of a flexible plastic film material. A negative characteristic of the flexible plastic film material is a glossy or “plastic” look and sticky tactile feel. It is desirable to produce absorbent devices which have a cloth-like look and feel to a user's skin.
Many types of films have been proposed to overcome these tactile problems, such as the film disclosed in U.S. Pat. No. 4,995,930, which depicts a system for laminating a perforated plastic film and a fibrous web material, wherein a pneumatic vacuum is used to perforate the film when it is in a thermoplastic condition. However, the prior art relies on the existence of a web, and does not teach the application of individual fibrils that are not in a web structure. In commonly-owned U.S. application Ser. No. 08/850,635, the lack of a web is compensated for by the presence of a continuous belt, which carries a controlled amount of individual fibrils onto the molten web. The resulting web is subsequently formed and apertured with the composite component of the fibrils affixed to the contour of the user-side surface.
U.S. application Ser. No. 08/850,635 does not teach that fibrils are bound together to form a web, therefore the film disclosed therein lacks the integrity and transport properties of a web; hence, it is taught that they are conveyed by a belt. Further, because the conveying belt or drum of U.S. application Ser. No. 08/850,635 is cumbersome and difficult to maintain in the precise operating parameters required, inventive means must be incorporated to deliver the fibrils to the film-forming step in order to create the composite structure of a film with a fibrilized surface that follows the contour of the funnel-like cells, rendering them unobstructed.
The method of this invention eliminates the need for the carrier/conveyor belt by providing a composite temporary web with web integrity that can be transported directly into the lamination/forming process. Once the temporary web is in contact with the molten face of the film forming web, the temporary web melts and fuses, thereby depositing and embedding the fibrils thereto.
SUMMARY OF THE INVENTION
In the first embodiment, a flocking or metering device is provided for dispensing a controlled amount of individual fibrils. The fibrils are delivered onto a moving conveyor belt, which in certain embodiments may comprise a vacuum belt having a porous surface for drawing the layer of fibrils thereto. The unbonded fibrils are individual or substantially individual during dispersion from the flocking device, and remain unbonded after dispersion. Next, the fibril layer is transported and held by the vacuum conveyor belt to a position under a slot cast extrusion die, where a low temperature polymer melt is released. Upon release of the low temperature polymer melt, a vacuum pulls the low temperature polymer melt onto the surface of the fibril layer with a predetermined amount of pressure. This pressure may be sufficient to cause the fibrils to embed in the contacting surface of the polymer film, especially if tacky polymers are employed such as EVA, EMA, EEA, and others.
If low melt temperature polyethylenes are used, one can then deliver the combined polymer film and fibril layer to a nip point between a pair of nip rollers to cause sufficient pressure to captivate the fibrils and create the composite temporary web. Proximity positioning or very light pressure of the nip rollers is preferable to avoid flattening the fibrils onto the polymer film. In this manner, only a portion of most of the fibrils becomes embedded and affixed to the temporary polymer film. The more substantial portion of the fibrils maintain at least one loose end protruding off the surface of the composite temporary web.
These composite temporary webs may next be spooled or wound into master rolls for further processing at a later time, or processed in-line with subsequent process equipment to be combined with the higher temperature polymer melt under a second slot cast extrusion die for formation of the permanent film. This second in-line option will provide a continuous process mode as opposed to the roll option, which requires a secondary batch process. These options are available for all embodiments described herein.
During the combination with the higher temperature polymer melt, the lower melt temperature portion of the composite temporary web melts and fuses into the higher temperature polymer melt. The resulting permanent film is drawn against a perforated vacuum forming screen having a pressure differential to create funnel-like contours and apertures in the film and allow the fibrils to embed into and follow contours of the permanent film. A majority of aperture openings remain free of fibrils. It is also contemplated within the scope of this invention that these methods can apply to any known film making process. Smooth films and embossed films, as well as the preferred three-dimensional apertured films, can benefit by being enhanced with a surface of soft fibrils.
In a second embodiment, a flocking or metering device is provided to dispense the fibrils. From the device, the fibrils are delivered onto a moving vacuum belt having a porous surface for drawing and holding the fibrils thereto. The unbonded fibrils are individual or substantially individual during dispersion and remain unbonded after dispersion. Next, the fibril layer is transported and held by the vacuum conveyor belt to a position under a nonwoven meltblown extrusion die, which has a plurality of air slots releasing air streams at converging angles. The converging air streams create a turbulent zone for the dispersion of the lower temperature polymer melt, which is released from the extrusion die in fiber-like strands.
The layer of fibrils is next combined with the lower temperature polymer melt on a porous surface of a conveyor belt wheel having an internal vacuum which creates a vacuum zone to form a composite temporary web. While the fibrils are somewhat adhered to but mostly entangled in the lower temperature polymer melt web, the fibrils do not melt or bond by fusing. Nonetheless, the fibrils are captivated in the lower temperature polymer melt to form the composite temporary web.
In a third embodiment of the present invention, a flocking device for dispersing a controlled amount of fibrils is suspended adjacent to a nonwoven meltblown extrusion die. Gravity and venturi forces cause the controlled amount of fibrils dispersed over a controlled slot-like area, as determined by the exit slot of the flocking/metering device, to fall and be pulled into the path of converging air streams of the nonwoven meltblown process. Then, being caught in the converging air streams, the fibrils become somewhat adhered to and mostly entangled in and thus captivated during the forming of the lower temperature polymer melt as it is drawn down to the vacuum belt, which flattens and forms the lower temperature polymer melt. This process creates the composite temporary web.
To summarize, the first embodiment extrudes a molten polymer film on a surface of a layer of fibrils combined with a light pressure to embed a portion of the fibrils into the polymer film surface, thereby captivating the fibril layer. The second and third embodiments introduce fibrils into a nonwoven meltblown web at various stages of the formation of the temporary composite web. A meltblown process extrudes multiple strands of hot polymer into converging air streams that create a turbulent zone. The turbulence causes the strands to ‘dance’ and entangle as a vacuum belt pulls the strands to the belt surface. As the strands strike the vacuum belt, they remain in a molten state to thereby fuse and bond at the interstices of the randomly dispersed fibers.
The second embodiment introduces the layer of fibrils onto the vacuum belt such that the nonwoven meltblown web lands on top of the layer of fibrils and partially adheres to, but mostly entangles, the upper ends of the fibrils to captivate the fibrils.
The third embodiment introduces the fibrils into the turbulent air stream formed in the nonwoven meltblown process wherein the fibrils become entangled and captivated.
In all embodiments, the material with the highest melt point stability is the fibril, whose temperature parameters are controlled to maintain the fibril softness and integrity. The material with the lowest melt point stability is the polymer used to form the temporary web. The material of the permanent film has a melt point in between, such that the permanent film melts and fuses the temporary film or web onto its contacting surface, thereby leaving the fibrils deposited and embedded thereto with most of the fibrils maintaining at least one loose end.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of a film forming system, including formation of a temporary composite web, according to the principles of the present invention.
FIG. 1A is a cross-sectional view of an apertured film formed by the system of FIG. 1 .
FIG. 2 is a side view of an alternate film forming system, including formation of a temporary composite web, according to the principles of the present invention.
FIG. 2A is a cross-sectional view of an apertured film formed by the system of FIG. 2 .
FIG. 3 is a side view of yet another alternate film forming system, including formation of a temporary composite web, according to the principles of the present invention.
FIG. 3A is a cross-sectional view of an apertured film formed by the system of FIG. 3 .
DETAILED DESCRIPTION
Referring first to FIG. 1, there is shown a side view of a film forming system 10 according to the principles of the present invention. A metering or flocking device 20 distributes individual fibrils 30 to form a layer 40 . It is to be understood that the present invention is especially useful in applying fibrous material which comprises loose individual fibrils (i.e., which are not bonded or entangled together to form a web). For purposes of this application, fibrils differ from fibers in that fibrils are microscopically short in length and are typically created by chopping fibers into the micro-scale length of fibrils. Fibrils are essentially individual and are not bonded to each other by adhesives, melt-fusing, pressure-fusing, intentional permanent entanglement, or other means. However, if several random fibrils become somewhat entwined together, they can be separated from each other with minuscule force and without breaking, distorting or otherwise changing their original integrity. Conversely, a fiber is a very long strand amongst thousands of other long strands combined and bonded together to form a web-most commonly known as a nonwoven web. Spun-bonded, melt-blown, carded, spunlaced, and other nonwoven webs are commonly known and would be appropriate material for use in the lamination art. Woven webs are made of woven threads, whereby the threads are made by twisting thousands of long fibers together.
The fibrils 30 ideally will have a predetermined micro-scale length such that the possibility is negligible for a single fibril or groups of entwined fibrils to bridge across the opening of a cell of a three-dimensionally formed and apertured film. This accounts for the soft feel of the fibrilized surface while avoiding any significant obstruction to the intended fluid flow through a topsheet's funnel-like formed and apertured cells or openings.
For a common 25 mesh pattern of cells for three-dimensionally formed and apertured topsheet films, the ideal fibril length will be determined as follows:
1. Since ‘mesh’ is the number of formed cells aligned in a one inch length, the distance from rim to rim of a single cell is about 40 mils;
2. For a fibril to have a length which could bridge entirely across the formed cell, it would require a length of at least about 40 mils;
3. To have an average fibril micro-length with negligible probability for bridging entirely across the formed cell, a length of less than about 40 mils will suffice;
4. No fiber chopping method exists which delivers a consistent micro-length to every fibril; hence, if the average micro-length of the fibril is set somewhat below the micro-length required to bridge across the cell, then the cell's openings will be caused to remain unobstructed due to the absence of fibril bridging.
Referring still to FIG. 1, the layer 40 of fibrils 30 is formed on and adheres to a conveyor belt 50 at first end 55 of the conveyor belt 50 . In a preferred embodiment, the conveyor belt 50 may comprise a porous medium so a vacuum 52 may cause suction therethrough. The conveyor belt 50 may be made of woven cloth, woven metallic wires, woven polymeric strands, nickel deposited screens, etch screens and the like.
The layer 40 of fibrils 30 is held on the surface of the conveyor belt 50 by suction of the vacuum 52 and is transported along the vacuum conveyor belt 50 to a second end 58 of the conveyor belt 50 , where an extrusion slot die 60 of a first extruder 62 releases lower temperature polymer melt 70 . The lower temperature polymer melt 70 preferably is a polymer web. The polymer web is comprised of a polymer, including but not limited to polyethylene, polypropylene, EVA, EMA and copolymers thereof. Polyethylene is a preferred component of the polymer web. The lower temperature polymer melt 70 is pulled down by suction from within the vacuum conveyor belt 50 into contact on the layer 40 of fibrils 30 . System parameters are controlled, as determined by experimentation, such that most of the fibrils 30 become imbedded and locked into the lower temperature polymer melt 70 . A pair of light pressure nip rollers 90 compresses the lower temperature polymer melt 70 and a layer 40 of fibrils 30 to form a composite temporary web 100 , which then cools by natural convective losses of heat or by assisted cooling.
The composite temporary web 100 may be collected onto a take-up roll, or next delivered in-line between a second nip roller 110 and a forming screen 120 at a nip point 121 . At the nip point 121 , the composite temporary web 100 is moved underneath a second extrusion slot die 122 of a second extruder 124 , where a higher temperature polymer melt 126 is released. The higher temperature polymer melt 126 is combined in a semi-molten state with the composite temporary web 100 and is drawn between the second nip roller 110 and forming screen 120 . Perforations 130 in the forming screen 120 allow suction from a second vacuum 140 within the forming screen 120 to draw the composite temporary web 100 through the perforations 130 and create apertures 160 on the resulting permanent film 150 . The film 150 is cooled by ambient air and the vacuum 140 , but also may be cooled by other available alternatives.
There are three basic components that are desirable for practicing this method: the fibrils 30 ; the lower temperature polymer melt 70 used to form the composite temporary web 100 which captivates the fibrils; and the higher temperature polymer melt 126 used to form the final permanent film 150 . The fibrils 30 are preferably composed of material having the highest melting point. Fibrils 30 can be derived from natural fibers, such as cotton, cellulosics from pulp, animal hair, or synthetic fibers from polyethylene, polypropylene, nylon, rayon and other materials. The lower temperature melt polymer 70 must be comprised of the lowest melting point material. Finally, the higher temperature melt polymer 126 used to form the permanent film 150 must have a melting point above the temporary web's melting point, yet below the fibril's melting point. Melting point separation of at least 10° F. and preferably, around 20° F. has been shown to be successful. A greater separation is of course desirable.
Because the selection of fibrils 30 prevents the fibrils 30 from melting or distorting by the thermal load of the other melt polymers 70 , 126 , the composite temporary web 100 will effectively ‘disappear’ into the face of the higher temperature melt polymer 126 during formation of the permanent film 150 while maintaining fibril integrity. It is therefore necessary to select a higher temperature melt polymer 126 that has a melting temperature above the melting point of the composite temporary web 100 , yet below the distortion temperature of the fibrils 30 .
To best meet the thermal requirements, the fibrils 30 are preferably composed of natural fibers. Natural fibers do not typically ‘melt’ but rather burn, and then only at extreme high temperatures—usually about two to three times the thermal load of extrusion temperatures used in the film forming system 10 . However, polymer fibrils are contemplated within the scope of this method. Nylon, rayon, polyethylene and polypropylene polymers exist with sufficiently high melting points for the purposes of this methodology.
The lower temperature polymer melt 70 is thin, preferably in the range of 0.1-0.5 mils. The fibrils 30 can vary in length, diameter, polymer type, and cross sectional shape. These parameters are decided via experimentation against targets of fluid acquisition, aesthetics and softness. Once defined and set, the metering device 20 is calibrated and loaded to deliver the correct “controlled” layer 40 of individual fibrils 30 onto a moving conveyor belt 50 .
Upon contact of the higher temperature polymer melt 126 and the ambient temperature composite temporary web 100 , the composite temporary web 100 melts and fuses into the mass of the higher temperature polymer melt 126 . The composite temporary web 100 then loses its own definition and integrity, and will move and behave as an incorporated part of the higher temperature polymer melt 126 . The resulting film 150 has the individual fibril layer 40 which follows the contour of the reshaping caused by the second nip roller 110 , forming screen 120 , perforations 130 , and vacuum 140 to result in a film 150 with a coating of individual fibrils 30 . It is important to note that after formation of the film 150 , a majority of the fibrils 30 do not block the apertures 160 that form in the film 150 .
Referring now to FIG. 2, there is shown a side view of an alternate film forming system 210 according to the principles of the present invention. A metering or flocking device 220 distributes individual fibrils 230 to form a layer 240 of fibrils 230 on a conveyor belt 250 . In this embodiment, it is preferable the conveyor belt 250 is made of a porous medium so suction from a vacuum 252 may be applied therethrough. The conveyor belt 250 may be made of woven cloth, woven metallic wires, woven polymeric strands, nickel deposited screens, etch screens and the like. Fibril selection and thermal requirements are made similar to that described for the previous embodiments.
The porous conveyor belt 250 serves two purposes: first, it aids in the formation of the composite temporary web 300 ; and second, it holds the delivered layer 240 of fibrils 230 in place while the lower temperature nonwoven melt polymer strands 270 is being delivered. As the lower temperature nonwoven melt polymer strands 270 lands on the fibril layer 240 in the suction zone 282 , the lower temperature nonwoven melt polymer strands 270 partially sticks to the layer 240 of fibrils 230 by melt-adhesion. More so, the semi-molten lower temperature nonwoven melt polymer strands 270 and layer 240 of fibrils 230 will entangle and mechanically lock together in the newly combined composite temporary web 300 having intermingled fibrils.
The layer 240 of fibrils 230 is held to the surface and transported along the conveyor belt 250 to a second end 258 at the conveyor belt 250 , where extrusion die slot orifices 260 of a nonwoven meltblown extruder 262 releases lower temperature nonwoven melt polymer strands 270 . The nonwoven meltblown extruder 262 has a plurality of air slots 264 at opposing sides of nonwoven meltblown die 266 with the extrusion die orifices 260 therebetween. The air slots 264 are positioned at a converging angle such that the air streams from each air slot 264 will intercept and collide to create a turbulence. The lower temperature nonwoven melt polymer strands 270 , which are nonwoven polymer melt-blown fibers, extrudes out of the nonwoven extrusion slot orifices 260 in fiber-like strands. The converging air streams from the adjacent air slots 264 collide in a turbulent zone 263 below the exit point of the extrusion die orifices 260 . The turbulent zone 263 pushes, elongates and thins the strands of the lower temperature nonwoven melt polymer strands 270 . The turbulent zone 263 also simultaneously causes the lower temperature nonwoven melt polymer strands 270 to dance in random disarray. The mass of randomly entangling, dancing, lower temperature nonwoven melt polymer strands 270 is drawn by suction from a second vacuum 265 in a conveyor wheel 267 into a suction zone 282 which pulls the nonwoven meltblown lower temperature nonwoven melt polymer strands 270 onto the porous conveyor belt 250 and conveyor wheel 267 . The air streams are heated such that the molten state of the elongating and entangling lower temperature nonwoven melt polymer strands 270 maintains its melting phase. Thereby, when the suction pulls the molten lower temperature nonwoven melt polymer strands 270 down upon itself, the fiber-like strands of the nonwoven meltblown lower temperature nonwoven melt polymer strands 270 fuse and bond while entangling the fibrils 230 to form a composite temporary web 300 , which then cools by natural convective losses of heat or by assisted cooling.
The composite temporary web 300 may be collected onto a take-up roll, or next delivered in-line between a nip roller 310 and a forming screen 320 at a nip point 321 . At the nip point 321 , the composite temporary web 300 is moved underneath a second extrusion slot die 322 ofa second extruder 324 , where a higher temperature melt polymer 326 is released. The higher temperature melt polymer 326 is combined in a semi-molten state with the composite temporary web 300 and is drawn between the second nip roller 310 and forming screen 320 . Perforations 330 and the forming screen 320 combined with a vacuum 340 in the forming screen 320 create apertures 360 therein to create a film 350 . The film 350 is cooled by ambient air and a vacuum 340 , but also may be cooled by other available alternatives.
As in process 10 , there are three basic components that are desirable for practicing this method: the fibrils 230 ; the lower temperature nonwoven melt polymer strands 270 used to form the composite temporary web 300 which captivates the fibrils; and the higher temperature melt polymer 326 used to form the final permanent film 350 . The fibrils 230 are preferably composed of material having the highest melting point. Fibrils 230 can be derived from natural fibers, such as cotton, cellulosics from pulp, animal hair, or synthetic fibers from polyethylene, polypropylene, nylon, rayon and other materials. The lower temperature nonwoven melt polymer strands 270 must be comprised of the lowest melting point material. Finally, the higher temperature melt polymer 326 used to form the permanent film 350 must have a melting point above the temporary web's melting point, yet below the fibril's melting point. Melting point separation of at least 10° F. and preferably, around 20° F. has been shown to be successful. A greater separation is of course desirable.
Since the selection of fibrils 230 prevents the fibrils 230 from melting or distorting by the thermal load of the other melt polymers 270 , 326 , the composite temporary web 300 will effectively ‘disappear’ into the face of the higher temperature melt polymer 326 during formation of the permanent film 350 while maintaining fibril integrity. It is therefore necessary to select a higher temperature melt polymer 326 that has a melting temperature above the melting point of the composite temporary web 300 , yet below the distortion temperature of the fibrils 230 .
To best meet the thermal requirements, the fibrils 230 are preferably composed of natural fibers. Natural fibers do not typically ‘melt’ but rather burn, and then only at extreme high temperatures—usually about two to three times the thermal load of extrusion temperatures used in the film forming system 210 . However, polymer fibrils are contemplated within the scope of this method. Nylon, rayon, polyethylene and polypropylene polymers exist with sufficiently high melting points for the purposes of this methodology.
The meltblown nonwoven material of the lower temperature nonwoven melt polymer strands 270 will preferably have a range of 2-10 gsm. The fibrils 230 can vary in length, diameter, polymer type, and cross sectional shape. These parameters are decided via experimentation against targets of fluid acquisition, aesthetics and softness. Once defined and set, the metering device 220 is calibrated and loaded to deliver the correct “controlled” layer 240 of individual fibrils 230 onto a moving conveyor belt 250 .
Upon contact of the higher temperature melt polymer 326 with the ambient temperature composite temporary web 300 , the composite temporary web 300 melts and fuses into the mass of the higher temperature melt polymer 326 . The composite temporary web 300 then loses its own definition and integrity, and will move and behave as an incorporated part of the higher temperature melt polymer 326 . The resulting film 350 has the individual fiber layer 240 which follows the contour of the reshaping caused by the nip roller 310 , forming screen 320 , perforations 330 , and vacuum 340 , to result in a three dimensional apertured film 350 with a coating of individual fibrils. It is important to note that a majority of the apertures 360 resultingly formed in the film 350 remain unblocked by the fibrils 230 .
Referring now to FIG. 3, there is shown a side view of yet another alternate film forming system 410 according to the principles of the present invention. A fibril metering or flocking device 420 is suspended adjacent to a nonwoven meltblown extrusion die 422 having a plurality of air slots 424 . The metering device 420 distributes individual fibrils 430 directly into an air stream 440 , which flows from the air slots 424 , and onto a rotating drum 450 . The air stream 440 forms a turbulent zone 442 and the venturi effect draws the fibrils 430 into the same turbulent zone 442 of lower temperature melt polymer strands 460 released from the die 422 . Then, a vacuum 480 pulls the fibrils 430 and polymer 460 together onto a screen 490 of the drum 450 over a vacuum zone 482 .
The fibrils 430 , being caught in the converging air streams 440 of the turbulent zone 442 , become somewhat adhered to, but mostly entangled in one another. The turbulent zone 442 causes the lower temperature melt polymer 460 and fibrils 430 to intermingle in the turbulent air flow, such that the lower temperature melt polymer 460 and fibrils 430 mechanically interlock to form a composite temporary web 500 . The composite web 500 hardens upon contact with the surface of the screen 490 .
After the composite web 500 has formed, it may be wound onto take-up rolls for collection, or delivered in-line to a nip roller 510 and a forming screen 520 at a nip point 521 . At the nip point 521 , the composite web 500 is moved underneath a second extrusion slot die 522 of a second extruder 524 , where a higher temperature melt polymer 526 is released. The higher temperature melt polymer 526 is combined in a semi-molten state with the composite web 500 and is drawn between the nip roller 510 and forming screen 520 . Perforations 530 on the forming screen 520 combined with a vacuum 540 in the forming screen 520 create apertures 560 therein, resulting in a film 550 . The film 550 is cooled by ambient air and a vacuum 540 , but also may be cooled by other available alternatives.
The fibrils 430 are preferably composed of material having the highest melting point. Fibrils 430 can be derived from natural fibers, such as cotton, cellulosics from pulp, animal hair, or synthetic fibers from polyethylene, polypropylene, nylon, rayon and other materials. The lower temperature melt polymer 460 must be comprised of the lowest melting point material and is preferably a nonwoven. Finally, the higher temperature melt polymer 526 used to form the permanent film 550 must have a melting point above the temporary web's melting point, yet below the melting point of the fibrils 430 . Melting point separation of at least 10° F. and preferably, around 20° F. has been shown to be successful. A greater separation is of course desirable.
Because the selection of fibrils 430 prevents the fibrils from melting or distorting by the thermal load of the other melt polymers 460 , 526 , the composite temporary web 500 will effectively ‘disappear’ into the face of the higher temperature melt polymer 526 during formation of the permanent film 550 while maintaining fibril integrity. It is therefore necessary to select a higher temperature melt polymer 526 that has a melting temperature above the melting point of the composite temporary web 500 , yet below the distortion temperature of the fibrils 430 .
To best meet thermal requirements, the fibrils 430 are preferably composed of natural fibers. Natural fibers do not typically ‘melt’ but rather burn, and then only at extreme high temperatures—usually about two to three times the thermal load of extrusion temperatures used in the film forming system 410 . However, polymer fibrils are contemplated within the scope of this method. Nylon, rayon, polyethylene and polypropylene polymers exist with sufficiently high melting points for the purposes of this methodology.
The lower temperature melt polymer 460 is preferably in the range of 2-10 gsm. The fibrils 430 can vary in length, diameter, polymer type, and cross sectional shape. These parameters are decided via experimentation against targets of fluid acquisition, aesthetics and softness. Once defined and set, the metering device 420 is calibrated and loaded to deliver the correct “controlled” amount of individual fibrils 430 .
Upon contact of the higher temperature melt 526 with the ambient temperature composite web 500 , the composite temporary web 500 melts and fuses into the mass of the higher temperature melt polymer 526 . The composite temporary web 500 then loses its own definition and integrity, and will move and behave as an incorporated part of the higher temperature melt polymer 526 . The resulting permanent film 550 has the individual fibrils 430 following the contour of the reshaping caused by the nip roller 510 , forming screen 520 , perforations 530 , and vacuum 540 , to result in a three dimensional apertured film 550 with a coating of individual fibrils. It is important to note that a majority of resulting apertures 560 that form on the film 550 remain unblocked by fibrils 430 .
The benefit in all embodiments of the present invention for affixing fibrils to a low melt temperature film or nonwoven web is to create a composite temporary web. This composite temporary web later melts and fuses into the contacting surface of the molten web of the film forming process, depositing and embedding the fibrils thereto.
It is thus believed that the operation and construction of the present invention will be apparent from the foregoing description of the preferred exemplary embodiments. It will be obvious to a person of ordinary skill in the art that various changes and modifications may be made herein without departing from the spirit and the scope of the invention.
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A method for producing a film with attached fibrils having a cloth-like look and feel. A flocking or metering device is provided for dispensing a layer of the fibrils. The fibrils are next delivered onto a moving vacuum belt, which has a porous surface for drawing the layer of fibrils thereto. After dispersion, the fibril layer is transported and held by the vacuum conveyor belt to a position under a slot cast extrusion die, where a lower temperature melt polymer is released. Upon release, the lower temperature melt polymer and fibril layer fuse and combine to interlock to create a composite temporary web. In one embodiment, the fibril layer and lower temperature melt polymer are delivered at a first nip point between a pair of nip rollers to create the composite temporary web. The composite temporary web may next be collected on collection rolls, or combined with a higher temperature melt polymer under a second slot cast extrusion die to form a permanent film with fibrils. During combination with the higher temperature melt polymer, the lower temperature melt polymer of the composite temporary web melts and fuses into the higher temperature melt polymer and is drawn between a nip roll and a perforated vacuum forming screen having a pressure differential at a second nip point to harden and create apertures in the film and allow the fibril layer to follow the contours of the film, while the openings of the apertures remain free from fibrils.
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FIELD OF THE INVENTION
The present invention relates to magnetic heads for use in rigid disc drive devices or the like serving as external memory devices for electronic computers, and more particularly to floating-type magnetic heads having the face to be opposed to recording media and a core chip having a magnetic gap portion and attached to the slider, the invention further relating to a process for producing the magnetic head.
BACKGROUND OF THE INVENTION
In recent years, it has been greatly required that rigid disc drive devices, like other devices, be small-sized, and high-density recording on recording media has become an important problem. Accordingly, magnetic discs of the thin metal film type having a high coercive force (Hc) have been developed for use in place of those of the conventional oxide-coated type.
On the other hand, as magnetic heads for hard discs, floating-type magnetic heads are in use which comprise a slider having the face to be opposed to the recording medium and a core chip incorporated in the slider. It has been proposed to provide a core chip of the so-called MIG type (metal-in-gap type) especially in floating-type magnetic heads for use with rigid discs of the thin metal type. The core chip of the MIG type includes a film of Sendust, amorphous magnetic alloy or like highly saturated magnetic flux material formed by sputtering and opposed to the magnetic gap portion of the chip (see, for example, Unexamined Japanese Patent Publication SHO 62-295207).
FIG. 11 is a plan view of a MIG-type core chip fabricated according to the present invention for use with rigid discs, to show the magnetic gap portion in its face to be opposed to the recording medium. As far as the structure appearing on the medium opposed face is concerned, the core chip has the same construction as known MIG-type core chips.
More specifically, the core chip 4 comprises a pair of core segments 1a, 1b made of Mn-Zn ferrite and butting against each other, and a thin film 2 of ferromagentic metal such as Sendust and a gap spacer 3 of SiO 2 or the like. The core chip 4 is secured to a slider (not shown) with bonding glass portions 5, 5 to provide the floating-type magnetic head.
Such floating type magnetic heads have heretofore been produced by the process illustrated in FIGS. 32 to 41.
First, two base plates of Mn-Zn ferrite are prepared, both surfaces of each of the base plates are polished to a mirror finish, and the first of the base plates, 6a, is coated on its upper surface (gap forming surface) with a thin ferromagnetic metal film 2 and then with a gap spacer 3 of a thickness corresponding to the desired gap length by sputtering as shown in FIG. 32. A plurality of precut grooves 7 are formed at a given pitch P in the upper surface (gap forming surface) of the second base plate 6b to obtain ridges with a preliminary track width t 1 slightly larger than the desired track width as shown in FIG. 33.
Next as shown in FIG. 34, a plurality of winding grooves 8 are formed in the gap forming surface of the second base plate 6b, and the two base plates 6a, 6b are fitted together with their gap forming surfaces opposed to each other. Further as seen in FIG. 35, glass bars 9 are inserted into the respective winding grooves 8, then melted and solidified, filling the precut grooves 7 with glass 10 as shown in FIG. 36 and giving a block 11 composed of the pair of base plates 6a, 6b bonded together with the glass.
Next, the block 11 is cut into a plurality of core blocks 14 along broken lines A-A'. A plurality of truck width defining grooves 12 are cut at a predetermined pitch in the head portion of each core block 14 to form a plurality of medium facing ridges 13 having the desired track width t 2 as shown in FIG. 37.
The core block 14, when sliced, affords core chips 4 each comprising a pair of core segments 1a, 1b, a thin ferromagnetic metal film 2 and a gap spacer 3 as seen in FIG. 38.
Next, sliders 16 as shown in FIG. 39 are prepared which are made of a nonmagnetic ceramic such as calcium titanate, each core chip 4 is fitted in a slit 15 formed in the slider 16, and a glass plate 17 having a lower softening point than the glass bar 9 is placed on the core chip 4 as shown in FIG. 40.
The glass plate 17 is thereafter melted and solidified, thereby filling the glass 5 into the spaces at opposite sides of the medium facing ridge 13 and into the clearance in the slider slit 15 around the core chip 4 and bonding the core chip 4 to the slider 16. Finally, the slider 16 is chamfered as at 18 to finish the exterior, whereby a floating-type magnetic head is completed as shown in FIG. 41.
In preparing the conventional magnetic head by the above process, the upper surface of the base plate 6a of Mn-Zn ferrite is coated by sputtering with the thin ferromagnetic metal film 2 which is different from the Mn-Zn ferrite in coefficient of expansion in the step of FIG. 32, with the result that the base plate 6a warps during sputtering due to a change in temperature to create a great error in the gap length of the magnetic gap portion finally obtained.
In the steps of FIG. 34 through FIG. 36, moreover, the SiO 2 film and the ferrite base plate, which are not satisfactorily wettable with glass, are bonded together with glass to fabricate the block 11. Consequently, the block 11 is very low in bond strength and is likely to fracture or crack in the subsequent step. The core chip 4 eventually obtained is also low in the strength of bond between the core segments 1a and 1b.
Further in bonding the two base plates to each other with glass, the glass bar 9 needs to be heated to a temperature about 150° to 250° C. higher than the softening point (e.g., 590° C.) of the glass. This permits a reaction to proceed at the interface between the ferrite base plate and the thin Sendust film, possibly forming a quasi-gap or a secondary gap at the interface.
Additionally, the step of FIG. 32 wherein the upper surface of the first base plate 6a is coated with the thin ferromagnetic metal film 2 by sputtering gives rise to the problem that sputtered metal particles disturb the crystallinity of the first base plate surface owing to the resulting impact or the like, consequently forming a nonmagnetic amorphous layer at the interface between the first base plate 6a and the metal film 2 for the amorphous layer to provide a secondary gap.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a magnetic head of the floating type which can be fabricated with an accurate gap length despite the temperature change involved in the thin film forming step and in which the core segments of the core chip are firmly bonded to each other, and a process for producing the magnetic head.
Another object of the invention is to provide a process for producing floating-type magnetic heads without creating any secondary gap at the interface between the core segment of the core chip and the thin ferro-magnetic metal film thereof.
The floating-type magnetic head of the present invention comprises a core chip composed of a pair of core segments, and a gap spacer and a thin ferromagnetic metal film provided at the joint between the pair of core segments, the gap spacer and the metal film being formed only over a portion of the entire area of the joint between the pair of core segments which portion has a larger width than the specified width, only glass for bonding the core segments to each other being present over the remaining portion of the joint area.
In producing the magnetic head of the invention, the core chip is fabricated by a process comprising the first step of preparing first and second base plates made of a ferromagnetic oxide and forming on the surface of the first base plate to be bonded to the second base plate a plurality of strips each composed of a thin ferromagnetic metal film and a gap spacer over the metal film and having a width larger than the desired truck width, the second step of bonding together the first base plate and the second base plate obtained by the first step with a first glass to prepare a core block, the third step of cutting truck width defining grooves in the core block to form a plurality of medium facing ridges each including the metal film and the gap spacer and having a width equal to the desired truck width, and the fourth step of cutting the resulting core block into core chips each including the metal film and the gap spacer. The core chip obtained by the fourth step is bonded to a slider with a second glass having a lower softening point than the first glass.
The two base plates are bonded together by forming a plurality of grooves in the second base plate between the strip-like surface areas thereof to be joined to the gap spacers and filling these grooves with the first glass in the first step, and melting and solidifying the first glass with the first and second base plates joined together in the second step.
With the magnetic head described above, the pair of core segments, each made of a ferromagnetic oxide which is highly wettable with glass, are directly bonded to each other with the glass at opposite sides of the area where the thin ferromagentic metal film and the gap spacer are present. This gives the joint of the core segments higher bond strength than heretofore possible.
With the process for producing the magnetic head, the thin ferromagnetic metal film is deposited over a smaller area than conventionally, consequently rendering the base plate free of warping and affording a magnetic gap portion with improved accuracy.
The two base plates are bonded to each other with the first glass as filled in the plurality of grooves in one of the base plates, so that the temperature to which the glass is heated for bonding can be lower than conventionally, e.g., a lower temperature which is about 80° C. higher than the softening point of the first glass. This serves to inhibit the reaction conventionally occurring at the interface between the first base plate and the metal film owing to the high temperature used to preclude the creation of a secondary gap.
When one of the base plates is to be coated with the thin ferromagnetic metal film and the gap spacer as by sputtering, the gap spacer may be formed over the base plate first. A nonmagnetic amorphous layer, if formed on the base plate, will then serve as part of the gap spacer without forming a secondary gap.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a floating-type magnetic head as a first embodiment;
FIG. 2 is a perspective view partly broken away and showing the magnetic head of FIG. 1 as used for a magnetic disc;
FIGS. 3 to 10 are views for illustrating stepwise a process for producing the magnetic head of FIG. 1;
FIG. 10A is a view in section taken along the joint between the core segments of the core chip shown in FIG. 10;
FIG. 11 is an enlarged plan view showing the magnetic gap portion of the magnetic head of FIG. 1;
FIG. 12 is a perspective view of another floating-type magnetic head as a second embodiment;
FIGS. 13 to 22 are views for illustrating stepwise a process for producing the magnetic head of FIG. 12;
FIG. 23 is a perspective view of another floating-type magnetic head as a third embodiment;
FIGS. 24 to 29 are views for illustrating stepwise a process for producing the magnetic head of FIG. 23;
FIGS. 30 and 31 are views showing steps of a process for producing another magnetic head as a fourth embodiment;
FIGS. 32 to 40 are views for illustrating stepwise the process for producing a conventional floating-type magnetic head; and
FIG. 41 is a perspective view of the conventional magnetic head.
DETAILED DESCRIPTION OF EMBODIMENTS
The present invention will be described below in greater detail with reference to first to fourth embodiments thereof.
First Embodiment
FIG. 1 shows a magnetic head of the floating type which comprises a slider 16 having a slit 15, and a core chip 25 fitted in the slit and bonded to the slider 16 with glass portions 5, 5. The core chip 25 includes a thin ferromagnetic metal film 2 facing a gap spacer 3 providing a magnetic gap portion.
With reference to FIG. 2, the magnetic head is disposed as opposed to a magnetic disc 56. The disc 56 is driven at a high speed in the direction of arrow A, whereby a layer of stabilized air current is formed between the disc and the head, thereby holding the head in a predetermined floating position off the disc surface.
Next, a process will be described for producing the magnetic head of FIG. 1 with reference to FIGS. 3 to 10.
First and second base plates 6a, 6b made of Mn-Zn ferrite are prepared, the upper surface (gap forming surface) and the lower surface of the first base plate 6a are polished to a mirror finish, and the upper surface of the first base plate 6a is coated with a thin film 2 of a ferromagnetic metal, such as Sendust, having a thickness of 3.5 μm. The upper surface of the thin film 2 is coated with a gap spacer 3 made, for example, of SiO 2 and having a thickness of 0.8 μm as seen in FIG. 3.
The thin ferromagnetic metal film 2 is formed using an opposite target sputtering device under the conditions of: base plate temperature 200° C., gas pressure 2 torr, discharge power 4 kW, bias voltage 50 V and film forming rate 1400 angstroms/min. The gap spacer 3 is formed by an ion plating device at a base plate temperature of 200° C., a vacuum of 1.0×10 -5 torr and a film forming rate of 600 angstroms/min.
With reference to FIG. 4, the coated surface of the first base plate 6a is etched using a dry etching device such as an ion beam etching device to leave strips of metal film 2 and gap spacer 3 on the surface at a predetermined pitch and remove the other portions of the film 2 and the spacer 3. The strips have a preliminary track width t 1 (about 50 μm) larger than the desired track width t 2 (about 13 μm). The ion beam etching operation is conducted under the conditions of: gas pressure 2×10 -4 torr, discharge voltage 34.5 V, acceleration voltage 750 V and incidence angle 40°, for about 135 minutes until the undesired portions of the metal film 2 and the gap spacer 3 are completely removed.
Instead of resorting to ion beam etching, the metal film 2 and the gap spacer 3 can be formed directly on the base plate 6a in the pattern shown in FIG. 4, for example, by mask sputtering.
On the other hand, precut grooves 7 are formed at a predetermined pitch in the upper surface (gap forming surface) of the second base plate 6b to form preliminary track faces 20 having a width equal to the width t 1 as seen in FIG. 5. A plurality of depth end grooves 19 are then formed in the second base plate 6b to intersect the precut grooves 7 perpendicular thereto as seen in FIG. 6.
Subsequently, the second base plate 6b is heated with a plate of first glass with a softening point of 590° pressed against the plate 6b, whereby the precut grooves 7 and the depth end grooves 19 are filled with the first glass 10 as shown in FIG. 7. The glass filled surface is then polished to a mirror finish. The glass is filled in by maintaining the second base plate 6b in a vacuum at 590° C. for 70 minutes.
With reference to FIG. 8, a plurality of winding grooves 8, rectangular in cross section, are formed in the gap forming surface of the second base plate 6b in parallel to the depth end grooves 19 and as so positioned as to partially remove the plate portions defining the depth end grooves 19. The two base plates 6a, 6b are thereafter fitted together with their gap forming surfaces opposed to each other and with the gap spacers 3 opposed to the respective preliminary track faces 20, and the first glass 10 is melted and solidified in this state, whereby the plates 6a, 6b are bonded together with the glass to make a block 21. For glass bonding, the assembly is maintained at 670° C. in a vacuum for 12 minutes. Consequently, the molten glass fills up every corner around the strips of metal film 2 and gap spacer 3 between the two base plates.
The block 21 is then cut into core blocks 22 along broken lines B-B'. Track defining grooves 12 are then cut at a predetermined pitch P in the head portion of the core block 22 to form a plurality of medium facing ridges 23 having the specified track width t 2 as shown in FIG. 9.
Next, the core block 22 is sliced at the hatched regions 24 shown in FIG. 9 to prepare core chips 25 as seen in FIG. 10. The core chip 25 comprises a pair of core segments 1a, 1b of Mn-Zn ferrite, with the metal film 2 and the gap spacer 3 provided at the joint therebetween, and are bonded to each other with the glass at the joint areas on opposite sides of the strip of film 2 and spacer 3.
The core chip 25 is inserted into the slit 15 of the nonmagnetic ceramic slider 16 shown in FIG. 1. A plate 17 of second glass having a softening point of 460° C. is placed on the core chip 25 as in the conventional process shown in FIG. 40 and melted and solidified, whereby the second glass 5 is filled into the spaces at opposite sides of the medium facing ridge 23 and into the clearance in the slit 15 around the core chip 25 as shown in FIG. 1 to bond the core chip 25 in the slit 15 to the slider. The glass is filled in by heating the assembly to 500° C. in atmosphere or a vacuum. Finally, the slider 16 is chamfered as at 18 to finish the exterior to provide a completed floating-type magnetic head.
In the thin film forming step of FIG. 3 included in the above process for producing the magnetic head, an internal stress, even if occurring, is almost completely released since a major portion of the thin film is removed by the etching step of FIG. 4. This precludes the warping of the base plate 6a shown in FIG. 4 that would otherwise occur owing to the stress. Consequently, the magnetic gap portion of the head eventually obtained has a very accurate gap length.
Further with the core chip 25 shown in FIG. 10, the thin ferromagnetic metal film 2 and the gap spacer 3 are present at the joint between the two core segments 1a, 1b over the central area 57 thereof shown in FIG. 10A and including the medium facing ridge 23, while at the areas 58, 58 on opposite sides of the area 57, the core segments 1a, 1b, each made of the ferrite which is satisfactorily wettable with glass, are directly bonded to each other with the glass. The core chip 25 therefore has high mechanical strength.
Further with the foregoing production process, the first and second base plates 6a, 6b are bonded with the first glass 10 as filled in the precut grooves 7 and the depth end grooves 19 in the second plate 6b as seen in FIG. 8 by softening the glass. Thus, the first glass 10, when merely heated to a temperature about 80° higher than its softening point, is allowed to fully penetrate the clearance between the two base plates. The temperature employed for glass bonding is therefore about 70° to 170° C. lower than conventionally, with the result that almost no reaction proceeds at the interface between the first base plate 6a and the thin metal film 2 to obviate the secondary gap that was conventionally formed by reaction.
Further even if the crystalline characteristics of the base plate 6a is somewhat disturbed owing to the collision of sputtered metal particles in the step of forming the thin ferromagentic metal film, the temperature to which the base plate is heated for glass bonding subsequently is lower than is used conventionally, with the result that the layer formed by the reaction between the amorphous layer due to disturbed crystals and the deposited metal film will not further develop into a secondary gap which would adversely affect the performance of the head.
Second Embodiment
FIG. 12 shows another floating-type magnetic head as a second embodiment, which is produced by the process to be described below with reference to FIGS. 13 to 22.
First, first and second base plates 26a, 26b made of a ferrimagnetic oxide material such as Mn-Zn ferrite are each polished to a mirror finish over the upper surface (gap forming surface) and the lower surface thereof. Precut grooves 28 are then cut at a predetermined pitch P in the upper surface of the second base plate 26b to leave preliminary truck faces 27 having a preliminary track width t 1 slightly larger than the desired track width t 2 as shown in FIG. 13.
As shown in FIG. 14, a plurality of depth end grooves 29 intersecting the precut grooves 28 perpendicular thereto are formed at a predetermined pitch Po in the upper surface of the second base plate 26b.
Next, a first glass 30 having a softening point of 590° is filled into the precut grooves 28 and the depth end grooves 29, and the glass filled surface is then polished to a mirror surface as seen in FIG. 15.
With reference to FIG. 16, the entire upper surface of the second base plate 26b is thereafter coated with a gap spacer 41 made of SiO 2 or the like and having a thickness of 0.8 μm, and the upper surface of the gap spacer 41 is coated with a thin film 31 made of a ferromagnetic metal such as Sendust and having a thickness of 3.5 μm by sputtering.
With reference to FIG. 17, the thin metal film and the gap spacer covering the first glass 30 are removed therefrom using a dry etching device such as ion beam etching device except for the spacer and film portions 41, 31 on the preliminary track faces 27. The width of the metal film 31 left unremoved by this step is equal to the width t 1 of the preliminary track faces 27.
With reference to FIG. 18, a plurality of winding grooves 32, rectangular in cross section, are formed in the upper surface of the second base plate 26b in parallel to the depth end grooves 29 so as to partially remove the portions of the plate defining the depth end grooves 29.
Next, the mirror-finished upper surface of the first base plate 26a shown in FIG. 19 is placed over the thin metal film 31 of the second base plate 26b shown in FIG. 18, and the first glass 30 is melted again and solidified in this state, whereby the two base plates 26a, 26b are bonded together with the glass, giving a block 33 as seen in FIG. 20.
The block 33 is cut along broken lines C-C' into core blocks 34. Track width defining grooves 35 are thereafter cut at a pitch P in the head portion of each core block 34 to form a plurality of medium facing ridges 37 with the specified track width t 2 as shown in FIG. 21.
The core block 34 is then sliced at hatched regions 38 to prepare core chips 39 as seen in FIG. 22. The core chip 39 comprises a pair of core segments 40a, 40b made of Mn-Zn ferrite and bonded together with the first glass 30, with the thin ferromagnetic metal film 31 and the gap spacer 41 provided at the joint between the segments.
The core chip 39 is thereafter treated in the same manner as in the first embodiment. The chip 39 is bonded to a slider 16, as fitted in its slit 15, and the slider 16 is chamfered as indicated at 18 to finish the exterior, whereby a completed floating-type magnetic head is obtained as shown in FIG. 12.
With the second embodiment as in the case of the first, the core segments 40a, 40b made of the ferrite which is satisfactorily wettable with glass are bonded directly to each other with the glass at opposite sides of the medium facing ridge 37 as shown in FIG. 22. The core chip 39 therefore has high mechanical stregnth.
Like the first embodiment, the first and second base plates 26a, 26b are bonded together with the first glass 30 filled in the precut grooves 28 and the depth end grooves 29 in the second base plate 26b by softening the glass, so that the plates can be bonded merely by heating the assembly to a temperature slightly higher than the softening point of the first glass 30. Accordingly, little or no reaction proceeds at the interface between the first base plate 26a and the metal film 31. This inhibits the formation of a secondary gap at the interface.
Since the metal film 31 is deposited on the gap spacer 41 formed over the second base plate 26b as seen in FIG. 16, the gap spacer 41 is interposed between the second base plate 26b and the metal film 31. This eliminates the likelihood that a nonmagnetic amorphous layer will be formed on the surface of the second base plate 26b during the deposition of the metal film 31, consequently further inhibiting the secondary gap.
Incidentally, even if an amorphous layer is formed on the upper surface of the second base plate 26b when the gap spacer 41 shown in FIG. 16 is formed, the amorphous layer merely makes a nonmagnetic layer integral with the gap spacer 41 without creating a secondary gap.
Third Embodiment
FIG. 23 shows another floating type magnetic head as a third embodiment, which is produced by the process to be described below with reference to FIGS. 24 to 29.
First, mirror-surfaced first and second base plates 42a, 42b are prepared which are made of a ferrimagnetic oxide material such as Mn-Zn ferrite. As seen in FIG. 24, a plurality of glass filling grooves 44 are formed in the gap forming surface of the second base plate 42 to leave preliminary truck faces 43 having a preliminary truck width t 1 slightly larger than the desired track width t 2 . A depth end groove 45 is also formed in the surface in a direction intersecting the glass filling grooves 44 perpendicular thereto. On the other hand, the first base plate 42a is coated with a thin ferromagnetic metal film 46 as of Sendust and a gap spacer 47 of SiO 2 or the like.
Next with reference to FIG. 25, a first glass 48 having a softening point of 590° C. is filled into the glass filling grooves 44 and the depth end groove 45 in the second base plate 42b, and the coated surface of the first base plate 42a is etched by an ion beam etching device or like dry etching device to form strips of metal film 46 and gap spacer 47 at a pitch P with the preliminary track width t 1 .
As shown in FIG. 26, the first glass 48 adhering to the preliminary track faces 43 of the second base plate 42b is removed by grinding or polishing to make the plate mirror-surfaced. A winding groove 49, rectangular in cross section, is formed in the base plate 42b in parallel to the depth end groove 45 so as to partially remove the grooved portion. Subsequently the two base plates 42a, 42b are fitted together with the truck faces 43 of the second base plate 42b opposed to the respective gap spacers 47 on the first base plate 42a, and the first glass 48 is then melted and solidified, whereby the two plates 42a, 42b are bonded together with the glass to give a core block 50.
With reference to FIG. 27, the core block 50 is cut along broken lines D--D' into core chip assemblies 51a as seen in FIG. 28.
Each core assembly 51a comprises a pair of core segments 52a, 52b of Mn-Zn ferrite directly bonded to each other with the first glass 48 in the glass filling groove 44, and the metal film 46 and the gap spacer 47 are provided at the core joint portions 53a, 53b at opposite sides of the groove 44.
The head portion of the core chip assembly is then grooved to partially remove the joint portion 53a, the portion defining the glass filling groove 44 and the other joint portion 53b to form a medium facing ridge 54 having a magnetic gap portion with the desired track width t 2 as shown in FIG. 29, whereby a core chip 51 is obtained.
The same procedure as in the case of the first and second embodiments is thereafter followed. With reference to FIG. 23, the core chip 51 is bonded to a slider 16, as fitted in its slit 15, and the slider 16 is chamfereed as at 18 to finish the exterior to afford a completed floating-type magnetic core.
With the third embodiment as in the case of the other embodiments, the core segments 52a, 52b, which are made of the ferrite satisfactorily wettable with glass, are directly bonded to each other with the glass at the portion where the glass filling groove 44 is formed as seen in FIG. 29. The core chip 51 therefore has high mechanical strength.
The first and second base plates 42a, 42b are bonded together with the first glass 48 filling the groove 44 and the depth end groove 45 in the second base plate 42b by softening the glass as shown in FIG. 26 also in the above production process, so that the plates can be bonded merely by heating the assembly at a temperature about 80° C. higher than the softening point of the first glass 48. Consequently, almost no reaction proceeds at the interface between the first base plate 42a and the thin ferromagnetic metal film 46. This inhibits formation of the secondary gap conventionally created by reaction.
Since the core segments 52a, 52b of the core chip assembly 51a shown in FIG. 28 are firmly bonded together with the first glass 48 filled in the groove 44, the assembly 51a will not fracture when machined to form the medium facing ridge 54 of FIG. 29. This results in an improved yield.
The medium facing ridge 54 can be formed alternatively at the joint portion 53a on the other side of the glass filling groove 44 in opposite relation to the one shown in FIG. 29. Accordingly, when the medium facing ridge is provided selectively at one of these two different positions, two kinds of magnetic heads can be fabricated; one for use above the magnetic disc and the other for use under the disc.
Fourth Embodiment
The magnetic head of a fourth embodiment is produced by substantially the same process as the third embodiment with the exception of the following feature. With reference to FIG. 30, a core chip assembly 51a is fabricated which comprises a pair of core segments 52a, 52b formed with winding grooves 49a, 49b, respectively. The assembly 51a is thereafter machined to form a medium facing ridge 54 as seen in FIG. 31.
With the magnetic head of the floating type thus obtained, the pair of core segments 52a, 52b provides an efficient magnetic path, enabling the head to exhibit improved recording-reproduction performance.
In brief, the floating-type magnetic heads of the floating type embodying the present invention have a magnetic gap with a very accurate length and are excellent in mechanical strength. These magnetic heads can be produced by the process of the invention with formation of a secondary gap inhibited effectively.
The construction of the magnetic head of the invention is not limited to those of the foregoing embodiments but can be modified variously by one skilled in the art without departing from the scope of the invention as defined in the appended claims.
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A floating-type magnetic head comprising a slider and a core chip secured thereto. The core chip comprises a pair of core segments joined together with a gap spacer and a thin ferromagnetic metal film which are formed at the joint only over a portion of the entire area of the joint which portion terminates at the face of the core chip to be opposed to magnetic recording media. The two core segments area bonded to each other with glass present over the remaining portion of the joint area. In producing the magnetic head, the core chip is prepared by fabricating a core block comprising a pair of base plates joined together and strips of thin ferromagnetic metal film and gap spacer provided at the joint, and machining the core block.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/536,715, filed Jan. 16, 2004.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates generally to electronic calculating devices. In particular, the invention relates to a handheld calculating device having a complete pipe reference source for solving a variety of piping problems.
[0004] 2. Description of Related Art
[0005] Pipe fitters, pipe fabricators, and plumbers all have jobs that require pipe fabrication and/or installation. Pipe fitting tasks typically require a person to use a calculator, and to refer to reference books for data and formulas for solving a variety of piping problems that occur during the fabrication and/or installation pipes. One problem is that most fitters, fabricators, welders, plumbers and others working with pipes do not learn enough mathematics to realize their full potential, so that many workers do not have the ability to remember the formulas required, or require considerable time to figure out how to use a formula properly, even with the assistance of an electronic calculator. This results in the craftsman having to use far less accurate calculations and more time consuming methods to fabricate or fit the piping being worked on.
[0006] Every project superintendent that has any sizable amount of piping on their job knows that among the journeyman there are many different skill levels. A person in supervision is charged with the duty of assigning the appropriate tasks to the appropriate journeyman. More often than not there is the problem of not enough craftsmen with a high level of skill to go around. The calculator of the present invention is the equalizer a craftsman needs to bring him or her to a higher level of performance in order to enjoy a previously unattainable level of success in their career. This translates into a higher earning potential and more efficient job performance.
[0007] Various calculating devices have been programmed to provide various functions for assisting work related activities. However, the relevant art does not provide a calculator capable of performing the necessary calculations required for pipe fabrication and/or installation. Nor does the relevant art provide such a calculator having a graphical interface to assist a user in performing the necessary calculations required for pipefitting applications.
[0008] U.S. Pat. No. 5,111,426, issued May 5, 1992 to Bergstresser, Sr. et al., shows a handheld calculator that allows welders to manipulate welding and cutting data for a job at hand. The calculator includes a complete welding reference source providing on-the-spot answers to problems and can calculate data necessary for the completion of a welding task. The calculator includes a saving and retrieving function that allows a user to quickly retrieve information from a subset or compare a calculation to a subset. Similarly, U.S. Pat. No. 6,167,412,. issued Dec. 26, 2000 to Simons, discloses a handheld medical calculator and medical reference device having an input keypad and an output screen connected to a processor with memory to perform specific clinical functions. Some of the clinical functions require accessing various medical reference tables to perform complex medical calculations.
[0009] U.S. Pat. No. 5,265,029, issued Nov. 23, 1993 to Ramsay, discloses a chemical calculator providing rapid and convenient ways to retrieve information and perform calculations of chemical elements and chemical formulas obtained by direct entry from a periodic table keypad. These calculations allow chemists to compute chemical transformations, reaction yields, limiting reactants, and empirical formulas. U.S. Pat. No. 4,744,044, issued May 10, 1988 to Stover et al., describes a handheld calculator for specialized dimensional calculations. The calculator may be used to calculate the dimensions and unit price of lumber.
[0010] U.S. Pat. No. 3,979,057, issued Sep. 7, 1976 to Katz et al., discloses an electronic calculator having a limited stored program capability and which is adapted to perform a plurality of problems particularly useful to aircraft pilots. The programs stored in the calculator cause sequential operation, including the demand for manual entry of necessary data, to calculate a desire result. U.S. patent Publication No. 2003/0126166, published Jul. 3, 2003, discloses a handheld computing device providing instructions for a user to graphically display vectors on a display screen. The device performs vector operations for one or more vectors using an input device while concurrently graphically viewing the vector and the vector changes on the display screen.
[0011] Several calculating devices include soft or programmable keys that provide a user with various functions that assist in performing desired calculations. U.S. Pat. No. 4,823,311, issued Apr. 18, 1989 to Hunter et al., shows a calculator keypad having keys with labels created by a display and subject to interactive change as the user desires. Specialized function keys with different functional labels provide a user with various desired functions. U.S. Pat. No. 4,107,782, issued to Cochran, discloses a user programmable calculator having special keys in addition to the numerical and function keys normally incorporated into a calculator in order to facilitate responding to data functional information requests by the calculator.
[0012] U.S. Pat. No. 4,680,455, issued Jul. 14, 1987 to Kuo, describes a method of manipulating a calculator using special function keys and instructions from a selected instruction card. The instruction cards provide formulas and equations to achieve various desired calculations. U.S. Pat. No. 4,035,627, issued Jul. 12, 1977 to Dickinson et al., describes a handheld calculator with keys for performing arithmetic, trigonometric, and logarithmic functions. U.S. Pat. No. 4,852,057, issued Jul. 25, 1989 to Patton, discloses a calculating device having stored menus with labels of operations that are performed on mathematical expressions.
[0013] U.S. Pat. No. 4,695,983, issued Sep. 22, 1987 to Oda et al., shows a calculator capable of executing formula calculations with different operational sequences. The calculator comprises means for selecting and designating either the sequential operation mode that sequentially executes formula calculations according to individual key operations, or a formula memory operation mode that executes operations after entry of the sequential operation mode. U.S. Pat. No. 4,078,251, issued Mar. 7, 1978 to Hamilton, describes an electronic calculator having an instruction word memory for storing instruction words that is addressable by the address register, and instruction word decoder logic for decoding the instruction words and for controlling the arithmetic unit in response thereto.
[0014] None of the above inventions and patents, taken either singly or in combination, is seen to describe the instant invention as claimed. Thus, a pipe reference and calculating device solving the aforementioned problems is desired.
SUMMARY OF THE INVENTION
[0015] The present invention is a pipe reference and calculating device. The device includes a housing dimensioned and configured for being held in a hand of a user. A processor is contained within the housing. A keypad is on the housing and is electrically connected to the processor. The keypad operates a plurality of switches, each switch controlling a circuit to produce an input signal to the processor for a desired function. A display screen is disposed in the housing and is electrically connected to the processor. A memory device is disposed in the housing and is electrically connected to the processor. Software is stored in the memory device. The software causes the processor access data from a database of pipe reference information and data, and formulas, perform pipefitting calculations with data accessed from the database, perform calculations on data input from the keypad, and perform pipefitting and geometric calculations using graphical images with labeled variables.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is a perspective view of a pipe reference and calculating device according to the present invention.
[0017] FIG. 2 is a block diagram of a pipe reference and calculating device according to the present invention.
[0018] FIG. 3 is a top plan view of a pipe reference and calculating device according to the present invention.
[0019] FIG. 4 is a flow chart for operation of the “calc” key of the pipe reference and calculating device of the present invention.
[0020] FIG. 5A is a flow chart for operation of the “reference” key of the pipe reference and calculating device of the present invention.
[0021] FIG. 5B is an example of a display screen resulting from pressing the “reference key” of the pipe reference and calculating device of the present invention.
[0022] FIG. 6A is a flow chart for operation of the “offset” key of the pipe reference and calculating device of the present invention.
[0023] FIG. 6B is an example of a display screen resulting from pressing the “offset” key of the pipe reference and calculating device of the present invention.
[0024] FIG. 6C is an example of a display screen for a 450 offset calculation using the pipe reference and calculating device of the present invention.
[0025] FIG. 7A is a flow chart for operation of the “layout” key of the pipe reference and calculating device of the present invention.
[0026] FIG. 7B is an example of a display screen resulting from pressing the “layout key” of the pipe reference and calculating device of the present invention.
[0027] FIG. 8A is a flow chart for operation of the “convert key” of the pipe reference and calculating device of the present invention.
[0028] FIG. 8B is an example of a display screen resulting from pressing the “convert” key of the pipe reference and calculating device of the present invention.
[0029] FIG. 9A is a flow chart for operation of the “right triangle solve” key of the pipe reference and calculating device of the present invention.
[0030] FIG. 9B is an example of a display screen resulting from pressing the “right triangle solve” key of the pipe reference and calculating device of the present invention.
[0031] FIG. 10A is a flow chart for operation of the “circle solve” key of the pipe reference and calculating device of the present invention.
[0032] FIG. 10B is an example of a display screen resulting from pressing the “circle solve” key of the pipe reference and calculating device of the present invention.
[0033] FIG. 11A is a flow chart for operation of the “arc solve key” of the pipe reference and calculating device of the present invention.
[0034] FIG. 11B is an example of a display screen resulting from pressing the “arc solve key” of the pipe reference and calculating device of the present invention.
[0035] Similar reference characters denote corresponding features consistently throughout the attached drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0036] The present invention is pipe reference and calculating device. The invention disclosed herein is, of course, susceptible of embodiment in many different forms. Shown in the drawings and described herein below in detail are preferred embodiments of the invention. It is to be understood, however, that the present disclosure is an exemplification of the principles of the invention and does not limit the invention to the illustrated embodiments.
[0037] The present invention, represented in FIG. 1 , is a pipe reference and calculating device having a software application adapted to assist in the fabrication of pipe and pipefitting related tasks of all types, generally represented as 20 in the drawings. The device 20 calculates the cut length for a vast array of piping offsets and solves pipefitting problems involving arcs, triangles, and circles. The device 20 is provided with a handheld case housing the calculator. The device 20 includes additional keys performing special functions not found on traditional scientific calculators. Keys for these functions are related to the fabrication of pipe and pipefitting related tasks and include a reference key 31 allowing a user to search a variety of reference topics to obtain detailed information about a particular subject; an offset key 33 that brings up a list of offset types to scroll through; a layout key 35 that brings up a list of common piping problems to scroll through; a trig key 55 that brings up a complete trigonometric table to scroll through; and a conversion key 57 that converts from one unit of measurement to another unit of measurement.
[0038] Additional keys for these functions include a right triangle solve key 67 for solving right triangles; a circle solve key 71 for solving circles; an arc solve key 75 for solving arc length; a feet/in key 61 for displaying the calculation in feet and inches; a fraction bar 65 for inserting a fraction bar when the calculator is in feet and inches mode; a files key 69 that brings up a list of previously saved files; and a save key 73 that saves the information on the screen 25 . Each key will be discussed later in greater detail.
[0039] Turning briefly now to FIG. 2 , a block diagram illustrates the basic components of the present invention. The device 20 includes a processor 115 , a display screen 25 , an input device 100 , and memory 120 . The display screen 25 and the input device 100 are electrically coupled to the processor 115 . The display screen 25 may be, e.g., a Liquid Crystal Display (LCD). The input device 100 comprises a keypad with a variety of buttons.
[0040] Each button operates an electrical switch controlling a circuit which sends an input signal to the processor 115 in order to carry out a desired function or operation. The display screen 25 has a large display area to accommodate drop down menus and visual aids, providing a graphical interface. Memory device 120 is also electrically coupled to processor 115 . Memory deice 120 may include areas of read only memory (ROM) and random access memory (RAM) for permanent and temporary memory storage, respectively. A software application is stored in the memory device 120 , and when executed by the processor 115 , the software application provides a reference source and a guide for layout information to be used in the fabrication of pipe and pipefitting related tasks of all types.
[0041] Turning now to FIG. 3 , the device 20 includes most of the keys found on many scientific calculators, including: alphanumeric keys 0-9 generally represented by 77 ; on/off keys 37 ; a clear key 38 for clearing the screen 25 ; trigonometric keys 41 for performing basic trigonometric functions, such as sine, cosine, and tangent functions; a second key 39 for performing a secondary function for the next key depressed of certain keys, such as the inverse sine, inverse cosine function, or inverse tangent obtained when depressing the second key 39 and then a trigonometric key 41 ; scroll arrow keys 43 , 45 , 47 , 49 for allowing a user to navigate through the various menus and lists or to move a cursor; an enter key 51 for bringing up the next list, screen, prompt or answers to problems; a tab key 53 for moving a cursor from point to point in the display; algebraic function keys (squares, square roots, reciprocals) 59 ; operational keys 81 , including division, multiplication, subtraction, addition, and equality signs; a % key 78 ; and ± key 79 .
[0042] Referring briefly back to FIG. 1 , a more detailed description of the additional keys performing special functions not found on traditional scientific calculators is given. The trig key 55 brings up a complete trigonometric table to scroll through. This allows users who have become accustomed to looking up trigonometric data in written tables to continue to do so. Files key 69 brings up a list of previously saved files. A user can scroll through the list until the desired file is found. By pressing the enter key 51 when the desired file is highlighted, the calculator 20 will bring the file up from memory. The save key 73 saves the information on the screen into a file. When the save key 73 is pressed, a cursor will appear in the lower portion of the screen 25 . A user can then type a number for a file name, or by pressing the alfa key 27 the user can then type notes and file name using the second function of the number keys 77 . The decimal key 58 will cause the calculator to display measurements in decimals. The feet and inches key 61 causes the calculator 20 to display measurements in feet and inches. The fraction bar 65 is pressed to insert the fraction bar when the calculator 20 is in feet and inches mode.
[0043] FIG. 4 shows a flow chart describing the function of the calculation or “calc” key 29 . When the calculation key 29 is pressed at step 202 , processor 115 checks if device 20 is already functioning as a scientific calculator, that is, functioning in calculator mode, at step 204 . If device 20 is in calculator mode, any operands and the calculator registers, including any results or instructions for pending calculator functions, are cleared at step 206 , and processor 115 enters or re-enters calculator mode at step 208 . If device 20 is not in already in calculator mode, processor 115 enters calculator mode at step 208 . Hence, pressing the “calc” key has the effect of clearing any pending calculations and re-starting the scientific calculator mode.
[0044] FIGS. 5A-5B illustrate operation of the reference key 31 . FIG. 5A shows a flow chart of operation when the reference key 31 is pressed. Upon pressing the reference key 31 at step 212 , a general or broad list of reference subjects is provided at step 260 . A keyword search prompt is simultaneously displayed adjacent a keyword text block at step 285 , so that the user can obtain access to the desired reference information. This can occur by selecting menu entries at step 265 through operation of scroll keys 43 , 47 , and the enter key 51 . This can also occur by pressing the tab 53 or horizontal scroll key 45 to move to the keyword search, and then using the alfa 27 , alphanumeric 77 , and enter 51 keys to perform a keyword search at step 290 .
[0045] If a menu subject is selected at step 265 , the user is presented with a further defined list of reference subjects under the first subtitle at step 275 . Once a desired general reference subject has been chosen at step 280 , the result is displayed at step 295 . If the user entered a keyword search term at step 290 , the user may be presented with a broad general reference menu at step 260 , or a detailed reference subject menu at step 280 , depending upon the keyword entered.
[0046] FIG. 5B provides an example of the display screen 25 resulting from the operation of the reference key 31 . As described above, upon pressing the reference key 31 , the processor 115 provides two methods of searching for desired reference material upon display screen 25 , including a drop-down menu reference list 320 to scroll through providing general reference list menu 330 . Only three reference topics are shown in the list box 330 in the drawing, the number of topics displayed being dependent upon screen size. The current selection may be indicated by highlighting the selection with bold print (as shown), by reverse video, by color-coding, by a selection arrow 332 , or any other manner. Additional selections may be viewed by scrolling through the list using arrow keys 43 and 47 until the desired selection is highlighted, and then pressing the enter key 51 .
[0047] The submenu list box 335 lists more detailed topics in the category selected, which is updated as the selection in the general menu list 330 is changed. In the example provided, the general drop-down reference menu list 330 is a plastics selections usage category, and the submenu 335 has more detailed topic categories of plastic pipes, including the subcategories of ABS, CPVC, PP, PPE, or PVC pipe. The currently selected subcategory topic may also be indicated by highlighting the selection in bold print (as shown), by reverse video, by color-coding, by a selection arrow 337 , or any other manner. The user scrolls to the desired subcategory in submenu list box 335 , selects the subcategory by pressing the enter key 51 , and the desired reference information is displayed (not shown). An exemplary keyword search prompt 325 is also shown on the display screen 25 when the reference key 31 is pressed. The user may leave the reference mode by pressing the “calc” key 29 .
[0048] FIG. 6A shows a flow chart illustrating operation of the offset key 33 . Upon pressing the offset key at step 350 , the device 20 displays a list of offset types at step 355 . An offset type may then be selected at step 357 in the same manner as a menu selection described with regard to FIG. 5B above. An illustration of the offsets with variables is then displayed at step 360 . Each offset type and measurements for the offset are entered in step 365 for the processor 115 of the device 20 to calculate the pipe offset cut lengths in step 370 . The result may be automatically calculated and displayed after entering sufficient measurements. Alternatively, a keyword search may be done at step 375 by tabbing to the keyword search prompt, entering the search term at step 385 , and pressing the enter key 51 at step 390 . The user is then directed to the display offset types list of step 355 , which will display a portion of the offset list that includes the search term.
[0049] FIGS. 6B-6C provide an example of the display screens 25 resulting from the operation of the offset key 33 . In FIG. 6B , an example of a search for a 45° offset is implemented. The search is carried out by selecting 45° offset from list menu 420 . Alternatively, a search for a 45° offset may be input into search prompt 405 . In FIG. 6C , an illustration of the display screen 25 which appears when a 45° offset calculation is shown to include a graphical illustration 425 of a 45° pipe offset provided with variable letters where the measurements are to be taken for the run R or offset O, and for the location of the travel T to be calculated. A corresponding list of variable letters 445 is below the illustration.
[0050] The user is prompted to enter the pipe type (i.e. cast iron, butt weld, copper, etc.) at list box 435 and size of pipe being worked with (i.e., 2″, 1½″, 48″, etc.) via list box 440 . Upon tabbing to the variable letters 445 and typing in either the run or the offset value and the enter key 51 , the calculator computes and displays the center-to-center travel length T and cut length C. The calculator automatically subtracts the take outs from T and this is represented by C. Other standard pipefitting offset calculations, such as around circular, around square corners, and rolling offsets, are performed in similar fashion using the offset key 33 to access the appropriate software routine as described above.
[0051] FIG. 7A shows a flow chart illustrating operation of the device 20 when the layout key 35 is pressed at step 450 . Upon pressing the layout key 35 , a list of common piping problems is displayed on the screen at step 455 so that the user may scroll through the list at step 460 . The user selects the pipe problem at step 465 by pressing the enter key 51 , and the device 20 displays detailed instructions to solve the pipe problem at step 470 . FIG. 7B provides an example of the display screens 25 resulting from a search for common piping layout problems. The search for common piping layout problems is performed by conducting a keyword search via prompt 510 or common piping problems layout drop down list menu 505 . In the example, a cut angle is selected from the drop down list menu 505 .
[0052] FIG. 8A shows a flow chart describing the operation of the convert key 57 . Upon pressing the convert key 57 at step 520 , the device displays a convert screen at step 525 , as exemplified in FIG. 8B . The user moves the cursor or focus to select a category of measurement (e.g., distance, weight, etc.) and enters the selection at step 527 by pressing the enter key 51 . The user then enters the number to be converted at step 530 and the units of measurement at step 535 . The user then enters the desired units of measurement the number is to be converted to at step 540 , presses the enter key at step 545 , and the device 20 performs the conversion and displays the numerical result in the desired units of measurement at step 550 .
[0053] FIG. 8B provides an exemplary display screen 25 that appears when the convert key 57 is pressed. A menu 625 of categories of units of measurement is displayed across the top of the screen 25 . The user may select the desired category by tabbing and operation of the arrow cursor control keys to highlight the desired category, and then select the category by pressing the enter key 51 . A first edit box 627 is provided for entering the numerical units of the quantity to be converted, and a list box 628 or scrollable list box is presented beneath the edit box 627 for selection of the dimensional units of the quantity to be converted. A second edit box 629 or a text box is provided adjacent the first edit box 627 for display of the numerical result, and a second list box 631 is provided beneath edit box 629 for selection of the dimensional units desired. The screen 25 may also include a keyword search prompt 633 for help in measurement units or other aspects of operation of the convert key 57 .
[0054] FIG. 9A shows a flow chart of the operation of the right triangle solve key 67 . Upon pressing the right triangle solve key 67 at step 634 , the device 20 displays a screen 25 having a graphical depiction of a right triangle with variables labeling the sides and angles of the triangle and edit boxes for entry of the known values at step 635 . The known variables are entered at step 640 . The enter key 51 is pressed at step 645 , and the device computes the unknown value and displays the results at step 650 .
[0055] FIG. 9B is an exemplary display screen 25 showing the right triangle solve key in operation. Pressing the right triangle solve key 67 results in a display screen having a graphical image 665 of a right triangle. All of the sides and angles are labeled with variables. Below the triangle 665 , there is a corresponding list of variables 670 . The user types in the known parts within the list of variables 670 , and the device 20 solves the remaining sides and angles. The user navigates between the variables using the tab key 53 and arrow cursor control keys 43 , 45 , 47 , and 49 . The screen 25 may have an edit box next to the variable currently having the focus, or the screen 25 may simply have a blinking underscore or cursor next to the variable having the focus to prompt for entry of a measurement, the user entering the numerical digits followed by the enter key 51 .
[0056] FIG. 10A shows a flow chart describing operation of the circle solve key 71 . Upon pressing the circle solve key 71 at step 702 , the device 20 presents a display screen 25 having a graphical image of a circle with variables noted on the figure and a list of variables for entry of known measurements at step 705 . The known variables are input at step 710 . After the enter key 51 is pressed at step 715 , the device 20 computes and displays the remaining unknown parts of the circle at step 720 .
[0057] FIG. 10B shows an exemplary display screen 25 illustrating operation of the circle solve key 71 . Pressing the circle solve key 71 produces a display screen 25 having a graphical image of a circle 755 . All parts of the circle 755 are labeled with a variable. A corresponding list of variables, such as the area 760 , diameter 765 , and circumference 770 , etc., are below the circle 755 . The user types in the known parts of the circle and the device 20 solves the remaining parts of the circle 755 .
[0058] FIG. 11A shows a flow chart describing operation of the arc solve key 75 . Upon pressing the arc solve key 75 at step 802 , a graphical image of an arc is displayed labeled with variables along with a list of variables for entry of the known values at step 805 . The known variables are entered at step 810 . After pressing the enter key 51 at step 815 , the device 20 computes and displays the unknown remaining parts of the arc at step 820 .
[0059] FIG. 11B shows an exemplary display screen 25 illustrating operation of the arc length solve key 75 . Pressing the arc key 75 causes the device 20 to present a graphical image of an arc 827 on the display 25 . All parts of the arc 827 are be labeled with variables. Below the arc 827 is a corresponding list of variables 830 , e.g., radius, angle, chord, and arc length. The user enters numerical digits for the known values, either into an edit box or at a blinking cursor. Upon pressing the enter key 51 , the calculated value for the arc length is displayed in the variable list 830 .
[0060] It will be understood that the display screens shown in the drawings are exemplary only, and that details of the display screen 25 and the interface for the entry of data and menu displays may vary in different implementations of the present invention, provided that the display screen 25 shows graphical images labeled with variables to provide an easy to use interface for solving pipefitting calculations.
[0061] While the invention has been described with references to its preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the true spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teaching of the invention without departing from its essential teachings.
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A pipe reference and calculating device pipe reference and calculating device includes a housing that can be held in a hand of a user. A processor is contained within the housing. A keypad is on the housing and is electrically connected to the processor. The keypad operates a plurality of switches, each switch controlling a circuit to produce an input signal to the processor for a desired function. A display screen and a memory device are disposed in the housing and are electrically connected to the processor. Software is stored in the memory device. The software causes the processor access data from a database of pipe reference information and data, and formulas, perform pipefitting calculations with data accessed from the database, perform calculations on data input from the keypad, and perform pipefitting and geometric calculations using graphical images with labeled variables.
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CROSS REFERENCE TO RELATED APPLICATIONS
The present application claims priority to U.S. Provisional Patent Application No. 60/603,610, which was filed Aug. 23, 2004 and which is hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
This invention is directed generally to forming anti-microbial materials, and more particularly to forming foam materials having anti-microbial activity and/or filtration properties.
BACKGROUND
There are several prior art methods that describe metallizing of foam substrates (e.g., Pat. Nos.: 6,395,402; 5,151,222; 3,661,597). Different methods have been used to metallize foam for various applications such as EMI shielding etc. Pat. No. 6,395,402 discuss the metallization of copper/nickel for EMI applications. While the adhesion of the metal to the foam may be good, the process cannot produce a good silver coating due to the difference in deposition rates of copper versus silver. In addition, these materials do not provide any-microbial activity as copper/nickel do not provide anti-microbial properties. The other patents listed produce rigid foam that cannot be used in a medical/anti-microbial application(s) or as a flexible filter.
Accordingly, what is needed is a method of metallizing foam that is capable of using silver. Also what is needed is a method of forming a foam material that has anti-microbial activity. Additionally what is needed is a method of forming a foam material that may be used as a filter and having anti-microbial activity.
SUMMARY OF THE INVENTION
The present invention provides a method of metallizing a foam material. The method may be used to form a foam material having anti-microbial activity by metallizing the foam with a metal, such as silver. The resulting foam may be used in a variety of different applications such as a filter material. The methods of the present invention are simpler than prior art methods since the foam materials may be metallized without the need for an activation/seeding step. The resulting foam may also be designed such that the product has a low resistance and/or an optimal metal ion release. The method of the present invention uses one or more of the steps of etching the foam, pre-metallizing the foam and metallizing the foam with silver. Depending on the selected properties of the final foam, the method may use some or all of these steps.
These and other embodiments are described in more detail below.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is more particularly described in the following description and examples that are intended to be illustrative only since numerous modifications and variations therein will be apparent to those skilled in the art. As used in the specification and in the claims, the singular form “a,” “an,” and “the” may include plural referents unless the context clearly dictates otherwise. Also, as used in the specification and in the claims, the term “comprising” may include the embodiments “consisting of” and “consisting essentially of.”
The present invention provides a method of metallizing a foam material. The method may be used to form a foam material having anti-microbial activity by metallizing the foam with a metal that provides anti-microbial activity to a material. The resulting foam may be used in a variety of different applications that may benefit from a material having anti-microbial activity including, but not limited to, the use of the metallized foam as a filter material. The methods of the present invention are simpler than prior art methods because the foam materials may be metallized without an activation/seeding step commonly associated with prior art methods. The resulting metallized foam materials are formed such that the metal adheres well to the foam. The resulting foam may be designed such that the product has a low resistance and/or an optimized silver ion release.
The methods of the present invention are designed to metallize foam without the need for an activator. As such, the methods of the present invention are capable of metallizing the film through one or more of the steps of etching the foam, pre-metallizing the foam and/or metallizing the foam with the selected metal. Depending on the selected properties of the final foam, one or more of these steps may be omitted while still achieving a metallized foam product. As used herein, an “etchant” is a material capable of etching or removing portions of the foam material to permit better adhesion of the metal to the foam substrate to be metallized.
Accordingly, in a first aspect, the methods of the present invention etch the foam to increase the surface area of the foam. To etch the foam, the foam substrate is first quenched using an etchant and then rinsed. The etchant may be, in one embodiment, a base solution. The type of base solution may be any base solution capable of removing or etching portions of the foam substrate. The type of base solution that may be used may vary depending on one or more factors including, but not limited to, the foam substrate to be etched, the metal to be applied, the degree of etching desired, and/or the final characteristics of the metallized foam. Examples of base solutions that may be used for the etchant include, but are not limited to, alkaline hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, francium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, or a combination thereof. In one embodiment, the base solution is sodium hydroxide.
The foam may be etched by immersing the foam substrate in a solution containing the etchant. As used herein, “immersed” is meant to include any method by which a solution may be contacted with at least a portion of a surface area of a foam substrate including, but not limited to, dipping, spraying, immersing, quenching, and/or any other method capable of applying a liquid to at least a portion of a substrate.
In one embodiment, the first step in the process may be performed either immediately prior to the second step or may be performed as a preparation step with subsequent steps taking place at a future time. As such, thicker foams and/or extended amounts of foam may be treated in a mass processing step. This would enable a manufacturer to quench thick foam (1′ thick) and 12 feet or more of length at a time. Alternatively, flame-treated non-etched foam may be etched in-house using a stronger solution of sodium hydroxide.
The first etching step may be performed under a range of operating temperatures and/or dwell or etch times, depending on the type of foam to be etched, the etchant used, and/or the selected characteristics of the finished product. Various embodiments for the methods of the present invention are set forth below, although it is to be understood that other embodiments are also included within the scope of the present invention. For the percentage of the foam that is etched:
Etching % First Embodiment 3-75 Second Embodiment 10-50 Third Embodiment 15-40 Fourth Embodiment ~25
For the temperature at which the process is to be operated:
Temperature range ° C. First Embodiment 10-60 Second Embodiment 15-50 Third Embodiment 20-40 Fourth Embodiment ~30
For the etch time of the process:
Etch Time in Minutes
First Embodiment
1-45
Second Embodiment
10-30
Third Embodiment
15-30
Fourth Embodiment
~25
The temperature and time of etch may be dependent on the concentration of the etchant solution.
After the foam has been etched, the foam may be conditioned with a non-ionic surfactant or other suitable material to enable the surface to be wet out and/or to clean the surface of any debris/dirt. A good rinsing process using de-ionized water with temperature under 70° C. follows may be used with the following embodiments:
Temperature of DI Water
First Embodiment
5-70
Second Embodiment
10-50
Third Embodiment
20-40
Fourth Embodiment
~30
Some polyether foams may not be etched since the chemistry as described below is sufficient to activate the surface of the foam material. As a result, for the methods of the present invention, when a polyether foam is used as the foam substrate, the foams may be metallized without the need for an activation/seeding step or an etching step for preparing the foam for metallization.
After the step of etching the foam, then the methods of the present invention may include a pre-metallization step. The pre-metallization step is utilized to prepare the foam for the application of the metal and to help facilitate attachment of the metal to the foam substrate. In one embodiment, the pre-metallization step may be accomplished by dipping the etched foam in an acid solution. An acid dip, such as with HCl, may then be used. The acid dip acts as a pre-metallizing step utilizing the acid as the solvent. Other acids, such as sulfuric acid or nitric acid, may be used for the pre-metallization step. A rinsing step may then be used upon completion of the pre-metallizing step.
For the dwell times of the pre-metallizing step, various embodiments are set forth below:
Dwell Time in acid (minutes) First Embodiment 1-35 Second Embodiment 3-30 Third Embodiment 5-20 Fourth Embodiment ~15
For the concentration of the acid in the pre-metallizing step, various embodiments include:
Concentration of acid (%)
First Embodiment
0.5-35
Second Embodiment
1-20
Third Embodiment
3-18
Fourth Embodiment
~15
The pre-metallization step may, in one embodiment, provide a mixture of stannous chloride and muriatic acid. The amount of stannous chloride may be, in one embodiment, selected to be between about 60 gm/l up to about 140 gm/l and the concentration of the muriatic acid may be between about 6 to about 15%. The dwell time may be selected to be between about 3 and 15 minutes. Once the pre-metallization step is completed, the process may be followed by a special counter flow rinsing with controlled water flow. This step enables the acid to remove any excess salts and acids from the substrates yet leave an optimum amount of activators on the surface. For the concentration of the muriatic acid, various embodiments are set forth below:
Concentration of acid (%) First Embodiment 4-25 Second Embodiment 5-20 Third Embodiment 8-18 Fourth Embodiment ~10
For the concentration of the stannous chloride, various embodiments are set forth below:
Concentration of Stannous Chloride First Embodiment 5-40 Second Embodiment 10-30 Third Embodiment 20-25 Fourth Embodiment ~10
For the dwell time, various embodiments for the present invention may include:
Dwell time in minutes
First Embodiment
5-60
Second Embodiment
10-50
Third Embodiment
20-30
Fourth Embodiment
~10
It is to be understood that embodiments for the concentration of the acid, the concentration of the stannous chloride and/or the dwell time are not required to be used in the order listed above in the respective tables, but may be used in any order or combination thereof. Accordingly, in one embodiment, the concentration of the acid may be from about 5 to about 20%, the concentration of the stannous chloride may be about 10%, and the dwell time may be from about 5 to about 60 minutes. Alternatively, in another embodiment, the concentration of the acid may be from about 8 to about 18%, the concentration of the stannous chloride may be from about 5 to about 40%, and the dwell time may be from about 10 to about 50 minutes.
Once the foam has been prepared, the methods of the present invention then include a final step of applying the metal to the foam. The step may be referred to as a metallization step. The metallization step may be performed using known metallization technologies such as those described in U.S. Pat. No. 3,877,965 or patent application Ser. No. 10/666,568, which are hereby incorporated by reference.
The metallized foam may then be placed in an oven at 60-70° C. for about 30 minutes to produce a semi-quenching effect to help attach the metal to the foam.
The methods of the present invention may be used with a variety of different metals that may be desired to be attached to a foam substrate. In one embodiment, the metal is silver. Silver provides anti-microbial, conductive and/or anti-static properties to the foam substrate. In alternative embodiments, the metal may be selected from copper, gold, aluminum, or any other metal capable of being attached to a foam substrate.
The present invention may be used with any type of foam. Examples of foams that may be used include, but are not limited to, polyurethane, polyester, polyether, or a combination thereof. The resulting foams have enhanced resistance (ohms/square), anti-microbial activity, ion release, or a combination thereof, as compared to prior art foams.
The metallized foam products made according to the methods of the present invention may be used in any application wherein the advantages offered by the metal may be utilized. For example, due to the anti-microbial benefits, if the metal is silver, the metallized foam may be used as a filter material for the filtration of liquids. In addition, the foam may be in the form of a thin layer, such that the resulting metallized foam may be used as a wrap for wounds to assist in healing of the wounds.
The present invention will now be further described through examples. It is to be understood that these examples are non-limiting and are presented to provide a better understanding of various embodiments of the present invention.
EXAMPLES
Example 1
A bath was prepared by dissolving 4.2 gm of silver nitrate in de-ionized water. It was then complexed with 3.3 ml of 27% aqua ammonia. A quenched foam sample weighing 24.0 gm was cleaned with non-ionic surfactant such as Triton X-100 and rinsed thoroughly. Foam was etched with 15% HCl for 20 minutes. The foam was then pre-metallized with solution having 10% HCl and 10 gm/l of anhydrous tin chloride for 20 minutes. The foam was then rinsed in counter flow de-ionized water. 0.63 gm of tetra sodium EDTA was dissolved in 2 liters of de-ionized water. 6.5 ml of NEL/AEM surfactant was also added to the bath. The foam was placed in the reactor and solution was agitated. Silver complex was added and then 1.8 ml of formaldehyde was added. After three hours the sample was removed and subjected to hot water rinse. Then a 0.2% NaOH solution was (50 mL volume) was made up and at 60° C. The metallized foam was then dipped into the solution. The color changed to a gold tone.
Example 2
The sample obtained from example 1 cut to produce a 1.5 gm sample. This was then placed in a beaker with 5% sodium chloride solution for 24-hour period at 37° C. The solution after 1-hour period was then tested for silver ions using a Perkin Elmer Analyst 300. The ion release was 0.5 ppm
Example 3
The sample obtained from example 1 was cut to weight 0.75 gm and was subjected to Dow Corning Corporate Test Method 0923 and/or ASTM-E2149 Test method. The organism used was Staphylococcus aureus ATCC 6538. The reduction of organism growth was over 99.9%.
Example 4
The Sample obtained from example 1 was subject to process similar to the one described in U.S. patent application Ser. No. 10/836,530, the disclosure of which is hereby incorporated by reference in its entirety. This sample was then subjected to the ion release protocol as described in example 2. The ion release was at 6.2 ppm in one hour
Example 5
The sample obtained from example 1 was subject to ASTM E-2149 test for antimicrobial efficacy. The organism used was Staphylococcus aureus ATCC 6538. The reduction of organism growth was over 99.9%.
The foregoing is provided for purposes of illustrating, explaining, and describing embodiments of this invention. Modifications and adaptations to these embodiments will be apparent to those skilled in the art and may be made without departing from the scope or spirit of this invention.
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A method of producing a metallized polymeric foam that produces an anti-microbial material using an advanced method of metallizing polymeric foam with a metal, such as silver. The foam material may be polyurethane, polyester, polyether, or a combination thereof. The method provides a 3-dimensional surface coating of the metal. The metallized substrate is durable and highly adherent. Such metallized foam is a highly effective filter and/or an anti-microbial product. The mechanism of filtration is mainly due to Vander Der Wal attraction. The anti-microbial activity may be due, in part, to the release of select metal ions as a response to stimuli.
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This application is a continuation of application Ser. No. 09/154,159, filed Sep. 16, 1998, now abandoned.
The present invention relates to coating of papers and cardboards. In particular the invention concerns a method according to the preamble of claim 1 for coating fibrous webs, such as base papers of fine papers.
According to a method of the present kind, a coating colour containing pigments is applied to the surface of a web and dried in order to form a coated web.
A disadvantage of known coating colours and pigments contained therein is the uneven distribution of the coating material, i.e. poor coverage. In particular with small amounts of the coating colour, the poor coverage gives rise to bad printability and patchy brightness of the paper. As a remedy, large amounts of coating have been used. Attempts have been made to improve the coverage also by producing a so-called structurized coating colours. This means that a destabilization of the coating mixture has been aimed at by e.g., a cationic substance. The problem of structurization is for example poor runability and poor surface hardness which create problems during printing. Large coating amounts lead to poor opacity, bulk and cracking problems in particular with light paper qualities.
High-speed coating with the film press method is hampered by mist-forming in the coating nip which interferes with runability and impairs the quality of paper. The problem arises when the film splitting in the nip is not under control and a part of the film does not accompany the paper web or the coating roller but is directly flung out from the nip. Uncontrolled film splitting may be caused by insufficient immobilization of the coating colour before splitting. The problem can be solved by raising the immobilization point of the coating colour by increasing the dry matter content of standard coating colour. This solution to the mist-forming, however, leads to another problem. Since the amount of coating is dependent on the dry matter content of the coating colour, the feed thickness of the film will have to be reduced. The thickness of the film on the coating roll is regulated with a rotating rod. The thickness of the film can to some extent, but not sufficiently, be regulated by varying the thickness and the rotational speed of the rod. When the rod load is increased too much, which happens when the dry matter is too high, the pasta film will, however, break between the rod and the coating roll. This phenomenon is called drop formation. The coating colour flies in the form of big drops to the coating roll and big lumps are thus transferred to the paper.
As will appear from the above, also when coating is carried out with the film transfer method at high speeds it is difficult to obtain sufficient coverage. Further, at high speeds two difficult problems relating to film press coating will emerge, namely mist-formation and drop-formation. These problems lead to both defects in quality and to poor coverage.
BRIEF SUMMARY OF THE INVENTION
It is an object of the present invention to eliminate the problems of the prior art and to provide an entirely novel solution for coating of paper webs, cardboard webs and similar fibrous webs.
The present invention is based on the concept of increasing the immobilization point of the coating colour by using in the coating colour a pigment, the proportion of smallest particles of which (<0.2 μm and <0.5 μm) is approximately the same or slightly smaller than conventional pigments. Preferably less than about 10% of the particles are smaller than 0.2 μm and a maximum of 35% are smaller than 0.5 μm. According to the invention, the proportion of mid-size pigment particles having a diameter of 0.5 to 2 μm is clearly larger than for conventional pigments, typically this proportion is over 20% greater. Within the scope of the present invention, this particle size distribution is called “steep”. We have found that when the distribution is steep a good coverage and simultaneously even a better surface strength is obtainable.
The above mentioned numerical values of the particle sizes hold for spherical or approximately spherical particles measured by a Sedigraph apparatus.
The above-mentioned coating mixture is used in particular for film transfer coating at high speed which exceed 1450 m/min, when aiming at small coating amounts.
More specifically, the process according to the present invention is mainly characterized by what is stated in the characterizing part of claim 1 .
The invention will provide considerable advantages. Thus, by means of the invention a product can be obtained, having excellent surface properties, excellent coverage and still good structural and optical properties. It is essential for the invention that the coating pigment which has a steep particle size distribution yield a coating colour, a paste, which immobilizes at a much lower dry matter content than traditional mixtures. In this way it becomes possible to control the aimed coating amounts at high speed without any runability and quality problems. In particular, it is possible to avoid the problems appearing during film press coating at high speeds; the coating colour immobilizes so rapidly that film splitting takes place controllably without mist-forming. Since the immobilization point can be raise without increasing the dry matter content, no drop formation occurs.
In the following the invention will be discussed more closely with the aid of a detailed description and a number of working examples.
BRIEF DESCRIPTION OF THE FIGURES
The attached drawings depict the normal and steep particle size distributions. FIG. 1 depicts the normal and steep particle size distribution of gypsum. FIG. 2 depicts the normal and steep particle size distribution of carbonate. FIG. 3 shows the cumulative particle size distribution determined by laser diffraction for the carbonates 1 to 3 used in Example 3.
DETAILED DESCRIPTION OF THE INVENTION
Within the scope of the present invention, the term web stands for a material comprising paper or cardboard a corresponding cellulosic substance, which is derived from wood or annual or perennial plants. Said material can be wood-free or wood-containing and it can be prepared from mechanical, semimechanical (chemimechanical) or chemical pulp. The chemical pulp can be bleached or unbleached. The material can also comprise recycled fibers, in particular reclaimed paper or cardboard. According to a particularly preferred embodiment the web is produced from a mixture of a mechanical pulp and a chemical pulp, the proportion of the mechanical pulp being 80 to 30%. This mixture may comprise pulp produced from hardwood or softwood by mechanical defibering methods, such as GW, PGW, TMP or CTMP pulp. The raw material used can be spruce. A preferred product is obtained by coating a base paper produced from a mixture of chemical pulp and a mechanical pulp of aspen or another wood species of the Populus family. Examples of wood species of the Populus family are P. tremula, P. tremuloides, P balsamea, P. balsamifera, P. trichocarpa ja P. heterophylla . Aspen (trembling aspen, P. tremula ; Canadian aspen P. tremuloides ), and aspen varieties known as hybride aspens produced from different base aspens by hybridizing as well as other species produced by recombinant technology, and poplar are considered particularly advantageous. The chemical pulp can be produced by any suitable method from hardwood or softwood, in particular from softwood. The thickness of the material web is typically in the range of 30 to 250 g/m 2 , preferably it is about 30 to 100 g/m 2 when coated paper is produced.
A preferred embodiment of the invention comprises coating a base paper manufactured from mechanical spruce pulp and chemical softwood pulp in order to produce LWC paper and coating a base paper manufactured from mechanical aspen pulp and chemical softwood pulp in order to produce fine papers.
The coating colours according to the invention can be used for single coating and as so called pre-coat and surface-coat colours. Preferably the material is double-coated, first with a precoating and then with a surface coating, whereby both coating colours contain pigments having a steep particle size distribution.
Generally for 10 to 100 parts by weight of at least one pigment or a mixture of pigments, the coating colour according to the invention contains about 0.1 to 30 parts by weight of at least one binder and 1 to 10 parts by weight of other known additives.
The composition of a typical pre-coat mixture is the following:
pigment/filler
100 parts by weight
(e.g. coarse calcium carbonate)
binder
1 to 20 parts by weight
additives
0.1 to 10 parts by weight
water
balance
The dry matter content of a pre-coat mix is generally 40 to 70%, preferably 50 to 65%, and the pH 7 to 9, when the coating speeds are over 1400 m/min.
The composition of a surface coating colour according to the present invention is, for example, the following:
coating pigment
30 to 90 parts by weight
(e.g. fine calcium carbonate)
coating pigment
10 to 50 parts by weight
(e.g. fine kaolin)
total pigment
100 parts by weight
binder
1 to 20 parts by weight
additives
0.1 to 10 parts by weight
water
balance
The dry matter content of a coating colour is typically 50 to 75%.
In the above-mentioned surface coating colours at least a part (1 to 100%, preferably about 20-100%) of the finely-divided calcium carbonate can be replaced by precipitated calcium carbonate, i.e. PCC, or kaolin.
According to the invention the pigments used in the coating colours have a steep particle size distribution, a maximum of 35% of the pigment particles being smaller than 0.5 μm, and preferably a maximum of 15% are smaller than 0.2 μm.
The attached FIGS. 1 and 2 show the particle size distributions according to the present invention for gypsum and calcium carbonate, respectively, compared to conventional particle size distributions. As apparent from the figures, due to the steep distribution the cumulative particles size distribution curve of the invention lies clearly below the corresponding curve of a conventional pigment for the small pigment fractions. Correspondingly, the curve of carbonate is above that of the traditional pigments for middle size particles.
The invention can be applied to any pigment. Pigments are, e.g., calcium carbonate, calcium sulphate, aluminium silicate, kaolin (aluminium silicate containing cristallization water), aluminium hydroxide, magnesium silicate, talc (magnesium silicate containing cristallization water) titanium oxide and barium sulphate and mixtures of these. Also synthetic pigments may be used. Primary pigments of those mentioned above are kaolin and calcium carbonate, usually amounting to over 50% of the dry matter of the coating composition. Calcinated kaolin, titanium oxide, precipitated carbonate, satin white, aluminium hydroxide, sodium silica aluminate and plastic pigments are additional pigments and the amounts of these are usually below 25% of the dry matter content of the mixture. Special pigments to be mentioned are special kaolins and calcium carbonates and barium sulphate and zinc oxide.
Preferably the invention is implemented to calcium carbonate, calcium sulphate, aluminium silicate and aluminium hydroxide, magnesium hydroxide, magnesium silicate, titanium dioxide and/or barium sulphate and mixtures thereof, whereby it is particularly preferred to use as the main pigment of the pre-coat mixtures calcium carbonate or gypsum and in the surface coating colours and in single-coating colours mixtures of calcium carbonate or gypsum and kaolin.
The particle size distribution of the invention can be obtained by regulating e.g. the precipitation conditions of precipitated calcium carbonate such that the desired distribution is achieved. Alternatively, the grinding of natural minerals can be adjusted such that the desired particle sizes are obtained. The coarsest fractions can be separated from the fines by generally known screening methods.
Any binding agent know per se, which is frequently used for manufacturing paper, can be used as a binder. In addition to individual binders it is also possible to use mixtures of binding agents. As specific examples of typical binding agents the following can be mentioned: synthetic latex-type binders consisting of polymers or copolymers of ethyleneically unsaturated compounds, such as butadiene-styrene type copolymers which can contain a comonomer with a carboxylic group, such as acrylic acid, itaconic acid or maleic acid, and poly(vinyl acetate) which contains comonomers having carboxylic groups. In combination with the afore-mentioned substances e.g. water-soluble polymers, starch, CMC, hydroxy ethyl cellulose and poly(vinyl alcohol) can be used as binders.
In the coating mixture there can further be used conventional additives and adjuvants, such as dispersing agents (e.g. sodium salt of poly(acrylic acid)), substances for adjusting the viscosity and water rentention of the mixture (e.g. CMC, hydroxyethyl cellulose, polyacrylates, alginates, benzoate), lubricating agents, hardeners for improving the water resistance, optical agents, anti-foaming agents and substances for regulating the pH and for preventing product degradation. The lubricating agents include sulphonated oils, esters, amines, calcium and ammonium stearates; the agents improving water resistance include glyoxal; optical agents include diaminostilben and derivatives of disulphonic acid; the anti-foaming agents include phosphate esters, silicones, alcohols, ethers, vegetable oils, the pH-regulators include sodium hydroxide and ammonia; and, finally, the anti-degradation agents include formaldehyde, phenol and quaternary ammonium salts.
The coating colour can be applied on the material web in a manner known per se. The method according to the invention for coating paper and/or paperboard can be carried out on-line or off-line by using a conventional coater, i.e. a doctor blade coater, or by film press coating or by surface spraying. It is particularly preferred to adapt the solution to film press coating, in which it is possible to control mist-forming and drop formation at high speeds and with small coating amounts.
According to a particularly preferred embodiment, the paper web is double coated, the first coating being carried out by the film press method and the other coating by blade coating. The precoating is preferably performed by the film press method at high speed (at least 1450 m/min, preferably even 1600 m/min or more). The aimed coating amount is in precoating 8 g/m 2 and in surface coating 10/m 2 per side. Generally, the amount of coating colour applied to the web is 5-25 g/m 2 by the film press method and 5-40 g/m 2 by the blade coating, whereby the coating weights have been calculated from the dry matter of the coating.
The dry matter content of the coating colour used is at least 40%, preferably at least 50%, and in particular 50 to 65%. The immobilization point of the coating colour according to the invention is clearly lower than that of a coating colour produced from pigments having a traditional distribution. The immobilization of the coating colour already at a lower dry matter content significantly reduces mist-forming at high-speed coating with the film press method. Coating with smaller coating amounts is facilitated and drop formation can be avoided when it is not necessary to increase the dry matter of the coating colour.
By means of the invention it is possible to produce coated webs having excellent printability, good smoothness and high opacity and brightness. A particularly preferred product comprises a coated fine paper, the base paper of which has a grammage of 30 to 100 g/m 2 and it is produced from mechanical aspen pulp and chemical softwood pulp, the proportion of the mechanical aspen pulp of the fibrous substance of the paper is 20 to 70 weight-%. By coating a base paper of this kind, having a grammage of about 50 g/m 2 with a precoating of 8 g and a surface coating of 10 g/m 2 /side a fine paper is obtained which has a grammage of 70 to 90 g/m 2 , a brightness of at least 90%, an opacity of at least 90% and a smoothness of 1 μm or less.
The following examples illustrate the invention. The properties of the paper have been determined by the following standard methods in the examples:
Brightness: SCAN-P3:93 (D65/10°)
Opacity: SCAN-P8:93 (C/2)
Smoothness: SCAN-P76:95
Bendtsen coarseness: SCAN-P21:67
Gloss: Tappi T480 (75°) and T653 (20°)
EXAMPLE 1
Gypsum Pigment Having a Steep Particle Size Distribution
Two coating colours were prepared from gypsum. The compositions were:
Gypsum
70 parts by weight
Kaolin
30 parts by weight
SB latex
11 parts by weight
CMC
1 part by weight
Optical brightners
1 part by weight
The dry matter contents of the coating colours were 63% and their viscosity 1500 cP (Brookfield 100 rpm).
The kaolin was a typical finely divided glazing kaolin. Two different kinds of gypsum qualities were used in the coating colours. The gypsum qualities differed from each other as regards the particle size distribution; gypsum 1 had a normal distribution and gypsum 2 a steep. The distributions are presented in Table 1:
TABLE 1
Particle size distributions of gypsum pigments
Max. particle size
Cumulative weight ratio
[μm]
Gypsum 1 (normal)
Gypsum 2 (steep)
10
99
99
5
98
98
2
80
80
1
57
54
0.5
36
25
0.2
22
9
The particle size distributions of the gypsum pigments are also shown in the appended FIG. 1 . As appear from the figure and the above table the amount of gypsum pigment particles is clearly smaller from the particle sizes of 1.8 μm downwards. Between 3 and 1.8 μm the amount of the particles is, again, somewhat larger than for traditional pigments.
When the above-described mixtures were used for coating, a better coverage was obtained with the steep distribution. Due to this the particularly important parameters for the printing result, viz. opacity, gloss and smoothness are improved by means of the invention with 5 to 20%.
EXAMPLE 2
Production of a Coated Fine Paper
A base paper was produced from a mechanical aspen pulp (GW) and chemical pine pulp, which were mixed at a weight ratio of 40 to 60. Ground calcium carbonate was added as a filler to the suspension in an amount of about 10% of the fibrous material.
The base paper was produced on a gap former. The properties of the base paper were the following:
grammage
53.3 g/m 2
bulk
1.45 cm 3 /g
opacity
88%
brightness
82.5%
coarseness
240 ml/min
porosity
170 ml/min
filler content
12%
The base paper was coated twice, first with the film press method and then with doctor blade coating.
In the coating colours three kinds of calcium carbonate pigments were used. Their particle size distributions are presented in Table 2:
TABLE 2
Particle size distributions of carbonate pigments
Cumulative weight ratio
Max. particle size
Carbonate 1
Carbonate 2
Carbonate 3
[μm]
(normal)
(normal)
(steep)
5
92
98
99
2
62
87
95
1
38
63
70
0.5
20
38
35
0.2
8
18
10
Traditionally, product Carbonate 1 (normal, coarse) is used for precoating and product Carbonate 2 (normal, fine) for surface coating.
The coating colours were prepared by methods known per se by mixing together the pigment, binder and the additives. The compositions of the mixtures are shown in Table 3:
TABLE 3
Compositions of coating colours
Precoat mixture
Surface coating mixture
(weight parts)
(weight parts
According to
According to
Conventional
the invention
Conventional
the invention
Carb. 1
100
Carb. 2
75
Carb. 3
100
75
Glazing kaolin
25
25
SB latex
10
10
11
11
CMC
0.5
0.5
1
1
Further, additives conventionally used in coating colours, such as optical brighteners were employed.
The dry matter content of the pre-coat mixtures were 60% and the corresponding dry matter content of surface coating colours were 61%.
The base paper mentioned at the beginning of this example was coated with the above described coating colours in the following conditions:
Precoating by the film press method: 9 g/m 2 per side; and the surface coating at a doctor blade station: 10.5 g/m 2 per side at a speed of 1500 m/min. The coated paper was super-calendered.
The properties of the end product obtained using carbonate 3 were determined and compared to those of two commercially available fine papers, viz. Lumiart (Enso) and Nopacoat (Nordland Papier). The results will appear from Table 4:
TABLE 4
Optical properties of a double-coated fine paper
Paper
according to
the invention
Lumiart
Nopacoat
Grammage [g/m 2 ]
80
100
99
Bulk
0.85
0.83
0.78
Opacity [%]
94
92.7
92.6
Brightness [%]
94
91
96.7
Smoothness pps 10 [μm]
0.8
1.2
0.8
Gloss [%]
73
66
71
Table 4 shows that the properties of a fine paper produced by the invention are better in all respects than those of comparative papers having corresponding bulk and grammage which is an evidence that the method according to the invention provides better coverage. By combining the coating according to the invention to the described base paper it is possible to provide a fine paper, which gives a yield gain of over 20% compared to conventional fine papers.
EXAMPLE 3
The Influence of a Steep Distribution on Immobilization Point
The immobilization points of pigments having a traditional and a steep distribution, respectively, were determined from carbonate/kaolin-based coating colours. FIG. 3 shows the cumulative particle size distribution for carbonates 4 to 6. The determination has been performed by a method based on laser diffraction. Table 5 indicates the compositions of the coating colours.
TABLE 5
The compositions of the coating colours
Precoating colours
Surface coating colours
(parts by weight)
(parts by weight)
According to
According to
Conventional
the invention
Conventional
the invention
Carb. 4
80
70
Carb. 5
80
Carb. 6
70
Kaol. 1
20
20
Kaol. 2
30
30
CMC
0.7
0.7
0.7
0.7
Latex
10
10
10
10
Additive 1
0.6
0.6
Additive 2
6.6
6.6
Additive 1 is an optical brightner. Additives 2 include an optical brightner and other typical additives of coating colours. In both surface coating colours the same additives are incorporated in the same amounts
The results will appear from Table 6:
TABLE 6
The immobilization poins of coating colours of Table 5
Immobilization
Coating colour
Dry matter, %
point, %
Pre-coat,
61.5
82.7
conventional
Pre-coat, according
61.8
78.1
to the invention
Surface coating
60.5
80.0
colour, conv.
Surface coating
60.8
78.5
colour, invention
As the above results show, the immobilization point of precoating colours comprising carbonate pigments having a steep distribution (carb 1) appear at 4.6% units lower dry matter contents and even for surface coating colours at dry matters which are 1.9% units lower than for the reference. In both cases the reduction of the immobilization point is clear, for precoating colours it is significant.
EXAMPLE 4
Mist-Formation of Coating Colours
By using the receipt of Example 1 precoating colours were prepared and used for coating of a web by the film press method. A pilot coater was employed having an operating speed of 1500 m/s. The mist-formation was determined by placing a collecting vessel below the nip. The collecting vessel was attached to a scale which measured the mist in g/m 2 . When the amount of coating applied on the paper was 10 g/m 2 and the dry matter of the conventional coating colour about 61% and that of the coating colour according to the invention was lower, i.e. about 60%, still the amount of collected mist was two times higher for the conventional coating colour than for that of the invention.
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The present invention relates to a method for coating of a fibrous web. According to the method a coating color with pigments is applied to the surface of the web and dried in order to form a coated web. The invention comprises using a coating color which contains pigments having a steep particle size distribution, a maximum of 35% of the pigment particles being smaller than 0.5 μm. The coating color is spread on the surface of the web with a coating speed of at least 1450 m/min, preferably over 1600 m/min. The coating pigment having a steep particle size distribution gives rise to a coating color which solidifies at much lower dry substance than conventional coating colors. In this way coating can be controlled at high speed without runnability and quality problems.
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FIELD OF THE INVENTION
The present invention relates to transporting apparatus and in particular, but not exclusively, to apparatus for transporting a reel having a substantially central, hollow core.
BACKGROUND OF THE INVENTION
In the printing industry it is common to use large reels or rolls of paper which comprise a continuous length of paper wrapped around a central core. These reels are mounted onto printing machinery by lifting the reel and locating the core onto a receiving rod.
The weight of these paper reels is often considerable and it can be extremely difficult for even several persons to manually lift them into place. In order to ease this task, specialized lifting apparatus have been designed for lifting large paper reels. Such lifting apparatus generally comprises a four-wheeled trolley on which is mounted hydraulic, electrical or mechanical lifting machinery. Typically, a mandrel projects from the lifting machinery and is arranged to be located within the core of the reel to be lifted. The mandrel is then raised vertically to position the reel at an appropriate height for receipt by the receiving rod of the printing apparatus. Generally, the mandrel extends only part-way through the core in order to leave enough room at the opposite end of the core so that the core can be transferred onto the receiving rod of the printing machinery.
Reel lifting apparatus comprising hydraulic and electrical lifting machinery tends to be relatively expensive. On the other hand, whilst mechanical, hand operated lifting machinery is cheaper, it still tends to be complex and can be difficult for persons of small stature to operate. Both types of machinery require a large amount of space in which to operate.
BRIEF SUMMARY OF THE INVENTION
It is an object of the present invention to overcome or at least mitigate the disadvantages of conventional reel lifting apparatus.
In particular, it is an object of the present invention to provide a reel lifting apparatus which can be operated by a single person, and in a relatively confined space.
According to the present invention there is provided a transporter for lifting and transporting a reel having a substantially central, hollow core, the transporter comprising:
a chassis;
a pair of ground engaging wheels coupled to the bottom of the chassis;
a pair of handlebars coupled to an upper region of the chassis and arranged to allow an operator to pivot the chassis relative to the ground; and
an elongate mandrel projecting from the front of the chassis and arranged to be received by a core of a reel to be lifted and transported, the mandrel comprising deflecting means arranged to be deflected outwardly from the longitudinal axis of the mandrel by the weight of a reel when the mandrel supports a reel, so as to self-lock the mandrel within the core of the reel.
It will be appreciated that the mandrel may be released from the core of a reel by relieving the weight of the reel from the mandrel.
In one embodiment of the invention, the mandrel comprises a first portion integral with or rigidly secured to the chassis, a second portion hingeably coupled at an upper region thereof to said first portion, and reaction means engaging said first portion and extending at least part-way along said second portion to engage deflecting means coupled to the second portion, wherein, when the mandrel is not supporting a reel, the hingeable coupling is open and the reaction means maintains the deflecting means in a non-deflected position and, when the mandrel is supporting a reel, the hingeable coupling is arranged to substantially close due to the weight of the reel, moving the reaction means along said first portion in turn to move the deflector member to a deflected position to cause the mandrel to tightly engage the core of the supported reel.
Preferably, said chassis comprises a substantially upright frame with said two wheels being attached to the chassis for rotation about a common axis. However the frame may be provided with more than two wheels, e.g. three or four, at the bottom of the frame. The handlebars are preferably provided at the top of the upright frame.
Preferably, the mandrel projects from a substantially central region of the upright frame. Preferably, the upright frame is provided with a footplate projecting from the rear of the frame, at the bottom of the frame, to assist an operator to pivot the frame. Preferably also the frame comprises a stand for supporting the chassis in a near upright position.
Preferably, the second mandrel portion is additionally coupled to the first mandrel portion, or is coupled to the chassis, by a spring or other resilient means which acts to maintain the hingeable coupling open when the mandrel is not supporting a reel. More preferably, this spring or resilient means is connected to a flange which extends about the second mandrel portion.
In one embodiment of the present invention, the deflecting means comprises a third mandrel portion hingeably coupled at an upper end region thereof to an upper end region of the second mandrel portion, remote from said first mandrel portion. The reaction means may comprise a pin located within a channel extending through the second mandrel portion, the pin being substantially free to move within said channel and engaging at its ends respective end walls of the first and third mandrel portions.
Preferably, the second and third mandrel portions comprise cylinders of similar cross-section. The second and third portions are substantially axially aligned when the mandrel is in the non-supporting configuration, with the second hingeable coupling being substantially closed. When the mandrel begins to support a reel, the first hingeable coupling closes, and the pin is displaced through the second portion causing the second hingeable coupling to open, deflecting the third portion relative to the second portion. This causes the third portion to be forced against the upper inner surface of the reel core whilst the second portion is forced against the lower inner surface of the core.
In a second embodiment of the present invention, the deflecting member is arranged to lie substantially within the second member when the mandrel is in the non-supporting configuration. When the mandrel begins to support the reel, the reaction means is arranged to move within the second portion, and to radially deflect the deflecting means into contact with the inner surface with the reel core. More preferably, the reaction means comprises a cam surface which engages an inner surface of the deflecting means as the reaction means is moved longitudinally through the second portion, the deflecting means being forced outward relative to the second portion. The reaction means may comprise a spring or similar resilient means arranged to force the reaction means against the first mandrel portion, such that the hingeable coupling between the first and second portions remains open when the mandrel is in the non-supporting configuration.
According to another aspect of the present invention there is provided a transporter for lifting and transporting an item having a hollow core, the transporter comprising:
a chassis;
wheel means for engaging the ground coupled to the bottom of the chassis;
an operator grip coupled to an upper region of the chassis and arranged to allow an operator to pivot the chassis relative to the ground; and
an elongate mandrel projecting from the front of the chassis and arranged to be received by a core of an item to be lifted and transported, the mandrel comprising deflecting means for deflection radially outwardly of the mandrel when the mandrel supports an item, so as to lock the mandrel within the core of the item.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF DRAWINGS
For a better understanding of the present invention and in order to show how the same may be carried into effect reference will now be made, by way of example, to the accompanying drawings, in which:
FIG. 1 shows a side view of a reel transporter embodying the present invention;
FIG. 2 shows a front view of the reel transporter of FIG. 1;
FIG. 3 shows in detail a mandrel of the transporter of a FIG. 1 where the mandrel is in a non reel supporting configuration;
FIG. 4 shows a side view of the mandrel of FIG. 3;
FIG. 5 shows the mandrel of FIG. 3 in a reel supporting configuration;
FIGS. 6a to 6c illustrate the operation of the reel transporter of FIG. 1; and
FIG. 7 shows an alternative mandrel for use with the transporter of FIG. 1.
DETAILED DESCRIPTION OF THE INVENTION
There is shown in FIGS. 1 and 2 a reel lifting apparatus and transporter designed to lift a reel of paper having a central, hollow core. The transporter comprises a chassis 1 having an upright frame member 2 and a horizontal cross member 3 coupled to the bottom end of the upright member 2. A pair of wheels 4 are coupled to respective ends of the cross member 3 for rotation relative thereto. A support member 5, having a `V` shape, is connected at one end to an intermediate portion of the upright member 2 and at the other end to the center of the cross member 3. The support member allows the transporter to stand in its near-upright position. A pair of bull horn handle bars 6 are secured to the upper end of the upright member 2.
A mandrel 7 projects from the front of the upright member 2 and is arranged to be located in, and to engage, the core of a reel of paper to be lifted. The mandrel is shown in more detail in FIGS. 3 to 5.
The mandrel 7 comprises three portions 8, 9, 10 which are nominally aligned along a common longitudinal axis 11. The first portion 8 is formed integral with the upright member 2 and projects therefrom at a height above the ground which corresponds substantially to the height of a reel core above the ground when the reel is resting on the ground. The first portion comprises a pair of parallel, vertically aligned plates spaced apart by a small distance.
The second mandrel portion 9 is cylindrical in shape, having its axis nominally aligned with the axis 11, and is hingeably coupled at an upper edge region to the first mandrel portion 8 by way of a lug 12 which extends from the second portion to the slot 13 between the parallel plates of the first portion 8. The third mandrel portion 10 is also cylindrical in shape, having its axis nominally aligned with the axis 11. The third portion 10 is hingeably coupled to the second portion by way of a lug 14 which extends from the third portion to engage a slot 15 provided in the second portion.
A cylindrical channel 16 extends longitudinally through the second mandrel portion 9, the channel being offset from the cylinder axis, below the axis. A cylindrical pin 17 extends through the channel 16 provided in the second mandrel portion 9 and has a length greater than the length of that portion so that it projects from one or both of the ends of the channel 16.
A circular flange 18 is provided at the end of the second mandrel portion 9 adjacent the first mandrel portion 8. A curved pin 19 projects from the flange 18, towards the upright member 2 of the transporter frame, and receives one end of a spring 20. The spring is secured at its opposite end to the upright frame member 2.
Providing that no downward force is applied on the second or third portions of the mandrel 7, the spring 20 holds the hingeable coupling, provided between the first and second mandrel portions, open so that the pin 17 projects from the second portion 9 to abut the first portion 8. As a result, the second and third portions tend to be aligned along a common longitudinal axis. This axis is arranged to extend substantially horizontally when the transporter is in the fully upright position (see FIG. 6).
When it is desired to lift and transport a paper reel, the transporter is held in the fully upright position, as shown in FIG. 6c, and is wheeled forward so that the second and third portions 9, 10 of the mandrel 7 enter the paper reel core 29. The combined length of the second and third portions of the mandrel 7 is such that the mandrel 7 projects only part-way along the reel core 29. In order to lift the reel, the operator applies a forward force to the cross-bar 3 with his or her foot whilst pulling back on the handle bars 6, causing the transporter to tilt backwards about the axis of the wheels 4. The mandrel portions 9, 10 are raised upward within the paper reel core 29 by this action until the front upper edge of the third mandrel portion 10 contacts the core 29.
As the transporter is tilted still further, the third mandrel portion 10 is forced downward relative to the first mandrel portion 8. This action causes the pin 17 to be displaced through the channel 16 in the second mandrel portion and forced against the abutting wall of the third mandrel portion 10. The hingeable coupling between the first and second mandrel portion 8, 9 therefore tends to close whilst the hingeable coupling between the second and third portions 9, 10 tends to open. The third mandrel portion 10 is displaced relative to the axis 11. The greater the weight supported by the mandrel 7, the greater the displacement force applied to the third mandrel portion 10. This arrangement therefore provides for self-locking of the mandrel within a reel core.
Once the paper reel is raised off the ground, the operator can push the transporter and the reel forward and can align the core of the paper reel with a receiving rod provided on a printing machine. Once aligned, the transporter is pushed forward to locate the open end of the reel core on the rod. The operator can then allow the transporter to tilt forward into an upright position to unlock the mandrel from within the core. If necessary, the operator can then push the paper reel forward to secure the reel core on the receiving rod. The transporter is then withdrawn from the reel core.
There is shown in FIG. 7 an alternative mandrel which can be substituted for the mandrel of FIG. 3 in the transporter of FIG. 1. The mandrel of FIG. 7 comprises first and second mandrel portions 21, 22, the first portion 21 being coupled to, or integral with, the upright member of the transporter in the same manner as the first portion of the mandrel of FIG. 3. Similarly, the second portion 22 is hingeably coupled to the first portion 21. An inner cylindrical member 23 is located within a channel 24 provided within the second portion 22 and is secured to a central pin 25 which projects from the second portion to contact the opposed end wall of the first mandrel portion 21. A spring 28 is disposed around one end of pin 25, between the end of the inner member 23 remote from the first mandrel portion 21, and the inner surface of the second mandrel portion.
The end of the inner member 23 is trusto-conical in shape so as to provide a cam portion 26 which contacts an inwardly projecting region of a deflecting pin 27. The deflecting pin 27 is substantially `T` shaped and is pivotally coupled to an outer region of the second mandrel portion 22.
As described above, in order to lift a paper reel, the mandrel is aligned and inserted into a core of a reel to be lifted. As the transporter is tilted backwards, the second mandrel portion 22 is forced into contact with the inner surface of the reel core. This causes the pin 25 to be forced against the abutting end wall of the first mandrel portion 21 which in turn causes the inner member 23 to compress the spring 28 and to drive the cam portion of the inner member across the deflecting member 27. The deflecting member 27 is driven outward into contact with the upper inner surface of the reel core. The reel can then be lifted and transported to engage the open end of the core with a receiving rod on a print machine. As the transporter is returned to the upright position, the force on the pin 25 is removed and the spring 28 forces the inner member 23 to return to its nominal position, returning the deflecting member 27 to lie wholly within the second portion 22. The transporter can then be moved to withdraw the mandrel from the reel core.
It will be appreciated that various modifications may be made to the above described embodiments without departing from the scope of the present invention. In particular, the mandrel may be attached to the transporter by way of a sliding coupling 30 to enable the height of the mandrel above the ground to be varied. This enables various sizes of reels to be lifted by the transporter.
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A transporter for lifting and transporting a paper reel having a central core. The transporter has an upright frame at the base of which are provided a pair of ground engaging wheels. A generally cylindrical mandrel, arranged to be received by the core of a reel to be lifted, projects from the front of the frame. The mandrel comprises a deflector member which is arranged to be deflected outwardly relative to the mandrel axis as the transporter frame is tilted backwards to cause the mandrel to take the weight of a paper reel. The deflector member is thus forced against the inside of the reel core, causing the mandrel to self-lock within the core.
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BACKGROUND OF THE INVENTION
[0001] Stator cores of electromagnetic machines are made up of many thin steel laminations stacked together to form a large cylindrical body. Each lamination comprises a segment of a circular cross-section making up the cylindrical body. Maintaining the integrity of these thin laminations as a stator core requires inward compression exerted from either end of the stacked laminations.
[0002] In known machines, this compressive force is imparted by a plurality of rigid key bars extending from one end of the stator to the other. Typically, the laminations include dovetail slots or similar features that correspond to a compatible dovetail or similar feature on the key bars. Individual components of the stator core are stacked at either end of the stator and compressive force applied to the stator core by torquing a nut at either or both end of each of the key bars. Typically, each lamination is placed onto an assembly frame or system of rails and a compressive force applied following the installation of each lamination or after a few laminations have been installed.
BRIEF DESCRIPTION OF THE INVENTION
[0003] In one embodiment, the invention provides a method of exerting a compressive force to components of a stator core of an electromagnetic machine, the method comprising: affixing a first end of a wire rope member to a first flange plate disposed adjacent a first end of a plurality of stator laminations; affixing a second end of the wire rope member to a second flange plate disposed adjacent a second end of the plurality of stator laminations; tensioning at least one of the first end or the second end of the wire rope member against at least one of the first flange plate and the second flange plate to exert a compressive force against the first flange plate, the second flange plate, and the plurality of stator laminations.
[0004] In another embodiment, the invention provides a stator core for an electromagnetic device, the stator core comprising: a plurality of stacked stator laminations; at least one flange member adjacent a first end of the plurality of stacked stator laminations; and a wire rope member attached to the at least one flange member, the at least one wire rope member, upon tensioning, exerting a compressive force against the at least one flange member.
[0005] In still another embodiment, the invention provides an electromagnetic device comprising: a plurality of stacked stator laminations; at least one flange member adjacent a first end of the plurality of stacked stator laminations; and a wire rope member attached to the at least one flange member, the at least one wire rope member, upon tensioning, exerting a compressive force against the at least one flange member.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] These and other features of this invention will be more readily understood from the following detailed description of the various aspects of the invention taken in conjunction with the accompanying drawings that depict various embodiments of the invention, in which:
[0007] FIG. 1 shows an axial cross-sectional view of a stator core according to an embodiment of the invention.
[0008] FIG. 2 shows a radial cross-sectional view of a stator core according to an embodiment of the invention.
[0009] FIGS. 3-4 show detailed radial cross-sectional views of portions of stator cores according to other embodiments of the invention.
[0010] FIG. 5 shows a schematic view of a portion of a wire rope member used in some embodiments of the invention.
[0011] FIGS. 6-7 show schematic cross-sectional views of wire rope members used in some embodiments of the invention.
[0012] FIG. 8 shows a cross-sectional side view of a wire rope member and attachment device used in some embodiments of the invention.
[0013] FIG. 9 shows a top view of FIG. 8 .
[0014] FIG. 10 shows a flow diagram of a method according to an embodiment of the invention.
[0015] It is noted that the drawings of the invention are not to scale. The drawings are intended to depict only typical aspects of the invention, and therefore should not be considered as limiting the scope of the invention. In the drawings, like numbering represents like elements among the drawings.
DETAILED DESCRIPTION OF THE INVENTION
[0016] Embodiments of the present invention comprise methods for the assembly of stator cores using flexible wire rope rather than rigid key bars, as well as systems for the assembly of such stator cores and stator cores assembled according to such methods or using such systems.
[0017] Turning now to the drawings, FIG. 1 shows a schematic side view of a stator core 100 according to one embodiment of the invention. Here, stator core 100 comprises a plurality 10 of stacked laminations A, B, C . . . X disposed between a pair of flange plates 20 , 22 . Typically, laminations A, B, C . . . X comprise thin insulated steel plates, which may number in the hundreds or thousands, depending on the application to which the stator core 100 will be put. Flange plates 20 , 22 are typically comprised of steel or aluminum, although other materials may be used.
[0018] A plurality of wire rope members 30 A through 30 H extend from the first flange plate 20 to the second flange plate 22 . Wire rope members may include any number of materials, including, for example, solid metal wires, twisted or braided metal wires, polyethylene fibers, nylon fibers, etc. In some embodiments of the invention, the wire rope members comprise wire rope made up of a plurality of braided metal strands surrounding a solid or braided metal core. Other materials are possible, of course, and the term “wire rope member,” as used herein, is intended to refer broadly to a flexible wire capable of imparting a compressive force to a plurality of stacked laminations.
[0019] FIG. 2 shows a cross-sectional view of the stator core 100 of FIG. 1 taken along the plane of lamination A. As can be seen in FIG. 2 , lamination A includes a plurality of segments A1 through A8. Although lamination A is shown as comprising eight segments in FIG. 2 , one skilled in the art will recognize that any number of segments may be employed. When assembled, segments A1 through A8 form a central bore 12 having a plurality of slots 14 for containing stator windings (not shown).
[0020] A plurality of wire rope members 30 A through 30 P are disposed around lamination A. As shown in FIG. 2 , each segment of lamination A includes two wire rope members along its outer surface, although this is not essential. Any number of wire rope members may be employed, with any portion of the total number of wire rope members being disposed adjacent each of the segments of lamination A.
[0021] FIG. 3 shows a detailed view of a portion of segments A1, A2 according to another embodiment of the invention. Here, segment A1, representative of each of the segments, includes channels 16 A, 16 B into which wire rope members 30 A, 30 B, respectively, may be disposed. In some embodiments, channels 16 A, 16 B include openings greater than the diameters of wire rope member 30 A, 30 B, respectively. In other embodiments, channels 16 A, 16 B include openings larger than the diameters of wire rope members 30 A, 30 B, respectively, such that wire rope members 30 A, 30 B may be threaded through adjacently stacked laminations of the stator core.
[0022] In other embodiments, such as that shown in FIG. 4 , the wire rope members 30 A, 30 C may be threaded through axial holes 26 A, 26 C, respectively, in segments A1 and A2. The placement of axial holes 26 A, 26 C may be matched to create uniform compressive stress in the stator core. One skilled in the art will recognize that some embodiments of the invention may include features of both FIG. 3 and FIG. 4 .
[0023] Embodiments of the invention, such as those shown in FIGS. 1-4 , may be useful in the assembly of stator core 100 ( FIG. 1 ). For example, pre-stress in the wire rope members may be adjusted during various stages of the assembly of a stator core and/or during the subsequent installation of the stator core in a supporting frame. Such adjustment of the tension may aid in the stacking of stator core laminations and/or movement of the assembled stator core.
[0024] FIGS. 5-6 show views of wire rope members according to various embodiments of the invention. FIG. 5 shows a side view of a wire rope member 30 comprising a plurality of braided wire strands 31 - 36 . FIG. 6 shows a radial cross-sectional view of wire rope member 30 , showing wire strands 31 - 36 disposed about a central wire strand 37 . In some embodiments, strands 31 - 36 may include flattened rather than rounded surfaces to improve contact friction.
[0025] FIG. 7 shows a radial cross-sectional view of wire rope member 30 including an optional insulating layer 38 . Insulating layer 38 may include any number of materials, including, for example, rubbers, vinyls, polypropylene, polyethylene, epoxies, polyethylene, etc. Insulating layer 38 reduces fretting of wire strands 31 - 36 , which might otherwise occur upon contact with flange plates 20 , 22 or the laminations of the stator core. It should be noted that insulating layer 38 may be affixed to wire rope member 30 or, in some embodiments of the invention, may surround wire rope member 30 , such that wire rope member 30 may be threaded into and through insulating layer 38 .
[0026] FIG. 8 shows a cross-sectional side view of flange plate 20 according to an embodiment of the invention. For the sake of simplicity, the interaction of wire rope members and flange plate 20 will be described with respect to wire rope member 30 H only. Flange plate 20 includes a conically-shaped passage 40 H through which wire rope member 30 H may be passed. Passage 40 H may include a locking mechanism for securing wire rope member 30 H within passage 40 H. As shown in FIG. 8 , such a locking mechanism includes a plurality of wedge-shaped members 42 H, 44 H adapted to compress and secure wire rope member 30 H within passage 40 H. Wedge-shaped member 42 H, 44 H include a first surface for contacting wire rope member 30 H and a second member for contacting a wall of passage 40 H. Wedge-shaped members 42 H, 44 H, as their name suggests, include a narrower end and a wider end. Wire rope member 30 H may be tensioned within passage 40 H by drawing wire rope member 30 H through passage 40 H, i.e., from the narrower end toward the wider end of wedge-shaped member 42 H, 44 H.
[0027] FIG. 9 shows a top view of a portion of flange plate 20 including passage 40 H. Here, three wedge-shaped members 42 H, 44 H, 46 H restrain wire rope member 30 H within passage 40 H.
[0028] Stator cores employing wire rope members as described above provide a number of advantages over conventional key bar stator cores. Wire rope, for example, has a higher breaking strength, typically greater than 250 ksi, than key bars. As a consequence, a greater compressive force may be exerted upon stacked laminations than is possible using key bars.
[0029] Wire rope members may also be secured and tensioned using any number of devices and techniques. For example, various devices are commercially available for tensioning wire rope members. Such devices may be employed to tension wire rope members from either or both ends of the stator core by drawing the wire rope members away from the flange plates and the laminations along a longitudinal axis of the stator core.
[0030] In addition, the use of wire ropes permits pre-assembly of a plurality of laminations and their segments, which is not possible using key bars to compress the stator core. Such pre-assembly can greatly reduce assembly time and costs.
[0031] FIG. 10 shows a flow diagram of a method according to an embodiment of the invention. At S 1 , a wire rope member is affixed to a first flange plate adjacent a first end of a plurality of stacked stator laminations. At S 2 , the wire rope member may optionally be inserted into a channel along each of the plurality of stacked stator laminations. At S 3 the wire rope member is affixed to a second flange plate adjacent a second end of the plurality of stacked stator laminations. At S 4 , the wire rope member is tensioned against at least one of the first flange plate and the second flange plate, thereby applying a compressive force against the plurality of stacked stator laminations.
[0032] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
[0033] This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any related or incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
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Embodiments of the invention relate generally to electromagnetic devices and, more particularly, to the compression of stator core laminations using wire rope members and to stator cores and electromagnetic devices employing such wire rope members. In one embodiment, the invention includes: affixing a first end of a wire rope member to a first flange plate disposed adjacent a first end of a plurality of stator laminations; affixing a second end of the wire rope member to a second flange plate disposed adjacent a second end of the plurality of stator laminations; tensioning at least one of the first end or the second end of the wire rope member against at least one of the first flange plate and the second flange plate to exert a compressive force against the first flange plate, the second flange plate, and the plurality of stator laminations.
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This is a Continuation in Part of Ser. No. 10/228,386, filed Aug. 27, 2002, scheduled to issue as U.S. Pat. No. 6,682,147 on Jan. 27, 2004. The invention relates to an adjustable support and, more particularly, to a foot rest support which can be adjusted in both height and width.
BACKGROUND OF THE INVENTION
1. Field of the Invention
2. Description of the Need for the Invention
Many persons, particularly elderly and disabled persons, often desire to have an accessory, such as a foot rest, which can be used in a variety of ways. In one usage, a person might wish to elevate the foot or both feet in order to alleviate a physical condition, such as pain that is occasioned by having the foot occupy a restrained position for a prolonged period of time. In other usages, the foot rest can provide a suitable support when the person is seated or is in a position where such support is desired.
The prior art provides a number of footrest. One type is provided by a frame that is inserted into separated slots of a plate, but this arrangement is not adjustable in height or width.
Other solutions have been proposed which typically are complex and costly.
Accordingly, it is a principal object of the invention to provide a support that is inexpensive and simple to construct and can meet the requirements of persons who wish to adjustably support body appendages such as legs in order to satisfy a physical or exercise requirement.
SUMMARY OF THE INVENTION
In accomplishing the foregoing and related objects, the invention provides a rest member having a support surface; and a stand for the rest member; which has apertures therein to permit the adjustment in height thereof with respect to the stand; and the stand has means thereon for inhibiting any tendency for the stand to become separated from the rest member during usage thereof.
In accordance with one aspect of the invention, the inhibiting means is compressible to permit the stand to be inserted thru the rest member and expandable thereafter to inhibit separation of the rest member from the stand. The inhibiting means can comprise at least one object. Alternatively, the inhibiting means can be a projection from the stand to inhibit separation of the rest member once it is positioned on the stand. The projection can can have the same or a lesser width that portion of the rest member that is inserted on the stand.
Where the stand has a tubular portion the object can be attached to the tubular portion, and the object can projects from the stand, being compressible if the object is wider than the tubular portion and being non-compressible if the object is equal or narrower than the tubular portion, which can have a variety of cross sections and include a rectilinear channel member having an open side. Alternatively, the stand can be a solid member.
In accordance with another aspect of the invention, the inhibiting member is movable inwardly and outwardly, and can comprise an elastomeric object, or a plurality of elastomeric objects, such as a rubber ring.
In accordance with a further aspect of the invention, the stand can have an apex and the inhibiting means can be positioned at the apex.
In a method of the invention for supporting an object, the steps can include (a) providing a rest member having a support surface; (b) forming a plurality of differently dimensioned constructs in the support surface; and (c) positioning the rest member on a stand therefor to permit the adjustment in height of the rest member with respect to the constructs
The method can include the step of positioning means for inhibiting the accidental separation of the stand from said rest member after the stand has engaged the constructs, which can be apertures.
The stand can have at least one apex and further include the step of positioning inhibiting means at the apex, with the inhibiting means comprising an elastomeric object and further include the step of engaging at least one of the constructs by the elastomeric object, which can take the form of a rubber ring and further include the step of engaging at least one construct by the rubber ring.
At least one of the constructs can be an aperture smaller than the maximum dimension of the rubber ring when positioned on the stand and further include compressing the rubber ring to allow insertion into the aperture, followed by the step of pushing the rubber ring thru the aperture.
The rubber ring can be variably positioned on the stand.
The method can further include the step of providing the rest member with a plurality of elongated apertures of different lengths, with the stand inserted into two of the apertures and inhibited from separation therefrom by the inhibiting means.
DESCRIPTION OF THE DRAWINGS
Other aspects of the invention will become apparent after considering several illustrative embodiments taken in conjunction with the drawings in which:
FIG. 1 is a perspective view of an adjustable support in accordance with the invention that permits forward and backward movement of its support surface and inhibits separation of the support surface from its stand;
FIG. 1A is a perspective view of an adjustable support in accordance with the invention that permits forward and backward movement of its support surface and alternatively inhibits separation of the support surface from its stand;
FIG. 2 is a perspective view of the support for the embodiment of FIG. 1 ;
FIG. 2A is a perspective view of the support for the embodiment of FIG. 1A ;
FIG. 3 is a perspective view of the support of FIG. 1 for which the support surface has been lowered by being moved to the outermost support position of the stand with inhibition of separation of the support surface from its stand at the lowered position;
FIG. 4 is a perspective view of the support of FIG. 3 which has been positioned for possible side-to-side movement of an object placed on the support surface with double inhibition of separation of the support surface from its stand;
FIG. 5 is a perspective view of an alternate embodiment in which the elongated support surface of FIG. 4 has been positioned for possible forward and backward movement;
FIG. 6 is a perspective view showing separation of the tubular members forming the stand and indicating the use of two objects for inhibiting the separation of the support surface from its stand at two different levels.
DETAILED DESCRIPTION
As shown in the perspective view of FIG. 1 , an adjustable support 10 in accordance with the invention is formed by a support member 20 having a support surface 22 and a plurality of pairs P 1 thru P 3 of elongated apertures in the support surface 22 . In the embodiment of FIG. 1 there are three pairs of apertures P 1 , P 2 and P 3 , with the first pair P 1 formed by elongated apertures P 1 - 1 and P 1 - 2 , the second, shorter pair P 2 formed by elongated apertures P 2 - 1 and P 2 - 2 , and the third pair P 3 - 1 and P 3 - 2 formed by a still shorter pair P 3 . The longer pair P 2 accompanies the shorter pairs P 1 and P 3 in order to permit adjustment in height of the support surface 22 with respect to a stand 30 . The support member 20 is positioned at its aperture positions over apex portions 31 - 1 and 31 - 2 of the stand 30 , which includes apex inhibiting grommets 41 - 1 and 41 - 2 .
As illustrated in FIG. 1 , the support member 20 has its apertures P 1 - 1 and P 1 - 2 on the apex members 31 - 1 and 31 - 2 so that the support surface is in its intermediate lower position. When the stand 30 is adjusted so that the apex members 31 - 1 and 31 - 2 respectively occupy the apertures P 3 - 1 and P 3 - 2 , the support surface is in an elevated position.
Whether the stand occupies the first pair of apertures P 1 , the second pair of apertures P 2 , or the third pair of apertures P 3 , the support 10 permits forward movement as indicated by the arrow F, and backward movement as indicated by the arrow B of the support surface 22 , with separation of the support 10 from the members 31 - 1 and 31 - 2 inhibited by the grommets 41 - 1 and 41 - 2 . Although the grommets 41 - 1 and 41 - 2 are shown at the apex positions, i.e. the peaks of the stand 30 , they may be positioned at other locations on the stand as illustrated in FIGS. 3-6 .
In addition the grommets 41 - 1 and 41 - 2 may be used singly or multiply and are illustratively constructed of elastomeric material to be larger, when place on the stand 30 than the apertures through which they are moved. This takes place by compression as the grommets are moved through their apertures, followed by expansion once they have cleared the apertures. Although the grommets are desirably elastomeric, non elastomeric grommets may also be employed to provide a measure of separational inhibition.
As shown in FIG. 2 , which is a perspective view of the support 10 for the embodiment of FIG. 1 , the stand 30 is formed by a pair of tubular members 32 - 1 and 32 - 2 . The members 32 - 1 and 32 - 2 are adjustable inwardly and outwardly by virtue of rods 33 which are inserted between adjoining legs of the tubular members 32 - 1 and 32 - 2 . Each tubular member 32 - 1 or 32 - 2 has a leg 34 - 1 or 34 - 2 extending to an upwardly disposed connector 35 - 1 that forms an acute angle A with respect to the leg 34 - 1 or 34 - 2 . The upward connector 35 - 1 or 35 - 2 can be extended to a downwardly disposed connector 36 - 1 or 36 - 2 attached to a leg 37 - 1 or 37 - 2 . At the apexes 31 - 1 and 31 - 2 of the legs 34 - 1 and 34 - 2 there arer respective grommets 41 - 1 and 41 - 2 .
Insertion of the rod 33 into a leg 34 - 1 of the stand 30 permits connection to an opposite leg 34 - 2 , and relative movement between the connected legs 34 - 1 and 34 - 2 . Similarly, insertion of the rod 33 into a leg 37 - 1 permits connection to an opposite leg 37 - 2 . Because of the adjustability of the stand 30 , the support member 20 is provided, as discussed above with a plurality of elongated apertures P 1 and P 2 of different lengths into which the stand 30 is insertable. As in the case of FIG. 1 , the support surface 22 can be moved forwardly in the direction of the arrow F or backwardly in the direction of the arrow B.
As shown in the perspective view of FIG. 1A an alternative support 10 ′ in accordance with the invention is formed by a support member 20 ′ having a support surface 22 ′ and a plurality of pairs P 1 thru P 2 of apertures in the support surface 22 ′.
In the embodiment of FIG. 1A there are two pairs of apertures P 1 and P 2 , with the first pair P 1 formed by apertures P 1 - 1 and P 1 - 2 , and the second, longer pair P 2 formed by apertures P 2 - 1 and P 2 - 2 . The longer pair P 2 accompanies the shorter pair P 1 in order to permit adjustment in height of the support surface 22 ′ with respect to a stand 30 ′. The support member 20 ′ is positioned at its aperture positions over apex portions 31 - 1 and 31 - 2 of the stand 30 , which includes apex inhibiting projections 42 - 1 and 42 - 2
As illustrated in FIG. 1A , the support member 20 ′ has its apertures P 1 - 1 and P 1 - 2 on the apex members 31 - 1 and 31 - 2 so that the support surface 22 ′ is in its highest position. When the stand 30 ′ is adjusted so that the apex members 31 - 1 and 31 - 2 respectively occupy the apertures P 2 - 1 and P 2 - 2 , the support surface 22 ′ is in a lower position.
Whether the stand occupies the first pair of apertures P 1 , or the second pair of apertures P 2 , the support 10 ′ permits forward movement as indicated by the arrow F, and backward movement as indicated by the arrow B of the support surface 22 ′, with separation of the support 10 from the members 31 - 1 and 31 - 2 inhibited by the projections 42 - 1 and 42 - 2 . Although the projections 42 - 1 and 42 - 2 are shown at the apex positions, i.e. the peaks of the stand 30 ′, they may be positioned at other locations.
In addition the projections 42 - 1 and 42 - 2 may be used singly or multiply and are illustratively constructed of rigid or flexible material to be equal in width or smaller, when place on the stand 30 ′ than the apertures through which they are moved. The projections 42 - 1 and 42 - 2 may be formed by a bend of the tubular members 36 - 1 and 36 - 2 .
As shown in FIG. 2A which is a perspective view of the stand 30 ′ for the embodiment of FIG. 1A , the stand 30 ′ is formed by a pair of members 32 - 1 and 32 - 2 . Although the tubular members 36 - 1 and 36 - 2 have circular cross-sections, other cross sections are suitable, including elliptical and rectangular. Alternatively the 32 - 1 and 32 - 2 may be solid rods or take the form of rectangular channel members having an open forth side.
In addition, although the members 32 - 1 and 32 - 2 are adjustable inwardly and outwardly by virtue of rods 33 which are inserted between adjoining legs 32 - 1 and 32 - 2 , the legs 32 - 1 and 32 - 2 may be separate structures that are independently movable with respect to the apertures P 1 and P 2 . Although the upwardly disposed connector 35 - 1 in FIG. 2A forms an acute angle A with respect to the leg 34 - 1 , the angle A may be increase to about ninety degrees and the legs 34 - 1 and 37 - 1 extended, for example at a right angle to provide base support for the connectors 35 - 1 and 36 - 1 .
At the apexes 31 - 1 and 31 - 2 of the legs 34 - 1 and 34 - 2 there are respective projections 42 - 1 and 42 - 2 . The projections 42 - 1 and 42 - 2 can take the form pins inserted thru the connectors 36 - 1 and 36 - 2 , and capped with a rounded end to avoid stick injuries to the user.
For adjustability of the stand 30 ′ of FIG. 1A , the support member 20 ′ is provided, as discussed above with a plurality of apertures P 1 and P 2 into which the stand 30 ′ is insertable. As in the case of FIG. 1 , the support surface 22 can be moved forwardly in the direction of the arrow F or backwardly in the direction of the arrow B.
As shown in FIG. 3 , which is a perspective view of the support of FIG. 1 , the support surface 22 has been lowered by being moved to the outermost support position provided by the apertures P 2 of the stand 30 . The grommets 41 - 1 and 41 - 2 have been lowered to stabilize the new position of the support surface 22 .
By contrast, with FIG. 3 , FIG. 4 is a perspective view of the support of FIG. 3 , which has been positioned for possible side-to-side movement indicated by the arrows S of an object placed on the support surface 22 . Each leg of the stand 30 includes two grommets 41 - 1 and 42 - 1 on one leg, and grommets 41 - 2 and 42 - 2 on the other leg.
In the alternative embodiment of FIG. 5 , the elongated support surface 22 of FIG. 4 has been positioned for possible forward and backward movement, again indicated by the arrows F and B by the use of an elongated pair of apertures P 1 - 1 and P 1 - 2 . In addition, a further set of shorter apertures P 3 - 1 and P 3 - 2 are positioned near the respective elongated edges 35 - 1 and 35 - 2 to permit forward and backward movement of the support surface 22 in the position of maximum elevation for the support 10 .
To clarify the relationship of the rods 33 to the stand members 32 - 1 and 32 - 2 , the portion 32 - 1 is shown in FIG. 6 separated from the portion 32 - 2 , with one rod 33 removed and the other rod 33 retained in only one leg. In addition the leg 32 - 1 is shown with two grommets 41 - 1 and 43 - 1 at two separated positions on the leg below the apex 31 - 1 . This provides inhibition of the separation of the support from the stand at two different positions. It is apparent that one or more grommets may be used for each different support position
It will be understood that the foregoing detailed description is illustrative only and that modifications may be made without the departing from the spirit and scope of the invention as defined in the appended claims.
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Method and apparatus providing a rest member having a support surface and a stand for the rest member, with the rest member having a plural multiplicity of apertures therein to permit the adjustment in height thereof with respect to the stand, which can take the form of an expandable member associated with the rest member and being contractable as well as expandable inwardly and outwardly and accompanied by means for inhibiting the separation of the rest member from stand after the rest member has been positioned on the stand.
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DESCRIPTION OF THE PREFERRED EMBODIMENT
The machine which is the subject of the present invention is characterized by a combination of high-pressure liquid jets acting over the entire breadth of the fabric being processed, said jets being very fine, the better to penetrate the fabric. The jets are projected by special nozzles, placed transversely in relation to the cloth and tangential to it, which act upon the fabric at the point where there is a receiving piece having an opening, parallel to and much broader than the aforementioned nozzles, which allows the partial or total passage of the liquid after it has passed through the textile band.
In addition to the aforementioned nozzles, the machine in question also has a system of supporting drums provided with fine wire or equivalent elements forming segments having a wire mesh placed above them for the reception of the textile band as well as to support the same while it is being processed by the liquid.
In addition, the machine according to this invention also comprises two pressure cylinders placed so that they act at the exit point of the textile band and provided therebelow with two low-pressure jets which impregnate the fabric with liquid, achieving by means of rollers of adequate hardness, improved treatment of the textile fabric by means of pressure.
The invention will be more specifically illustrated by the following drawings and the description relating thereto, wherein:
FIG. 1 is a diagrammatic section of a machine built according to the present invention;
FIG. 2 shows a cross-section along the plane II--II of FIG. 1;
FIGS. 3 and 4 represent a detailed cross-section of the nozzles;
FIGS. 5 and 6 show details of the supporting wire drum for the textile band;
FIG. 7 is a view in perspective and in detail of the aforementioned drum;
FIG. 8 is a diagrammatic section of an alternate construction for the collection tank of a machine according to this invention.
As shown in the foregoing figures, the machine of the subject invention has a main processing chamber 1 where several linear nozzles are arranged as in 2, 3, 4 and 5, the structure of which is shown in detail in FIGS. 3 and 4. As can be seen, the nozzles have tubular cavities in which a fine radial nozzle 6 opens transversely with respect to the width of the textile band, said nozzle being, for example, approximately 2 or 3 tenths of a millimeter in width and able to project a jet of liquid at high pressure against the textile band 7 which is mechanically guided to pass in front of said nozzles and tangentially to it, so that the liquid partially or totally passes through said textile band. The action of the nozzles FIG. 3 is completed by a support in the form of a slit formed by two braces or similar members 8 and 9, separated from each other by a small space but of considerably greater breadth than the aperture of nozzle 6 for receiving the liquid that has passed through the textile band. Said braces 8 and 9 are movably constructed to approach each other or separate in order to attain the desired width for form a channel for receiving the liquid from the nozzle.
The aforesaid nozzles may also act, as shown, at the extremes of the main chamber 1, over corresponding drums 10 and 11, the detailed structure of which is shown in FIGS. 5, 6 and 7.
The aforesaid drums consist of a hub or central axle 12 and multiple wire parts 13 radiating from the rings with plates at each end 14 and 15 solidly attached to the axle 12, and extending longitudinally of axle 12 to form a series of projections 16 and indentations 17, in order to allow the textile band to receive the processing liquid that passes through it. A wire mesh 24 is fitted on the periphery of the wire drum.
The main treatment chamber 1 has removable access lids 18, 19 and 43 which improve the performance of the entire zone of nozzles, drums and adjustable supports.
In addition, the machine is complemented by a set of upper rollers 20 and 21 placed at the exit of the machine which, together with the low-pressure nozzles 22 and 23, located before arriving at said cylinder and near the tangency zone, dispense fresh treating liquid, which may be water for washing if so desired. The joint action of the jets towards the tangency zone and the interplay of appropriately hard rollers, make it possible to press out the liquid absorbed by the fabric, thus partially renewing it. In addition, the liquid not absorbed by the fabric acts by means of gravity and adherence to the textile band before reaching the rollers, thus improving the processing.
From the second wire drum 11 to the cylinders 20 and 21, a conventional stretching attachment 44 is located to prevent wrinkling of the fabric.
The machine connects through a small-diameter, vertical channel 25 with a lower tank 26 where a roller 27 receives the textile band coming from outside, allowing it to be fed back towards the interior of the connecting chamber 25 where a part of the treatment is carried out. The tank 26 has a given level of processing liquid 28 which is made to re-circulate, by means of a system of pumps, towards the impulsion nozzles, after passing through filters.
In the alternate receiving tank of FIG. 8, intended for knitted fabrics, the drum 29 is of considerable size and is so disposed in the interior of the chamber 30 corresponding to lower tank 26 in FIG. 1 that the textile band 31 enters said chamber from a pair of rollers 32 and 33 and fits over the rounded outer section of the aforesaid drum which is closed at the ends and has several nozzles such as 34, 35, 36 and 37, distributed over its periphery with their respective outlets for liquid disposed in radial fashion.
It is a characteristic of this alternate that the tangential velocity of the roller 32 is slightly greater than that of the drum 29 and also that the processing liquid should circulate from the interior of the drum 29 by means of lines 45 leading to the pump 38 and from this, by means of the pipes 39, 40, 41 and 42 towards the lineal nozzles, thus establishing a closed circuit which may be complemented by a system of filters and dispensers for the addition of processing products.
Resort may be had to such modifications and equivalents as fall within the spirit of the invention and the scope of the appended claims.
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A machine is described for the processing of textile fabrics, arranged breadthwise and in a loop so that the fabrics run continuously, said machine having such structural characteristics as to achieve the most intimate possible contact of processing liquid with the fabric which, arranged as specified gradually is carried down the length of the machine.
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FIELD OF INVENTION
The present invention generally relates to automated fairing and painting of marine vessels, and the present invention specifically relates to the use of computer controlled robotic equipment for analyzing surface imperfections, fairing, applying a sprayable fairing compound, and painting.
BACKGROUND OF INVENTION
Custom marine vessels are constructed today using time proven techniques and methods. Part of this process is known as fairing. Fairing is a process whereby a less than smooth surface is filled, sanded and primed in preparation for painting. Fairing, as applied in the marine industry, is done almost exclusively on the exteriors of yachts, where the greatly enhanced aesthetic quality of paint on a professionally faired hull or superstructure imparts a uniform mirror like quality to the paint finish. Commercial or military marine vessels are almost never faired due to the cost and time involved as well as the purely aesthetic nature of such a process.
Fairing is accomplished by analyzing a marine vessel's exterior surface for imperfections and then utilizing certain techniques for removing the imperfections from the hull or superstructure. Traditionally, a crew of skilled craftsmen using hand operated air tools, hand operated electric tools, simple hand tools or any combination thereof has performed this process. The first step is to analyze the imperfections in the hull or superstructure surface by using a straight edged, elongated board or batten to “map” or mark imperfections in the vessel surface. The next step involves applying a primer, usually a spray applied primer. After the “mapping” and priming steps, any imperfections greater than approximately ⅛″ in depth are manually filled with trowelable fairing compound, applied using hand trowels and long metal spreaders. When the troweled filler has cured, it is hand sanded using hand blocks and “longboards” with sandpaper attached and with manually operated power sanders. When the surface being faired is relatively smooth and fair, a final optional application of sprayable fairing compound may be applied using manually operated spray equipment. Once all of the fairing compound has been applied and manually sanded,, priming and painting the faired hull or superstructure then completes the fairing and painting process.
Using current methods, a surface with 5,000 square feet of fairable area takes approximately 2.2 man-hours per square foot or 11,000 total man-hours to fair from an unfaired surface to a high quality, i.e. “yacht quality”, painted finish. Related industries, such as the automobile manufacturing industry, have attempted to solve the inefficiency corresponding to large tasks performed by hand, by automating certain aspects of production. For example, U.S. Pat. No. 4,532,148, to Veciello, describes an automated painting system for automobiles performed primarily by robots with rotary bell-type atomizing devices attached to the robot arm. While this invention is adequate for painting mass-production automobiles, it only serves to paint.
U.S. Pat. No., 4,498,414, to Kiba, et al., describes an automobile painting robot. This robot was designed to paint automobiles on an assembly line with the additional feature of being able to open the car door for greater access for painting.
While the above patents relate to automated painting robots and a system for painting with robots, U.S. Pat. No. 5,571,312, to Andoe, describes a coating material that could be applied by the robots to a marine vessel.
None of the above references, each of which is incorporated herein by reference, describe a method for fairing a marine vessel. In addition, the marine vessel industry has not devised an automated method to save the time and expense expended in fairing a vessel hull and superstructure.
As a consequence, there is a need in the art for a method of automated fairing of marine vessels in order to save time and expense, and to ensure precision fairing.
There is a further need in the art for a method of automated fairing that employs multi-function robots with interchangeable operative heads.
SUMMARY OF INVENTION
The present invention satisfies the needs in the art by providing automation technology to analyze, fair and paint the hulls and superstructures of marine vessels in order to save material cost, labor and to provide computer-controlled precision fairing.
The preferred embodiment of the invention is a computer-implemented method for fairing the hull or superstructure of a marine vessel, utilizing a robot system which includes multiple robots positioned on moveable means and having arms provided with various attachments, moveable about various control axes, comprising the steps of positioning the marine vessel so as to provide the robots access to the hull and superstructure; analyzing the vessel's hull and superstructure for imperfections; applying a fairing compound to the imperfections; sanding the fairing compound in alignment with the hull or superstructure; removing any compound dust generated by the sanding process; and priming and painting the hull or superstructure.
In another preferred embodiment the robots are positioned on glide tracks or a gantry for movement.
In another preferred embodiment the robots are provided with arms adaptable for affixing and using various attachments.
In another preferred embodiment the analyzing step further comprises using a surface mapping system utilizing lasers, affixed to the robot.
In another preferred embodiment the analyzing step further comprises using a surface mapping system utilizing radar, affixed to the robot.
In another preferred embodiment the fairing compound application step further comprises using a spraying apparatus, affixed to the end of the robot arm.
In another preferred embodiment the fairing step further comprises using a milling apparatus and vacuum apparatus in conjunction with one another, affixed to end of the robot arm.
In another preferred embodiment the painting step further comprises using a second spraying apparatus, affixed to the end of the robot arm.
In another preferred embodiment the steps further comprise using interchangeable attachments for use by the robots.
Accordingly, it is an object of the invention to use robots to analyze the imperfections in a marine vessel's hull or superstructure by utilizing a surface mapping laser or radar.
It is a further object of the invention to use robots to apply any sprayable fairing compound as may be necessary to correct the detected imperfections in a marine vessel's hull or superstructure by utilizing spraying equipment to apply the compound.
Another object of the invention is to use robots to sand the fairing compound once it has been applied to the vessel in order to achieve a smooth surface by use of a milling or sanding head.
A still further object of the invention is to remove, from the work area, the fairing compound dust created by the sanding process by a vacuum tube or other similar cleaning means.
A still further object of the invention is to use robots to apply the final paint coat to the vessel surface by utilizing spraying equipment to apply the paint.
A still further object is to provide moveable means for the robots for the purpose of allowing the robots complete access to the vessel's hull and superstructure surfaces.
Another object of the invention is to provide the robots with interchangeable heads for accomplishing the tasks of analyzing the hull for imperfections, applying fairing compound, sanding the hull and painting.
The above objects and advantages of the present invention will become apparent from the following description and appended claims, taken in conjunction with the accompanying drawings which show by way of example some preferred embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view of a vessel located in the operational area of the automated fairing system and approximate layout of said system according to the present invention;
FIG. 2 is a perspective view of the automated fairing system including a gantry mounted robot, according to a preferred embodiment;
FIG. 3 is an elevational side view illustrating a track mounted fairing robot and a gantry mounted robot as utilized in the automated fairing system and method according to the present invention; and
FIGS. 4A-4D are perspective views of the various heads to be used in conjunction with the robots according to the present invention.
DETAILED DESCRIPTION OF INVENTION
Referring to the drawings, and more particularly FIG. 1 thereof, an automated fairing system 10 is shown which includes a controller 12 for directing the movement of robots 14 . Said controller is capable of receiving various electrical input signals for initiating the operation of the robots 14 in accordance with a preprogrammed sequence of operation. The robots 14 are located on parallel tracks 16 for movement along the longitudinal axis of the marine vessel 18 . The vessel 18 is situated in the operational area of the robots 14 , between the tracks 16 , allowing said robots complete access along the length of the vessel 18 .
FIG. 2 represents a perspective view of an alternative embodiment of the system 10 , in which the robots 14 on tracks 16 can be seen working on the vessel 18 in conjunction with a gantry 20 and gantry mounted robot 22 , said gantry 20 and gantry mounted robot 22 are also controlled by the controller 12 . According to the alternative embodiment, the gantry 20 would have the capability of linear movement 24 up and down the longitudinal axis of the vessel 18 and the robot 22 on the gantry 20 is would have side to side movement and telescoping means 35 to raise or lower to the work surface. As stated in the description of FIG. 1, this invention operates with, and the apparatus thereof includes, robots 14 (FIG. 1 ), without a gantry 20 . Additionally, when using gantry 20 , various alternative structures are operative within the bounds of this invention, such as when the “legs”, as are shown in FIG. 2, or with “legs” as shown but suspending the gantry from above.
As can be seen in FIG. 3, the robots, 14 and 22 , are hydraulically operated units which include a base 30 , a primary arm 32 , a secondary arm 34 and a wrist 36 that terminates in a support head 38 , which interlocks with any one of the interchangeable tools 50 , 60 , 70 and 80 . The controller 12 and the base 30 , the primary arm 32 , the secondary arm 34 , the wrist 36 , the support head 38 and the interchangeable tools 50 , 60 , 70 , and 80 are operatively connected for achieving the end result of movement of the interchangeable tools 50 , 60 , 70 , and 80 in a desired manner.
FIGS. 4A-4D illustrate the various interchangeable tools 50 , 60 , 70 , and 80 as utilized in the automated fairing system 10 . The optional analyzer tool 50 in FIG. 4A is used for analyzing the vessel's surface 19 , through the use of surface mapping laser or radar 53 , This tool is affixed using a connective means 51 which interlocks with wrist 36 . The analyzing process may be accomplished with the analyzing means attached to the base 30 of the robots 14 and 22 rather than at the end of the secondary arm 34 .
The fairing compound application tool 60 in FIG. 4B, employs a spray nozzle 62 supplied with compressed air 64 and fairing compound 66 through hoses 65 and 67 respectively. The tool is affixed using a connective means 61 that interlocks with the wrist 36 .
FIG. 4C portrays an interchangeable sanding tool 70 useable for sanding the areas treated with fairing compound 66 . The tool uses a means for sanding 72 in conjunction with a vacuum hose 74 for the removal of the toxic dust created from smoothing the fairing compound 66 . A hood 76 encloses the sanding means 72 and the vacuum hose 74 the vacuum hose projecting through the tool 70 and within the hood 76 , proximate sanding means 72 , which is not shown in the drawing of FIG. 4C for the sake of clarity, but is to be understood that way, as previously described herein. The hood 76 is used to prevent the dust from escaping and is also used to enhance the suction capability of the vacuum 74 . The sanding tool 70 is interchangeably affixed to the wrist 36 by a connective means 71 . Also, usable for cleaning the surfaces, analyzed and treated with fairing compound 66 , are various alternative means; e.g. a water-blasting means is used in one of the tools, but this requires sufficient connections for handling water, and this potentially requires a drying means for use after the water-blasting or power-washing. When water-blasting is used for cleaning, the pressure is adjusted for the size of the vessel (less for a yacht, than for a large ship). Furthermore, particularly with large ships, the present invention method involves only the steps of positioning the vessel, cleaning with water-blasting, and analyzing for imperfections or contours before repairing and/or painting.
An interchangeable painting tool 80 is shown in FIG. 4D, a perspective view. Paint 86 is applied through a spray nozzle 82 that is supplied by hoses 85 and 87 with compressed air 84 and paint 86 respectively. The painting tool 80 is interchangeably affixed to the wrist 36 by a connective means 81 .
It will be understood that the preferred embodiments 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.
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A computer controlled method utilizing robots for the fairing and painting of marine vessel surfaces comprising the steps of analyzing the vessel hull and/or superstructure for imperfections; applying a fairing compound to the imperfections; smoothing the imperfections into alignment with the hull and/or superstructure; and applying a final paint finish to the hull and/or superstructure.
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BACKGROUND OF THE INVENTION
(1) Field of the Invention
The present invention relates to a cell safety valve in which a thin valve plate is formed in an opening hole in a sealing plate for sealing a cell such that if an internal cell pressure exceeds a predetermined value this valve plate may break so as to release a gas in the cell out of the cell, and a method for manufacturing the same.
(2) Description of the Related Art
Recently, besides LiCoO 2 and other lithium-containing composite oxides used as the positive electrode material, non-aqueous electrolyte cells using as the negative electrode material, such materials as lithium-aluminum alloy and carbon materials, which are capable of intercalating and deintercalating lithium ions, are attracting public attention as being capable of improving capacity.
When such a non-aqueous electrolyte cell is mishandled, e.g., put in fire, recharged, or discharged under abnormal conditions, a great amount of gas may be produced in the cell. Unless the gas in the cell is released out quickly, it may burst or ignite problematically. To prevent such a problem, such a cell is provided with a safety valve for releasing the gas in the cell out of it quickly at the time of abnormality. As such a safety valve, the following valves have been proposed:
(1) a valve that, as described in Japanese Unexamined Patent Application No. 11-250885 (see FIGS. 1 through 4 ), in an opening hole 21 a in a ring-shaped base material 21 , a cladding material 22 (with a thickness of about 10% of that of the base material) formed by two sheets of aluminum-based materials and constituting a valve plate is welded or pressure-welded to form a safety valve 23 , which is in turn mounted to a sealing plate 24 (one that is a so-called cladding-material-spec safety valve);
(2) a valve that, as described in Japanese Unexamined Patent Application No. 11-250885 (see FIGS. 5 and 6 ), a break groove 26 is formed at around the middle of an opening hole 25 a in a sealing plate 25 ; and
(3) a valve that, as described in Japanese Unexamined Patent Application No. 11-273640 (see FIGS. 7 and 8 ), a dome-shaped thin valve plate 29 is formed starting from the lower end of an opening hole 28 a in a sealing plate 28 .
Those conventional safety valves, however, have had the following problems.
Problems of Type (1) Safety Valve
This safety valve 23 may have irregularities in strength of welding or pressure welding of the base material 21 and the cladding material 22 , which may in turn damage the cladding material 22 when the safety valve 23 is mounted to the sealing plate 24 , thus causing leakage of an electrolyte or increasing the cell-to-cell difference in the operating pressure of the safety valve.
Problems of Type (2) Safety Valve
This safety valve, although it reduces the cell-to-cell difference in the safety-valve's operating pressure, may have irregularities in the open area of a valve plate 27 upon the breaking of the safety valve, so that in case the open area is small, amount of gas production may be more than the amount of gas release. This may prevent the safety valve from having its own functions sufficiently, thus causing the cell to ignite or burst problematically.
Problems of Type (3) Safety Valve
This safety valve, although it can release a lot of gas produced quickly due to an enlarged open area of the valve plate 29 , has the thin valve plate 29 formed from the lower end of the opening hole 28 a , so that the valve plate 29 may be damaged by a jig etc. to produce cracks etc. if it had vibration or shock on it during assembly of the cells, thus causing the leakage of the electrolyte.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide such a cell safety valve and a method for manufacturing the same that can ensure a sufficient open area during the operation of the safety valve while reducing the cell-to-cell difference in the operating pressure of the safety valve.
It is another object of the present invention to provide such a safety valve and a method for manufacturing the same that can prevent an electrolyte from leaking.
To achieve the above-mentioned objects, a cell safety valve according to a first aspect of the invention has its thin valve plate formed on a sheet-shaped sealing plate for sealing the cells such that if the internal cell pressure exceeds a predetermined value, the valve plate may break to release the gas in the cell to the outside, wherein the valve plate has a dome-shaped dome portion formed thereon and also at its middle or near it has a break groove for facilitating the breakage thereof.
Since thus the valve plate has the break groove at its middle or near it for facilitating the breakage thereof, if the internal cell pressure rises abnormally, the valve plate breaks surely starting from the break groove; in addition, as the valve plate has the dome-shaped dome portion formed thereon, after the valve plate has thus started breaking starting from the break groove, the peripheries of the dome portion also break by increased stress due to the gas. Therefore, even with some irregularities in the thickness of the valve plate, the cell-to-cell difference can be reduced in the operating pressure of the safety valve.
A second aspect of the invention is characterized in that the cell safety valve according to the first aspect of the invention, wherein the above-mentioned dome portion is provided one.
A third aspect of the invention is characterized in that the cell safety valve according to the second aspect of the invention, wherein the above-mentioned break groove is formed in the periphery of the above-mentioned dome portion.
The break groove is thus formed in the periphery of the dome portion, to further facilitate the breaking of the valve plate, thus reducing the cell-to-cell difference in the operating pressure of the safety valve.
A forth aspect of the invention is characterized in that the safety valve according to the first aspect of the invention, wherein the above-mentioned dome portion is provided two or more.
The dome portion is thus provided two or more, to ensure a sufficient open area during the operation of the safety valve.
A fifth aspect of the invention is characterized in that the safety valve according to the forth aspect of the invention, wherein the above-mentioned break groove is formed in the periphery of at least one of the above-mentioned two dome portions or more.
Such a configuration gives almost the same actions and effects as those of the third aspect of the invention.
A sixth aspect of the invention is characterized in that the safety valve according to the first aspect of the invention, wherein the above-mentioned valve plate as a whole is disposed between an imaginary plane flush with the outside surface of the above-mentioned sealing plate and an imaginary plane flush with the inside surface of the above-mentioned sealing plate.
In such a configuration, the valve plate does not come in direct contact with the jig etc., so that even in case of a vibration or shock during the assembly of the cells, it does not cause the jig etc. to damage the valve plate, thus inhibiting the electrolyte from leaking.
A seventh aspect of the invention is characterized in that the safety valve according to the first aspect of the invention, wherein the above-mentioned dome portion bulges in a direction toward the outside of the cell so as to form a dome shape.
Such a configuration further ensures the operations of the safety valve.
An eighth aspect of the invention is characterized in that the safety valve according to the first aspect of the invention, wherein the thickness of the above-mentioned valve plate is regulated to 0.1 through 10% of that of the above-mentioned sealing plate.
The thickness of the valve plate is thus regulated because a valve plate thickness of less than 0.1% of the sealing plate thickness is so thin that may cause leakage of the electrolyte, while a valve plate thickness of more than 10% of the sealing plate is so thick that excessively increase the cell-to-cell difference in the operating pressure of the safety valve.
A ninth aspect of the invention is characterized in that the safety valve according to the first aspect of the invention, wherein the plane shape of the above-mentioned valve plate is a true circle, an ellipse, or a quadrangle.
Among a true circle, an ellipse, and a quadrangle exemplified as the plane shape of the valve plate, an ellipse or a quadrangle is desirable. This is because in contrast to a true-circular shape of the valve plate that causes uniform stress to be applied on its peripheries and makes it difficult to break which in turn increases the cell-to-cell difference in the operating pressure of the safety valve, while an elliptic or rectangular shape of the valve plate causes stronger stress to be applied on the longer side and surely causes the valve plate to break starting from the longer side, thus reducing the cell-to-cell difference in the operating pressure of the safety valve.
A tenth aspect of the invention is characterized in that the safety valve according to the first aspect of the invention, wherein the valve plate and the sealing plate are molded in one piece.
Such a configuration reduces the number of components of the safety valve and makes it possible to decrease the costs for manufacturing the cells.
An eleventh aspect of the invention is characterized in that the safety valve according to the first aspect of the invention, wherein besides the above-mentioned break groove, a break aiding groove is formed near the periphery of the above-mentioned valve plate.
In such a configuration, as the internal cell pressure rises, a displacement also increases near the breaks of the dome portion, so that particularly for cells with a small-sized valve plate (thin cells), even a small rise in the internal cell pressure ensures stable operations. Further, in the manufacturing of the valve plate, its tolerance can be relaxed, to facilitate quality control and metal-mold adjustment, thus improving the productivity.
To achieve the above-mentioned objects, a twelfth aspect of the invention comprises a valve plate forming step of forming a valve plate wherein a sheet-shaped sealing plate for sealing the cells is provided with a dome-shaped dome portion and a break groove is formed at the middle or near it for facilitating the breaking of the valve plate by plasticity working.
By such a method, the cell safety valve according to the first aspect of the invention can be formed when the components of the sealing plate are worked, thus improving the productivity.
A thirteenth aspect of the invention is characterized in that the method according to the twelfth aspect of the invention, wherein during the above-mentioned valve plate forming step, the valve plate is formed between an imaginary plane flush with the outside surface of the above-mentioned sealing plate and an imaginary plane flush with the inside surface of the above-mentioned sealing plate.
By such a method, the cell safety valve according to the sixth aspect of the invention can be prevented from being damaged when it comes in contact with jigs or any other sealing elements during manufacturing.
A fourteenth aspect of the invention is characterized in that the method according to the twelfth aspect of the invention, wherein during the above-mentioned valve plate forming step, the dome portion is formed in such a way as to bulge in a direction toward the outside of the cells.
By such a method, a further surely operating valve can be made in manufacturing of the cell safety valve according to the seventh aspect of the invention.
A fifteenth aspect of the invention is characterized in that the method according to the twelfth aspect of the invention, wherein during the above-mentioned valve plate forming step, besides the above-mentioned break groove, a break aiding groove is formed near the periphery of the above-mentioned valve plate.
By such a method, a more surely operating valve plate can be made in manufacturing the cell safety valve according to the eleventh aspect of the invention.
A sixteenth aspect of the invention is characterized in that the method according to the twelfth aspect of the invention, wherein after the above-mentioned valve plate forming step, there is included an annealing step of annealing the valve plate.
If a thin valve plate is formed by drawing, the material for the valve plate has higher hardness, so that with the increasing mechanical strength of the material itself, the cell-to-cell difference in the operating pressure of the safety valve may be larger. By annealing the valve plate after the valve plate forming step, however, the valve plate material has lower hardness, so that with the decreasing mechanical strength of the material itself, the cell-to-cell difference in the operating pressure of the safety valve is reduced.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view of a safety valve related to a prior art example.
FIG. 2 is a cross-sectional view taken along arrow A—A of FIG. 1 .
FIG. 3 is a plan view of a non-aqueous electrolyte cell using the safety valve related to the prior art example.
FIG. 4 is a cross-sectional view taken along arrow B—B of FIG. 3 .
FIG. 5 is a plan view of a safety valve related to another prior art example.
FIG. 6 is a cross-sectional view taken along arrow C—C of FIG. 5 .
FIG. 7 is a plan view of a safety valve related to further another prior art example.
FIG. 8 is a cross-sectional view taken along arrow D—D of FIG. 7 .
FIG. 9 is a plan view of a safety valve related to an embodiment of the present invention.
FIG. 10 is a cross-sectional view taken along arrow E—E of FIG. 9 .
FIG. 11 is a plan view of a non-aqueous electrolyte cell using the safety valve related to the present invention.
FIG. 12 is a cross-sectional view taken along arrow F—F of FIG. 11 .
FIG. 13 is a plan view of a safety valve related to another embodiment of the present invention.
FIG. 14 is an illustration showing an operating state of the safety valve of FIG. 13 when the inner pressure of a cell provided with it has risen.
FIG. 15 is en enlarged view of an important portion of FIG. 14 .
FIG. 16 is a plan view showing a portion of the valve plate that has higher bending strength.
FIG. 17 is an illustration showing an operating state of the safety valve of FIG. 16 when the inner pressure of a cell provided with it has risen.
FIG. 18 is an enlarged view of an important portion of FIG. 17 .
FIG. 19 is a plan view of a safety valve related to further another embodiment of the present invention.
FIG. 20 is a plan view of a safety valve related to further another embodiment of the present invention.
FIG. 21 is a plan view of a safety valve related to further another embodiment of the present invention.
FIG. 22 is a plan view of a safety valve related to further another embodiment of the present invention.
FIG. 23 is a plan view of a safety valve related to further another embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following will describe embodiments of the present invention with reference to FIGS. 9 through 23.
First Embodiment
EXAMPLE 1
As shown in FIGS. 11 and 12, a non-aqueous electrolyte cell according to the present invention has a rectangular cell case 8 , which houses therein a flat spiral generating element 7 comprising a positive electrode with an aluminum-alloy made foil having an active material layer mainly made of LiCoO 2 formed thereon, a negative electrode with a copper-made foil having an active material layer mainly made of graphite formed thereon, and a separator for separating these two electrodes. In the above-mentioned cell can 8 is also poured an electrolyte wherein LiPF 6 is dissolved at a ratio of 1 M (mole/liter) in a mixture solvent in which ethylene carbonate (EC) and dimethyl carbonate (DMC) are mixed at a volumetric ratio of 4:6. Further, in the opening hole in the above-mentioned cell can 8 is laser-welded a sealing plate 6 (thickness: 1 mm) made of an aluminum alloy for sealing the cell.
The above-mentioned sealing plate 6 is sandwiched by a sandwiching member 16 together with a gasket 11 , an insulating plate 12 , and a conducting plate 14 , on which sandwiching member 16 is fixed a negative-electrode terminal cap 10 . Also, a negative-electrode tab 15 extending from the above-mentioned negative electrode is electrically connected with the above-mentioned negative-electrode terminal cap 10 via the conducting plate 14 and the sandwiching member 16 , while the above-mentioned positive electrode is electrically connected with the above-mentioned cell can 8 via a positive-electrode tab (not shown).
In this configuration, the above-mentioned sealing plate 6 and the above-mentioned insulating plate 12 have an opening hole 17 , in which the opening hole 17 is provided a safety valve 9 (made of an aluminum alloy like the sealing plate 6 ) which comprises a thin valve plate (as thick as 50 μm, which is 5.0% of the thickness of the sealing plate 6 ) and is molded in one piece with the above-mentioned sealing plate 6 . This safety valve 9 has such a construction that it breaks to release the gas in the cell to the outside of the cell if the internal cell pressure exceeds a predetermined value. The above-mentioned valve plate has two dome portions 2 which are bulged in a dome shape in a direction toward the outside of the cell, on the peripheries of which dome portions 2 • 2 are formed break grooves 4 • 4 in such a manner as to be adjacent with each other at around the middle of the safety valve 9 for facilitating the breaking of the valve plate. Also, the safety valve 9 as a whole is formed between an imaginary plane 18 a flush with an outside surface 6 a of the above-mentioned sealing plate 6 and an imaginary plane 18 b flush with an inside surface 6 b of the above-mentioned sealing plate 6 .
The non-aqueous electrolyte cell having the above-mentioned construction was made as follows.
First, a 90 weight % of LiCoO 2 as a positive-electrode activating material, a 5 weight % of carbon black as a conducting agent, another 5 weight % of poly-vinylidene fluoride as a binder, and an N-methyl-2-pyrolidon (NMP) as a solvent were mixed to prepare slurry, which was then applied to both surfaces of aluminum foil acting as the positive-electrode collector. Then, the solvent was dried and compressed by a roller to a predetermined thickness and then cut to predetermined width and length, to subsequently weld a positive-electrode collector tab made of an aluminum alloy.
Concurrently with this step, a 95 weight % of graphite powder as a negative-electrode activating material, a 5 weight % of poly-vinylidene fluoride as a binder, and an NMP solution as a solvent were mixed to prepare slurry, which was then applied to both surfaces of copper foil acting as a negative-electrode collector. Then, the solvent was dried and compressed by a roller to a predetermined thickness and cut to predetermined width and length, to subsequently weld a negative-electrode collector tab made of nickel.
Next, the above-mentioned positive and negative electrodes were wound with a separator formed by a polyethylene-made micro-porous thin film therebetween to form a flat spiral power-generating element 7 , which was inserted to the cell can 8 .
Concurrently with this step, on the other hand, a thin-sheet portion was formed at a predetermined position on the sealing plate by forging (a type of plasticity working) and then subjected to coining (another type of plasticity working) to form a break groove 4 to thereby provide the dome portion 2 , thus forming a safety valve 9 molded in one piece with the sealing plate 6 . Then, the sealing plate 6 , the gasket 11 , the insulating plate 12 , and the conducting plate 14 were sandwiched by the sandwiching member 16 .
Then, the cell can 8 and the sealing plate 6 were laser-welded to each other, to pour an electrolyte into the cell can 8 and fix the negative-electrode terminal cap 10 on the sandwiching member 16 , thus making the non-aqueous electrolyte cell.
Thus made cell is hereinafter referred to as a cell A 1 according to the present invention.
EXAMPLE 2
This example is the same as the above-mentioned example 1 except that after the sealing plate 6 with the safety valve 9 formed thereon was made, the safety valve 9 is annealed.
Thus made cell is hereinafter referred to as a cell A 2 according to the present invention.
EXAMPLE 3
This example is the same as the above-mentioned example 1 except that the break groove 4 for facilitating the breaking of the valve plate was formed in the periphery of only one of the two dome portions 2 • 2 .
Thus made cell is hereinafter referred to as a cell A 3 according to the present invention.
COMPARATIVE EXAMPLE 1
This Comparative example used such a prior art valve as described in Japanese Unexamined Patent Application No. 10-106524 (see FIGS. 1 through 4 ).
Thus made cell is hereinafter referred to as a comparison cell X 1 .
COMPARATIVE EXAMPLE 2
This Comparative example used such a prior art valve as described in Japanese Unexamined Patent Application No. 11-250885 (see FIGS. 5 and 6 ).
Thus made cell is hereinafter referred to as a comparison cell X 2 .
COMPARATIVE EXAMPLE 3
This Comparative example used such a prior art valve as described in Japanese Unexamined Patent Application No. 11-273640 (see FIGS. 7 and 8 ).
Thus made cell is hereinafter referred to as a comparison cell X 3 .
Experiment 1
The above-mentioned cells A 1 and A 2 according to the present invention and comparison cells X 1 through X 3 were subjected to a thermal shock test consisting of 100 repetitive cycles of a thermal shock each of the cycles keeping them at 70° C. for one hour and then at −30° C. for another one hour to subsequently checked for the number of leakage cases of the electrolyte, a thermal test checking for breaking and ignition of the cells after they are heated with a burner, and an operating-pressure difference test checking a cell-to-cell difference in the operating pressure of the safety valve, the results of which are given in Table 1 below.
TABLE 1
Cell A1
Cell A2
according
according
Compari-
Compari-
Compari-
to the
to the
son
son
son
invention
invention
cell X1
cell X2
cell X3
Planar shape
Ellipse
Ellipse
True circle
—
Ellipse
of safety
valve
Break
Circle
Circle
Circle
Y-shape
Ellipse
portion
shape
Annealing
Not done
Done
Not done
—
Not done
Break
Formed
Formed
Not
Formed
Not
groove at
formed
formed
middle of
safety valve
Electrolyte
0/50P
0/50P
22/50P
0/50P
17/50P
leakage as a
result of
thermal
shock
Number of
0/10P
0/10P
0/10P
3/10P
0/10P
cell break
ignition and
break cases
as a result of
thermal test
Operating
±0.29
±0.19
±0.68
±0.39
±0.39
pressure
difference
(MPa)
As can be apparent from Table 1 above, the comparison cell X 1 encountered leakage of the electrolyte in the thermal shock test and an increase in the operating pressure difference in the operating-pressure difference test, the comparison cell X 2 encountered burst and ignition of the cell in the thermal test, and the comparison cell X 3 encountered leakage of the electrolyte. In contrast to these, the cells A 1 and A 2 according to the present invention encountered no leakage of the electrolyte in the thermal shock test nor burst nor ignition in the thermal test but encountered even a decrease in the operating pressure difference in the operating-pressure difference test.
These results indicate that the cells A 1 and A 2 according to the present invention have been improved in various items of performance required for the safety valve 9 as compared to the comparison cells X 1 through X 3 .
The cell A 2 according to the present invention, however, has been recognized to have a smaller operating-pressure difference in the operating-pressure difference test than the cell A 1 according to the present invention. With this, therefore, it is apparent that in order to decrease the difference in the operating pressure, the safety valve should preferably be subjected to annealing processing.
Experiment 2
The thermal shock test and the operating-pressure difference test were conducted on safety valves having a variety of thickness values under almost the same conditions as the above-mentioned experiment 1, the results of which are given in Table 2. Note here that in this experiment 2, the thickness of the sealing plate was kept at 1.0 mm and the safety valve 9 was not annealed.
TABLE 2
Thickness of
0.5 μm
1.0 μm
10 μm
50 μm
100 μm
150 μm
safety valve
Ratio of safety
0.05%
0.1%
1.0%
5.0%
10.0%
15.0%
valve thickness
with respect to
sealing plate
thickness
Operating
±0.19
±0.24
±0.27
±0.39
±0.44
±0.88
pressure
difference
(MPa)
Leakage of
20/50P
0/50P
0/50P
0/50P
0/50P
0/50P
electrolyte as a
result of
thermal shock
test
As can be apparent from Table 2 above, a safety valve with a thickness of 0.5 μm (which is 0.05% of the thickness of the sealing plate) encountered leakage of the electrolyte in the thermal shock test, while a safety valve with a thickness of 150 μm (which is 15.0% of the thickness of the sealing plate) encountered an increase in the operating-pressure difference in the operating-pressure difference test. As against these, safety valves with thickness values of 1 through 100 μm (which are 0.1 through 10.0% of the thickness of the sealing plate) encountered no leakage of the electrolyte in the thermal shock test and even a reduced operating-pressure difference in the operating-pressure difference test.
Those results indicate that the safety valve preferably has a thickness of 0.1 through 10.0% of the thickness of the sealing plate.
Experiment 3
The operating-pressure difference test was conducted on the above-mentioned cells A 1 and A 3 according to the present invention under the same conditions as the above-mentioned experiment 1, the results of which are given in Table 3 below. Note here that the thickness of the sealing plate was kept at 1.0 mm.
TABLE 3
Cell A1 according
Cell A3 according
to the invention
to the invention
Planar shape of safety valve
Ellipse
Shape of break groove
Circle
Annealing
Done
Ratio of safety valve
5.0%
thickness with respect to
sealing plate thickness
Number of break grooves
2
1
provided
Operating pressure
±0.19
±0.29
difference (MPa)
As can be seen from Table 3, the cell A 1 according to the present invention with the break groove 4 formed in the periphery of both dome portions 2 encountered a decrease in the operating-pressure difference, whereas the cell A 3 according to the present invention with the break groove 4 formed in the periphery of only one of the two dome portions 2 encountered an increase in the operating-pressure difference.
Therefore, it can be seen that the break groove 4 should preferably be formed in the periphery of both dome portions 2 .
Second Embodiment
As shown in FIG. 13, this embodiment has the same configuration as the above-mentioned first embodiment except that as shown in FIG. 13, two break aiding grooves 19 • 19 are formed in sites (i.e., those separate from the dome portions 2 • 2 ) in which the break groove 4 is not formed near the periphery of the safety valve 9 .
Such a configuration has the following effects.
That is, as shown in FIG. 16, when the above-mentioned break aiding groove 19 is not formed, the sites (hatched areas in FIG. 16) separate from the dome portions 2 • 2 have higher bending strength, so that when the internal cell pressure rises, a displacement (a flexure of the safety valve 9 ) 52 decreases near a break at the dome portions 2 • 2 . Therefore, particularly for a thin cell (i.e., a cell with a small safety valve 9 ), a small rise in the inner pressure is not enough for stable operations. Further, the tolerance for the thickness of the break groove is stringent in manufacturing of the safety valve 9 , to make the quality control and metal mold adjustment difficult, thus decreasing the productivity.
In contrast, when the two break aiding grooves 19 • 19 are formed as shown in FIG. 13, the sites (i.e., those in FIG. 13 corresponding to the hatched areas in FIG. 16) separate from the dome portions 2 • 2 have lower bending strength, so that as shown in FIGS. 14 and 15, when the internal cell pressure rises, a displacement 51 increases near a break at the dome portions 2 • 2 . Therefore, particularly for a cell with a small safety valve 9 , even a small rise in the inner pressure is enough for stable operations. Further, the tolerance for the thickness of the break grooves 3 and 4 can be lenient in the manufacturing of the safety valve 9 , to facilitate the quality control and metal mold adjustment, thus improving the productivity.
The break aiding grooves 19 • 19 , however, are not limited to such a construction as having two dome portions 2 but may have three dome portions 2 or, as shown in FIG. 19, three dome portions 2 or more. Also, as shown in FIG. 19, they may have only one dome portion 2 . In this case also, the break aiding grooves 19 are formed in a site where the break groove 4 is not formed near the periphery of the safety valve 9 .
Other Items
Although the above-mentioned two embodiments employed an ellipse as the planar shape of the safety valve and a true circle as the planar shape of the dome portions 2 • 2 , they are not limiting. For example, as shown in FIGS. 20 and 21, the planar shape of the safety valve 9 may be a true circle and a quadrangle, and the dome portions 2 • 2 may be elliptic or, as shown in FIG. 22, although the planer shape of the safety valve 9 is elliptical, both of them may be elliptic to be interconnected via the break groove 3 .
Also, although the safety valve 9 and the sealing plate 6 are molded in one piece, this construction is not limiting, so that as shown in FIG. 23, the framework 1 and the valve plate of the safety valve 9 may be integrated with each other so that the framework 1 and the sealing plate 6 can be fixed to each other by use of laser welding in construction.
Further, the thickness of the valve plate of the safety valve 9 is not limited to 5.0% of the thickness of the sealing plate 6 but may be in a range of 0.1 through 10% for obtaining good results.
In addition, the materials of the sealing plate 6 and the safety valve 9 are not limited to aluminum alloys but may be a pure aluminum, while the present invention of course is not limited in application to the above-mentioned non-aqueous electrolyte cell but to those cells using vulnerable materials as aluminum etc. for the sealing plate 6 or the safety valve 9 .
If the present invention is applied to the above-mentioned non-aqueous electrolyte cell, however, as the material of the positive electrode such substances may appropriately be used as, besides the above-mentioned LiCoO 2 , for example LiNiO 2 , LiMn 2 O 4 or their composite substances such as composite oxides containing lithium, while as the material of the negative electrode such substances may appropriately be used as, besides the above-mentioned carbon materials, lithium metals, lithium alloys, or metal oxides (tin oxides etc.). Further, the solvent of the electrolyte is not limited to the above-mentioned substance but may be a mixture obtained by mixing at an appropriate ratio such a solution having a relatively high dielectric constant as propylene carbonate, ethylene carbonate, vinylene carbonate, or γ-butyrolactane and such a solution having a low viscosity and a low boiling point as diethyl carbonate, dimethyl carbonate, methyl-ethyl carbonate, tetra-hydrofuran, 1,2-dimethoxylethane, 1,3-dioxolanation, 2-methoxytetrahydrofuran, or dimethylether. Also, the electrolyte of the cells may be, besides the above-mentioned LiPF 6 , LiAsF 6 , LiClO 4 , LiBF 4 , LiCF 3 SO 3 , etc.
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A cell safety valve which has a thin valve plate formed on a sheet-shaped sealing plate for sealing the cell such that if the inner pressure of the cell exceeds a predetermined value, the valve plate breaks to release a gas in the cell to the outside, in which the valve plate has a dome-shaped dome portion formed thereon and, at its middle or near it, a break groove formed for facilitating the breaking of the valve.
By this construction, it is possible to prevent the electrolyte from leaking while reducing the cell-to-cell difference in the operating pressure of the safety valve and ensuring a sufficient open area at the time of the operations of the safety valve.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a vertical bright-annealing furnace for continuous heat treatment of metal strips and, more particularly, to a structure of a heating zone of a vertical bright-annealing furnace in which strips of a metal such as, for example, a stainless steel, copper or aluminum, are continuously annealed while keeping the brightness of surfaces thereof by heating the metal strips to an annealing temperature in a protective gas to prevent them from oxidation and decarbonization and then cooling the heated metal strips to a predetermined low temperature.
2. Description of the Prior Art
Conventionally, an up-heat type vertical bright-annealing furnace for annealing strips of a stainless steel is composed of (i) a heating zone which heats up an upward-moving strip to the first pre-set temperature, e.g. 1,100° C.; (ii) a slow-cooling zone which gradually reduces the temperature of the strip; (iii) a second cooling zone which reduces the temperature of the strip to the second pre-set temperature, e.g. 80° C.; (iv) a top-roll chamber which directs the cooled strip downward; (v) an outlet chute which directs and exits the downward-moving strip; and (vi) an inlet seal section, located at a section of the heating zone where the strip enters, and an outlet seal section located at the outlet chute section, both of which are located substantially at the same level to prevent the protective gas in the furnace from leaking out as well as to prevent the outside air from entering the furnace.
According to the structure of the heating zone, such vertical bright-annealing furnaces can be roughly classified into two types, i.e., (a) a muffle-type furnace and a refractory-type furnace. The former has a cylindrical muffle which is supported at its top and covers the entire heating zone; and burners and electric heaters heat the muffle which, in turns, heats the strip moving inside the muffle. The latter has walls made up of firebricks inside, covering the entire heating zone; and electric heaters heat the strip, moving inside the walls.
When comparing the muffle-type furnace with the refractory-type furnace, although the former has two advantages: (i) its dew-point adjustment time, i.e., a time required for adjustment of the protective gas in the furnace to the working condition, is only about twenty-four hours, and (ii) its running cost is low because of its low consumption of the protective gas, there are two disadvantages: (i) the maximum temperature in the furnace is only about 1,150° C. because of the heat-resistant steel used in the muffle, and (ii) the maximum length of the heating zone, i.e., the length of the muffle, is limited because of its weight, thus making it very difficult to make the furnace larger and more productive.
On the other hand, the latter refractory-type furnace is easier to make the furnace larger and enables to obtain the same level of productivity of the muffle-type with only seventy percent of the furnace length as the maximum temperature can be raised to 1,250° C. and above by use of high-heat resistant firebricks. However, it has disadvantages in that it takes about four to five days to bring up to the working condition at the beginning, and its running cost is high because of its high consumption of the protective gas.
SUMMARY OF THE INVENTION
It is therefore a main object of the present invention to provide a vertical bright-annealing furnace for continuous heat treatment of metal strips, which enables to achieve high productivity, short dew-point temperature adjustment time, low consumption of the protective gas, low running cost, and a large heating zone.
The above object of the present invention is achieved by combining the advantages of the both types of the furnaces to cancel the aforesaid disadvantages of the both types of the furnaces.
According to the present invention, there is provided a vertical continuous bright-annealing furnace for metal strips, comprising two heating stations, i.e., a muffle-type heating station and a refractory-type heating station, both stations being connected to one another by a flexible connecting unit, whereby a metal strip is heated up to a predetermined temperature in the refractory-type heating station after being heated in the muffle-type heating station.
The muffle-type heating station includes a cylindrical muffle through which a metal strip is conveyed, a metal shell that is lined with heat-insulating material, and first heating means for heating the muffle so as to indirectly heat the metal strip transported therein. The refractory-type heating station includes a metal shell lined with firebricks through which the metal strip is conveyed, and second heating means for heating the metal strip, which has been heated in the muffle-type heating station, to a predetermined temperature. These stations are connected by a flexible connecting unit so that the muffle-type heating station and the refractory-type station are in alignment with one another. The first heating means may comprises a plurality of burners or a plurality of electric heaters. Moreover, the metal shell of the muffle-type heating station may be divided into a fixed main part and a detachable part which is mounted on the muffle.
According to the present invention, the metal strip is conveyed through the muffle-type heating station and heated by a radiant heat from the muffle heated directly by the first heating means. After that, the metal strip is conveyed through the refractory-type heating station and heated by the second heating means up to the predetermined temperature.
Thus, according to the present invention, there is provided a vertical bright-annealing furnace for continuous heat treatment of metal strips, comprising a heating zone for heating a metal strip to a predetermined annealing temperature and a cooling zone for cooling the heated metal strip to a predetermined low temperature, said heating zone comprising:
a muffle-type heating station composed of a metal shell lined with a heat-insulating material, a muffle arranged in said shell, and a first heating means for heating said muffle; and
a refractory-type heating station arranged just above said muffle-type heating station and composed of a metal shell lined with a heat-insulating material, and a second heating means for heating said metal strip;
said heating stations being connected to one another by a flexible connecting unit which is extensible in the longitudinal direction of the heating zone, whereby allowing the metal strip to pass through the refractory-type heating station subsequent to the muffle-type heating station to heat it to a predetermined annealing temperature.
The vertical bright-annealing furnace described above, which is a combination of the muffle-type and refractory-type heating stations, may allow the annealing furnace to be upsized.
Further, since the metal strip is finally heated up to about 1,100° C. in the refractory-type station, it is not necessary to heat the metal strip up to the same temperature but about 800° C. Consequently, the period of durability is further extended, which results in reduction in maintenance, running, and manufacturing costs.
Moreover, the stainless steel contains some chromium, and hydrogen in the atmospheric gas provides less deoxidization under the circumstance having temperature of about 800° C. or less, such that it is necessary to keep a humidity in the furnace as low as possible. With the vertical bright-annealing furnace of the present invention, the metal strip is heated up to the approximately same temperature, that is about 800°, in the muffle, and the humidity in the muffle will easily be kept lower than that in the refractory-type station. Consequently, the annealing furnace of the present invention is effected to anneal the metal strip with no its brightness deteriorated substantially.
Furthermore, the vertical bright-annealing furnace of the present invention requires less consumption of the atmospheric gas, less running expenses, and less controlling time for seasoning as compared with those of the refractory-type furnace.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects and features of the present invention will become clear from the following description taken in conjunction with a preferred embodiment thereof with reference to the accompanying drawings throughout which like parts are designated by like reference numerals, and in which:
FIG. 1 is a schematic front view of a vertical bright-annealing furnace according to the present invention;
FIG. 2 is a side sectional view of a heating zone of the vertical bright-annealing furnace according to the present invention;
FIG. 3 is a cross-sectional view of a lower portion of a muffle-type heating station taken along the line III--III in FIG. 2;
FIG. 4 is a cross-sectional view of a lower portion of a refractory-type heating station taken along the line IV--IV in FIG. 2;
FIG. 5 is a cross-sectional view of a lower portion of a refractory-type heating station taken along the line V--V in FIG. 2;
FIG. 6 is a fragmentary side sectional view showing the manner in which a muffle is detached from the heating station;
FIG. 7 is fragmentary transverse sectional view showing the manner in which a muffle is detached from the heating station;
FIG. 8 is a partially side sectional view showing a connecting unit for the muffle-type and refractory-type heating stations;
FIG. 9 is a vertical sectional view of a roll type seal unit;
FIG. 10 is a vertical sectional view of a felt type seal unit; and
FIG. 11 is a graph showing changes in temperature of the metal strip in a heating zone.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1, there is shown a vertical furnace to be used for the continuous bright-annealing of the metal strip such as stainless steel indicated generally by 1.
This furnace 1 includes, along a one-way strip conveying path 2 illustrated by the phantom line, from downward to upward in order, a heating zone 3 for heating the metal strip at room temperature of about 20° C. up to about 1,100° C., a first cooling zone or slow-cooling zone 4 for cooling the heated metal strip slowly, and a second cooling zone 5 for cooling the metal strip down to about 80° C. The furnace 1 also includes a top-roll chamber 6 for deflecting the metal strip, which has been continuously transported upwardly, so as to move downward by suitable means, and an outlet chute 7 for the protection of the downward-moving metal strip. This furnace 1 of the above described construction is supported by a frame, only a part of which is shown by 8 in the FIGS. 1 and 2. Inside the heating zone 3, first cooling zone 4, second cooling zone 5, top-roll chamber 6 and outlet chute 7, there is formed a metal strip conveying channel 9 (see FIG. 2) surrounding the strip conveying path 2. This channel 9 has inlet and outlet portions defined at the same level with inlet and outlet sealing units 10 and 11 disposed at the inlet and outlet portions of the channel 9, respectively. The inlet sealing unit 10 is so designed to prevent the atmospheric gas inside the furnace from leaking to the outside while the outlet sealing unit 11 is so designed as to avoid an entry of an outdoor atmosphere or air into the furnace.
The heating zone 3 comprises a muffle-type heating station 12 and a refractory-type heating station 13 arranged downstream of the station 12 with respect to the direction of transport of the metal strip, that is, adjacent to the slow-cooling zone 4, these two stations 12 and 13 being joined together through a connecting unit 14.
As shown in FIGS. 2 and 3, the muffle-type heating station 13 is constructed of a metal shell 15 that is lined with heat-insulating material 15a such as, for example, ceramic fibers and a muffle 16 made of special heat-resistant steel such as one known under a trademark "Inconel 600" available from Inco Alloys International Ltd. of Canada. The interior space of the muffle 16 defines a part of the metal strip conveying channel 9. The muffle-type heating station 12 has first heating means which may be a plurality of burners 17 arranged in zigzag fashion so that air-fuel mixtures may be burned within the interior of the muffle-type heating station.
As shown in FIGS. 6, 7, and 8, the metal shell 15 is of two-piece construction including a main part 20 and a detachable part 21 detachably joined to the main part 20. The muffle 16 is carried by the detachable part 21. These two parts 20 and 21 are defined by dividing the metal shell 15 longitudinally along longitudinal sections 18 and 19 spaced generally 90° about a longitudinal axis of the metal shell 15.
The main part 20 is fixed at its lower end to the structure 8, while the detachable part 21 is supported by the muffle 16 which is engaged at its upper portion with a carriage 22. The carriage 22 is movably mounted on parallel rails 23 disposed on the structure 8. The rails 23 extend in such a direction perpendicular to the longitudinal axis of the metal shell 15 and at an approximate angle of 45° relative to side faces of the respective sections 18 and 19 that the carriage 22 can be moved between a separated position, shown by the phantom line in FIGS. 6 and 7, and a closed position in which the detachable part 21 and the main part 20 together form the metal shell 15.
Therefore, when the muffle-type heating station 12 is released from the connecting unit 14 and the detachable part 21 is then released from the main part 20 the carriage 22 can be moved along the rails 23 so that the detachable part 21 accompanying the muffle 16 will be separated from the main part 20 as shown by the phantom line in FIGS. 6 and 7, and eventually the muffle 16 may be repaired and/or exchanged for a new one. Preferably, the muffle 16 has a wall thickness which decreases stepwise from top to bottom so that a tensile stress at the uppermost portion thereof due to its weight may be reduced.
The refractory-type heating station 13, which is fixed to the structure 8 through lower brackets 25, comprises a metal shell 24 having a rectangular cross-section as shown in FIGS. 4 and 5, and also having an interior space thereof defining another part of the metal strip conveying channel 9. The metal shell 24 has its inner surface formed of an insulating layer 26 which is made by lining firebricks to a predetermined height. On a radially inward surface of the insulating layer 26, there is provided second heating means which may be a plurality of electric heaters 27 disposed at regular intervals. Each electric heater 27 is preferably in the form of a heater of a type utilizing a corrugated heating wire made of, for example, molybdenum or a panel heater having the heating wire built therein.
The connecting unit 14, which is expandable along the longitudinal axis of the heating zone 3, communicates respective interior spaces of the muffle 16 and the refractory-type heating station 13 with each other in a gas-tight construction. Therefore, when the muffle 16 is to be separated from the metal shell 15, it can readily and easily be accomplished by a slight upward contraction of the connecting unit 14. Further, a heat expansion of the refractory-type heating station 13 is absorbed by the connecting unit 14.
The first and second cooling zone 4 and 5 include an slow-cooling unit 28 and a cooling unit 29, respectively. These units 28 and 29 are coupled with a gas supplying unit (not shown) from which air and/or gas of a required temperature is fed thereto. The number of the cooling unit 29 in the cooling zone 5 may be determined according its ability.
Each of the top-roll chamber 6 and the outlet chute 7 comprises a tubular shell having a rectangular or circular cross section. The top-roll chamber 6 has two guide rollers 30 accommodated therein for guiding the upward-moving metal so as to deflect downwardly towards the outlet chute 7.
Various types of seal units may be used in the inlet and outlet seal units 10 and 11. For example, roll type seal units having a pair of seal rolls 31 as shown in FIG. 9, or felt type seal units comprising felts 32 and metal members 33 for bringing the felt 32 contact with the metal strip may be used therefor.
In operating the annealing furnace 1, the atmospheric gas to be charged into the channel 9 may be an HN gas, that is, a mixture of hydrogen H 2 with nitrogen N 2 in a predetermined mixing ratio. Leakage of the atmospheric gas from the inlet portion of the heating zone 3 and the outlet portion of the outlet chute 7 are prevented by the respective seal units 10 and 11. The amount of supply of the atmospheric gas is preferably controlled so as to keep a pressure of about +25 to +50 mmAg in the channel 9. A gaseous mixture of fuel and air is fed to the burners 7 in the muffle-type heating station 12, and is burned within the interior of the station 12. The heater 27 of the refractory-type heating station 13 is electrically energized by the supply of predetermined voltage to emit heat.
As a result, the stainless strip S moving along the path 2 is, as shown in FIG. 11, heated up to about 700° C. by radiant heat from the muffle 16 in the muffle-type heating station 12. Next, the strip S is further heated up to about 1,100° C. by the electric heaters 27 in the refractory-type heating station 13. Then, the strip S is cooled down to about 800° C. in the slow-cooling zone 4 and, after having been further cooled down to about 80° C. in the cooling zone 5, transported to the subsequent process through the top-roll chamber 6 and the outlet chute 7.
While there has shown and described herein the up-heat type vertical annealing furnace in which the heating zone 3, first and second cooling zones 4 and 5 are disposed from bottom to top in this order so that the metal strip is annealed while being transported upwardly, this invention can be equally applied to a down-heat type in which the heating zone 3 is disposed above the first cooling zone, i.e., the slow-cooling zone 4 and the second cooling zone 5 is disposed beneath the first cooling zone 4 so that the metal strip can be annealed while being transported downwardly.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included in the scope of the following claims.
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A vertical bright-annealing furnace 1 for metal strips includes a muffle-type heating station 12, a refractory-type heating station 13. The refractory-type heating station 13 includes a shell 24 lined with a heat-insulating material 26 and a second heater 27. These two stations 12 and 13 are connected to one another by a flexible connecting unit 14 which is extensible in the longitudinal direction of the heating zone. A metal strip S conveyed in the furnace 1 is heated in the muffle-type heating station 12 and subsequently heated in the refractory-type heating station 13 up to a predetermined temperature, for example, about 1,100° C. According to this constitution, a large-sized vertical annealing furnace may be constructed. Also, the period of durability of the muffle may be extended, the running expenses may be decreased, and metal strip having good brightness may be produced.
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BACKGROUND OF THE INVENTION
Bellows for a compensator and associated compensator and method for producing a bellows
1. Field of the Invention
The invention relates to a bellows for a compensator as an elastic connection between two duct connection pieces which are arranged [lacuna] from each other in the longitudinal direction, and to a corresponding compensator using a bellows of this type according to the preamble of claim 1 and 20, and to a method for producing a bellows according to claim 25.
2. Description of Related Art
Compensators of this type having a bellows structure which is known in accordance with the preamble of claim 1 are used in particular for decoupling structure-borne noise and/or as an expansion-compensating means in ventilation ducts in air conditioning technology. They are also suitable for compensating for thermal expansions and installation inaccuracies.
Ducts, in particular ventilation ducts in air conditioning technology, may, as is known, have different cross sectional shapes. EP 0 148 286 A1 basically discloses a flange connection for the mutual fastening of duct subsections, which are essentially rectangular in cross section, for air-conditioning duct systems, in which case the flange connection known therefrom can be used both for the installation of fixed duct walls and for the installation of an elastic wall so as to form a bellows.
EP 0 282 608 A1 discloses a duct structure which is comparable with regard to the flange profile, but is suitable for duct pieces which are circular in cross section. In this case too, the flange connection known therefrom can be used with fixed duct walls, which generally consist of sheet metal, or with the insertion of an elastic wall material to form a bellows.
DE 41 40 870 A1 which forms the generic type has disclosed a duct connecting piece in the form of a compensator. In the longitudinal direction or direction of attachment, the compensator contains two encircling flange structures which are spaced apart in the longitudinal direction or direction of attachment and are oriented transversely with respect to the longitudinal direction, said flange structures being used to enable the compensator to be fixedly connected to a next duct piece. The flange structure may be rectangular or generally polygonal in plan view, but in a modified embodiment may also be circular or oval. In this case, the bellows consists of a duct skin which is produced from a material web in an appropriate size and is tightly joined together to form a tube which is closed in the circumferential direction. Furthermore, both a sealing lip and a securing section are also formed on the duct skin, in order thereby to secure the duct skin in a suitable manner in a bead-shaped depression of the flange profiles.
Although these structures are in principle well-established, it is the object of the present invention to provide bellows and a compensator which have been improved further with respect to said structures, and to provide a corresponding process for producing bellows of this type.
BRIEF SUMMARY OF THE INVENTION
According to the invention, the object is achieved with regard to the bellows [lacuna] features specified according to claim 1 and, with regard to the compensator, according to claim 21 and, with regard to a method of producing a bellows according to the invention, according to claim 25 . Advantageous refinements are specified in the subclaims.
The bellows according to the invention and the compensator according to the invention have clear advantages over the prior art.
According to the invention, the bellows now consists not only of a flexible or elastic duct skin, but is designed as a double-walled hollow chamber system. In this case, the bellows according to the invention can be referred to in the widest sense as tubular, on account of its double wall system, even before it is used and before it is fitted in a compensator.
The bellows according to the invention and the compensator according to the invention have the surprising and advantageous effect that on account of its tubular, double-walled design, the bellows does not form any pronounced depressions or any material overlaps in its bending regions when it buckles at the corners of a square, rectangular or polygonal compensator, but also in the case of a compensator which is round or partially round in cross section. In the case of structures according to the prior art, this results in the formation of virtually dead corners, angles and pockets through which air, if used, does not flow or virtually no longer flows. In contrast, instead of the pronounced depressions or overlaps of the bellows material which occur in conventional structures according to the prior art and include the formation of shielded or dead zones and pockets, in the case of the bellows according to the invention the wall material lying on the inside is, if the need arises, deformed by static compressions, and the outer bellows material by static expansions in such a manner that deformations of a comparatively large size are produced and are formed over a large area comparable to gentle hills and valleys. This reliably avoids it being possible for the bellows material to be so distorted that it protrudes in a comparatively pronounced manner into the duct interior, through which air flows, partially overlaps with adjacent wall material and forms shielded dead corners and pockets through which the air basically flowing through the duct piece during use does not flow.
The bellows material according to the invention and the compensators according to the invention are therefore particularly suitable also for use in critical regions, for example in clinics where the intention is to reliably prevent bacteria from being able to permanently settle and become lodged in such dead corners and pockets as are formed in the prior art.
Within the scope of further refinements, the bellows material according to the invention can have numerous additional advantages.
It has proven advantageous if the bellows material is, in its entire width, i.e. in other words in the fitted state, of double-walled design in the longitudinal direction of the compensator and preferably does not have any inner webs. As a result, the inner wall ensures maximum freedom for the deformations with respect to the outer wall, advantageously assisting in the resultant, abovementioned aims and advantages.
Furthermore, there are formed, preferably on the tubular bellows material, not only corresponding sealing lips and sealing projections which interact with corresponding sealing lips or sealing projections of an adjacent channel subsection (so as in general to ensure the tightest possible connection of the duct pieces to be connected to one another), but there are also provided, preferably on the bellows, further securing projections, for example securing lips. These can preferably be provided with a barbed strip or barbed lip via which the bellows formed in this manner can be inserted without any problem and without further assisting means or tools in a corresponding groove-shaped depression or bead, provided with an undercut, in the flange pieces and can thereby be connected fixedly to the flange pieces.
The bellows material can be produced from all suitable materials, for example from polymeric material, elastic and/or flexible material, elastomeric material. EDPM material or else other sorts of plastic, for example polyester, PVC, etc, are likewise suitable.
The bellows material can be manufactured from flame-resistant, ray-absorbing, noncombustible, acid proof, heat-deflecting and/or thermally stable material.
The bellows is preferably produced by extrusion. In this case, the bellows can simultaneously also be produced together with a flange piece by extrusion, so that an additional connection of the thus formed bellows to flange pieces is no longer necessary. Should the stiffness and hardness of the flange region extruded with it not be sufficient, then an additional part used for reinforcing purposes, for example a metal flange piece or a plastic flange piece, may possibly also be attached and connected here to the flange leg.
In this case, preferably in the case of a flange section extruded together with a bellows, there can be cut in or punched out at intervals along the longitudinal side of the flange extruded with it, corresponding to the size of the compensator to be dimensioned, transverse recesses at corresponding intervals, in order to pivot the bellows together with the flange, for example through 90° with respect to each other, at these points. Suitable corner pieces, for example made of plastic or of steel comparable to the other corner pieces used, can then be inserted at the thus formed corner regions. Said corner pieces may, for example, be correspondingly plugged in or clipped in, in particular if there are formed on the flange pieces extruded with it corresponding counter recesses, i.e. grid-type [sic] depressions or grid-type [sic] projections which make possible the desired, fixed connection to the corner piece.
Both in the last-mentioned case, but also in the formation of a securing lip on the bellows, it is likewise possible to use different materials in the bellows, which is thus of integral design. In terms of manufacturing, provision may be made here that, in particular in the region of [sic] the securing lip or—if the bellows is equipped at the same time with a flange section—this flange section is produced with a significantly harder material than the rest of the remaining bellows material. A “coextrusion process” is conventionally also mentioned here, said process making it possible to produce a plastic part having a different material composition and, for example, hardness via two extruder dies.
Further advantageous effects can be obtained, particularly in the fitted state, by the cavity being filled with suitable materials, for example sheet-like materials, such as woven inserts, wire meshes, rubber mats, plastic lattices etc., or, for example, is stuffed or filled by other, tear-resistant materials.
In general, the hollow chamber system of the bellows can be filled with reinforcing, heat-insulating and/or sound-absorbing materials or else with materials which bring about an overall increase and improvement in the stability and/or load-bearing capacity of the bellows.
It is likewise possible to fill the hollow chamber, i.e. the double wall system of the bellows, with materials in the form of granules, for example styropor beads, quartz materials, metallic powder or similar materials.
Finally, materials used for the security against tearing and for the strength can additionally be inserted not only into the hollow chamber system, but, for example, reinforcing materials can also be incorporated into the bellows material during the extrusion or general production process.
In order to increase the strength against tearing, i.e. in particular with regard to the tensile stress possibly acting in the longitudinal direction of a compensator formed in this manner, provision may be made for a woven insert or other reinforcing insert to be inserted at the same time, for example in the bellows, preferably in the hollow chamber system, which insert is preferably nonextensible, with the consequence that once the fitted state has been reached, the edge of the reinforcing insert is clamped at the opposite end sections of the double-walled bellows system, with the result that the tensile forces are absorbed and supported via the reinforcing insert.
Finally, the bellows may also be provided [sic] by the introduction of fins preferably running in the longitudinal direction of the compensator (i.e. transversely with respect to the direction of extrusion) during extrusion, in order thereby to make the bellows material, and therefore the compensator in its longitudinal direction, even more stable, since a limitation on expansion is obtained thereby. Instead of the fins, steel elements or spring steel elements can be incorporated corresponding to the direction or connected in another manner to the bellows material in order to obtain this limitation on expansion.
The invention will be explained below with reference to exemplary embodiments, in which in detail:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 : shows the schematic, perspective illustration of a compensator which is rectangular in cross section;
FIG. 2 : shows a schematic, perspective illustration of a compensator which is circular in cross section;
FIG. 3 : shows a schematic end view of part of an encircling flange connection structure for connecting a compensator to a next duct piece, the said structure being in a dismantled state;
FIG. 4 : shows a transverse view along the arrow direction IV in FIG. 3;
FIG. 5 : shows a cross sectional illustration through a flange profile corresponding to the line V—V in FIG. 1, FIG. 2 and FIG. 3 together with a first, exemplary embodiment, in schematic form, of a bellows according to the invention;
FIG. 6 : shows an exemplary embodiment of a bellows according to the invention modified with respect to FIG. 5;
FIG. 7 : shows a modified exemplary embodiment in a partial schematic cross sectional illustration, transverse with respect to the extrusion direction, through a bellows provided with a flange projection extruded with it;
FIG. 8 : shows a partial plan view corresponding to the partial illustration VIII in FIG. 7;
FIG. 9 : shows a corresponding cross sectional illustration comparable to the exemplary embodiment according to FIG. 7, but in which the flange section extruded with it is formed in an angular orientation of approximately 90° with respect to the central bellows section;
FIG. 10 : shows a plan view of FIG. 8 corresponding to the arrow illustration IX in FIG. 8; and
FIG. 11 : shows an exemplary embodiment which has been modified with respect to FIG. 9 and in which a plastic corner has been clipped to the bellows with the extruded flange projection, in order to produce a compensator.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows, in a schematic, perspective illustration, an elastic connector which is also referred to below as a compensator and is used in practice in particular for the coupling structure-borne noise and as an expansion-compensating means in ventilation ducts for air conditioning systems.
The compensator 1 shown in FIG. 1 has a polygonal cross section i.e. a rectangular cross section. In contrast, the compensator shown in FIG. 2 is cylindrical and therefore has a circular cross section. However, the profile cross sections of the flange profiles, which are provided on the end side in each case in the direction of attachment, may be identical, which will be discussed below.
The rectangular flange connection for the compensator shown in FIG. 1 is partially reproduced in an exploded illustration in FIGS. 3 and 4. It can be seen therefrom that four flange profiles 5 can be put together [lacuna] the rectangular frame and can be joined together via corner brackets 7 to form an integral flange frame 9 to which the bellows 11 , which is visible from the outside in FIGS. 1 and 2, is then fastened.
The flange profile 5 , which is produced in plan view and in a side view rotated 90° with respect thereto, in FIGS. 3 and 4 and in a cross sectional illustration in FIG. 5 (where the sectional illustration according to FIG. 5 reproduces, in cross section, both an upper flange profile 5 and an opposite, lower flange profile 5 , as connected to an embodiment of a bellows which is yet to be discussed below) has a central installation leg 15 which, in the fitted state, lies oriented transversely with respect to the longitudinal direction or direction of attachment 3 of the compensator, i.e. parallel to the directly adjacent, next flange profile 5 of a flange arm 9 of a subsequent duct piece.
On the inside of the duct, i.e. lying facing the duct interior 16 , the installation leg 15 merges into a U-shaped groove 17 which does not absolutely have to be rectangular, but may, for example, also have an undercut which is more circular, in the manner of a bead, as is basically known from DE 41 40 870 A1.
The inner material end 18 of the flange material is, in the cross section according to FIG. 5, folded back protruding in a barb-like manner in the direction of the groove 17 and therefore forms a barb-like retaining strip 19 whose function will be discussed in greater detail below.
In order to obtain greater stiffness by forming an angular stiffening portion 27 which extends transversely with respect to the installation leg 15 and protrudes over the latter, the outer boundary edge 21 of the flange profile 5 , which edge lies opposite the material end 18 , is folded twice convexly and once concavely, then merges into a parallel leg 23 which runs at a small distance adjacent to and parallel to, or at least in places parallel to the installation leg 15 . The boundary edge 21 then ends shortly before the groove 17 which is U-shaped in cross section.
The plug-inlet 15 ′ of the installation leg 15 can then be plugged in each case into the thus formed, slight gap 29 between the installation leg and the parallel leg 15 , 23 , in which case a secure, fixed connection is formed by the gap 29 , when not plugged in, being smaller than the material thickness of the stretch [sic] leg 15 ′.
Recesses 33 , for example in the form of elongated holes, can then be made in the direct corner region of the installation leg 15 , and can be used to fixedly connect together two flange frames 9 , whose end side can be brought together, of two duct pieces, for example a duct piece and a compensator shown in FIG. 1 .
As also emerges from the illustration according to FIGS. 3 and 4, a bead 35 , which has a semicircular profile in plan view, is made directly on the inside in the corner of the installation leg 15 , in a direct extension of the groove- or bead-shaped depression 17 .
In the case of a circular comparator [sic] according to FIG. 2, the flange profile 5 explained above has the same cross section as reproduced in FIG. 5, i.e. corresponds with regard to the cross section to a flange profile 5 which does not have a curved profile, as is used for forming a comparator [sic] which is rectangular in cross section in accordance with FIG. 1 .
The bellows structure will be discussed in the following text.
FIG. 5 furthermore shows a first exemplary embodiment for a bellows according to the invention which is of double-wall design in a cross sectional illustration and comprises an outer wall 41 and an inner wall 43 lying on the inside of the duct. As a result, a cavity 45 is formed between the outer wall and the inner wall 41 , 43 , which cavity extends virtually over the entire width of the bellows 11 , i.e. over the entire axial length of the compensator shown in FIG. 1 or 2 , arrow 3 reproducing the direction of attachment, which corresponds to the axial longitudinal direction of the duct piece.
This bellows may, for example, be produced by extrusion as an endless bellows of any desired length running perpendicular with respect to the plane of the drawing.
According to the exemplary embodiment according to Figure [lacuna], this bellows, at the upper and lower edge thereof, is angled at approximately 90° with respect to its central, double-walled section in a manner such that it runs away from the inside of the duct, the outer and inner walls 41 , 43 being connected to each other at their end via a respective curved section 47 .
A respective securing lip 55 having a hook lip 57 protruding in the direction of the outer wall 41 is formed directly adjacent to the curved section 47 , on those sides 51 of the two end sections 53 which point toward each other, said lips being arranged symmetrically with respect to a central longitudinal plane 59 .
Formed on the end sections 53 , on the opposite side to the hook lips 57 , is a respective sealing projection 61 which, in the exemplary embodiment shown, comprises a plurality of longitudinal ribs 63 which are arranged next to one another and run in the longitudinal direction.
For installation purposes, a bellows formed in this manner has only to be inserted by the sealing lip 65 into the abovementioned, U-shaped groove 17 until the hook lip 57 grips behind the barb-like retaining element 19 in the U-shaped groove 17 , so that after this sealing lip of the bellows is fitted into the correspondingly encircling groove 19 of a flange frame 9 , this bellows is fastened captively and fixedly to the flange profile 5 . In order to produce a bellows which is closed in the circumferential direction, the latter has merely to be cut, i.e. cut off, to the correspondingly correct length, with reference to the size of the compensator, and then inserted in an encircling manner in the U-shaped groove 17 .
The bellows can then be bonded, welded or sealed in a suitable manner in some other way to one another [sic] at the intersecting points lying adjacent to one another.
The exemplary embodiment which has been explained reveals that the bellows material, i.e. the double wall system with a cavity being formed between the outer wall and inner wall is already tubular in itself, and the bellows can be produced in this longitudinal direction, for example by extrusion. In use, i.e. in the fitted state for producing a compensator, the side edges of the bellows, i.e. its transverse extent, then lie in the axial longitudinal direction of the compensator, since the bellows, after having been cut to an appropriate length in the circumferential direction with formation of a duct interior is shaped to form a closed, double-walled casing, and its cut edges, which then lie next to one another, are tightly closed by [sic] a suitable manner.
Since, in the case of a rectangular comparator [sic] according to FIGS. 1, 3 and 4 , a corresponding bead 35 is also formed on the inside of the installation leg 15 , the sealing lip 55 can continue there from the one U-shaped groove 17 in one flange profile 5 to the corresponding groove in a next flange profile which is offset by 90°.
In the following text, a slightly modified exemplary embodiment will be explained with reference to FIG. 6, which differs from that of FIG. 5 especially by the fact that the double-walled bellows is not at the outset provided with end sections 53 angled by approximately 90°.
The expansion bellows shown in cross section in FIG. 6 tapers off at its end sections 53 , essentially without being angled, in extension of the inner wall and outer wall 41 , 43 , in which case the sealing projection 61 and the securing lip 55 of the hook lip 57 are formed lying opposite each other adjacent to the curved section 47 lying at the end.
With reference to this exemplary embodiment, it is also shown that the two walls may, for example, also differ in thickness. In the exemplary embodiment shown, the inner wall 43 is slightly thinner than the outer wall 41 . In addition, the outer wall 41 is slightly convex in shape outwardly, i.e. bulges from its original shape.
In this exemplary embodiment, the installation and fitting take place in such a manner that first of all the one hook strip 57 is inserted, on one end side of the bellows formed in this manner, into the securing groove 17 of a flange profile 5 , and then the tubular bellows is bent over downwards and its opposite securing and hook lip 57 is inserted into the flange frame 9 , which is offset on the end side, of the grooves 17 formed there. After installation has taken place, a configuration having folded-over, i.e. bent-over end sections 53 comparable to the bellows structure according to FIG. 5 is produced.
Since the bellows is produced from a suitable material, for example from plastic, from EDPM, from rubber or rubber-like materials, from polymeric materials, from flexible or at least slightly elastic materials, it is ensured that the material cannot buckle and come to lie in a sheet-like manner on other sections of the bellows material when the latter is fitted into a corresponding compensator. Even in the case of rectangular compensators, the material can only take on deformations in the manner of gentle humps and depressions, comparable to hills and valleys, with the result that no undercut or shielded pockets can be formed. The deformations thus do not have any buckling points, but are rather characterized by bending radii which are of comparatively large dimensions, at least compared with other plastic sheets or fabric-like materials for the duct skin. Deformations forming on the inner wall generally have bending radii which are not, or not on average, smaller than 5 mm, and are generally even larger than 8 mm, 10 mm, 12 mm or even 15 mm.
The material which [sic] a Shore hardness of about 150 to 170 at least in the inner wall region, in which case at least the securing lip, and in the process, in particular the hook lip 57 , can be produced from harder material, for example having a Shore hardness of over D65, i.e. from D65 to D90.
The corresponding material can be formed [sic] a thickness of more than 1 mm, for example by 2 mm or even thicker still, and in the process can be made in elastic configuration so as to be comparatively flexible and easily deformable. On account of the curved end sections 53 , in particular, the tubular bellows material has the tendency to form a gentle curve profile on the inner wall, with the formation of undercuts and of an air flow and pockets through which the flow does not pass being avoided.
Depending on requirements, the bellows material which has been explained can be provided with additional woven reinforcements serving to strengthen it or by [sic] placing fibers 520 into the material etc. It may be of integral design, or it can consist of parts which can be joined together by sewing, welding, riveting or by other elements. A further, sheet-like reinforcement 510 can be placed in the hollow chamber and is used to absorb tensile loads in the axial longitudinal direction, and therefore in the transverse direction with respect to the extrusion direction of the bellows material, and for this purpose consists, for example, of a fabric web. This fabric web should preferably reach as far as the end sections 53 in the cavity 45 . Since when fitting a compensator formed in this manner to a next duct piece a sheet-like insert which is inserted on the inside, for example a woven insert, can also be clamped in place at the same time, said insert, when it is of shorter dimensions than the inner wall or outer wall 43 , 41 , can absorb the tensile forces without them having to be absorbed by the bellows material.
Finally, ribs or fins running transversely with respect to the longitudinal direction of the bellows, i.e. from one end section 53 to the opposite end section 53 , and serving as expansion-limiting means in the longitudinal direction of the compensator may also be put in place during the production process.
Otherwise, depending on the intended use and requirements, the material can be manufactured from flame-resistant, ray-absorbing, noncombustible, acidproof, heat-deflecting and/or thermally stable material.
Furthermore, the abovementioned cavity 45 of the tubular bellows material can be filled or stuffed, depending on requirements, with suitable sheet-like materials, for example fabric inserts, wire meshes, rubber mats, plastic lattices etc., which are used, in particular, to give the bellows a greater load-bearing capacity. However, other tear-resistant materials can equally well be inserted and used too.
Moreover, however, the cavity 43 may also be filled with other suitable amorphous material, for example material in the form of granules, styropor, quartz or similar materials.
With reference to FIG. 7, a modification is shown in which flange profiles 5 are extruded together with the bellows material. The shaping of the lateral flange projection is at least similar as in the use of the flange profiles explained with reference to FIGS. 1 to 6 .
In the exemplary embodiment according to FIG. 7, the flange profiles 5 extruded at the same time are provided on the rear with a corresponding, rearwardly open recess 71 having opposite undercuts 73 which ultimately serve for the insertion of the plug-in legs 15 ′.
During production of a cross section rectangular compensator made of bellows material and a flange profile extruded with it, there are made in the bellows material, corresponding to the height and width of the compensator, from the flange side 75 , corresponding to the plan view according to FIG. 8, lateral slots or incisions 77 (for example by punching), which start from the longitudinal edges 81 , specifically running at right angles thereto, which reach close to the sealing projection 61 . The flange sections separated in this manner can then be pivoted away from one another about a pivot axis 78 , which is perpendicular with respect to the plane of the drawing in FIG. 8, at the inner end of the incision until the cut edges 82 , which are parallel in FIG. 8, of the flange sections articulated in this manner lie at right angles to each other. If the flange sections formed in this manner are then further pivoted to the rear through 90° with respect to the central, double-walled tube section, then they take up a position which is reproduced in FIG. 9 and in which the corresponding plug-in leg 15 ′ of a corner bracket can then be plugged into the undercuts or recesses 71 formed in this manner. If the plug-in legs 15 ′ are shaped in accordance with the above-explained recess 71 with a corresponding undercut 73 , then the plug-in legs can be plugged in here, so that all in all a stable flange frame 9 is produced. In the process, the plug-in leg can also be directly clipped in from the rear in accordance with the wedge-shaped run-on surface 84 adjacent to the undercuts 73 until the undercuts 73 fit over the relevant plug-in leg 15 ′ of a corner piece and thereby produce a fixed connection to the corner bracket.
A slightly modified exemplary embodiment is shown with reference to FIGS. 10 and 11, once in cross section and once in plan view and comparable to the illustration according to FIGS. 8 and 9, the exemplary embodiment differing from FIGS. 8 and 9 only in that the flange projection together with the end section of the bellows has already been produced during the extruding process at an approximately 90° orientation to the central, double-walled bellows section, in a comparable manner to the flange projection in the exemplary embodiment according to FIG. 5 . The further processing to produce a compensator then takes place as explained in principle with reference to FIGS. 8 and 9.
As an alternative and supplement, a corner bracket 7 which has plug-in legs 15 ′ and is formed from plastic can also be plugged in in accordance with the cross sectional illustration according to FIG. 11 . In this exemplary embodiment, the recess 71 is likewise provided with undercuts 73 , namely undercuts formed in a V shape in cross section, with the result that the plug-in legs can be plugged here into the recess 71 formed in this manner and provided with an undercut 73 , simply by pressing from the rear. A rectangular flange frame, and therefore ultimately a rectangular compensator, can also be produced easily and without any problem as a result.
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A bellows for a compensator as an elastic connection between two duct connection pieces or flange frames arranged from each other in the longitudinal direction is presented. The bellows contains a cavity arrangement between an outer wall, an inner wall, and curved sections at each end of the outer and inner walls. The outer wall, inner wall and curved sections are continuously connected. The cavity arrangement between the outer wall and the inner wall is designed as a single-chamber cavity. The single-chamber cavity between the outer wall and the inner wall is formed in a manner such that it is free from connecting webs. The material of the bellows is flexible.
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BACKGROUND OF THE INVENTION
This invention relates generally to electronic keyboards, and is particularly directed to the detection of simultaneously engaged keys in a multi-key, high speed keyboard.
An experienced typist typically engages in rapid sequence desired keys on a multi-key keyboard. Although each key is sequentially engaged, at any given instant in time more than one key may be down. This requires high speed key detection and the ability to distinguish between simultaneously engaged keys. In a typical matrix-type keyboard, this calls for rapid scanning of the matrix by sequencing input signals to the columns, or rows, of the matrix and detecting an output signal representing a selected key in a given row, or column. The matrix keyboard includes a plurality of mechanical switches, each located at the intersection of a row and a column. Selection of a key results in closure of the switch and provides a signal path for indicating which key has been engaged.
A matrix switch arrangement utilizing mechanical switches possesses inherent limitations in detecting the simultaneous engagement of multiple keys. This is due to the manner in which the rows and columns are sequentially scanned and the ambiguities inherent in the simultaneous selection of more than one switch in a given row or column. One approach for solving this problem attempts to detect three simultaneously engaged keys forming a right angle in the matrix keyboard. If such an orientation of engaged keys is detected, the microprocessor controlling keyboard scan waits to report engagement of the third key until one of the first two keys is deselected. While this approach claims to solve the problem of "ghost key" engagement, it involves a somewhat complicated algorithm implemented by the microprocessor for detecting the required right angle orientation of the selected keys. In addition, this approach results in a relatively slow scan of the keyboard which raises the possibility of missed keys during high speed operation. The ideal system would be capable of detecting the simultaneous engagement of all keys (N) on the keyboard and of keeping track of the sequence in which each of the keys was selected. This capability is generally referred to as "N-key rollover" and while many systems claim to have this capability, virtually none do as it would require an overly complicated and expensive microprocessor controlled keyboard scanning routine. Most available systems offer something less than "N-key rollover" and represent a trade-off between capability and expense.
The present invention is intended to provide an improved keyboard scanning system and method particularly adapted for use in a mechanical matrix-type, multi-key keyboard which is inexpensive and highly reliable in rejecting spurious keyboard entry signals.
OBJECTS OF THE INVENTION
Accordingly, it is an object of the present invention to provide an improved keyboard scanning technique.
It is another object of the present invention to provide for the detection of simultaneously engaged keys in a multi-key, high speed keyboard.
A further object of the present invention is to provide an inexpensive and accurate means and method for the detection of simultaneously engaged keys in a high speed keyboard.
Still another object of the present invention is to provide an improved microprocessor-controlled keyboard entry scheme particularly adapted for high speed applications which reduces the possibility of erroneous key detection.
BRIEF DESCRIPTION OF THE DRAWINGS
The appended claims set forth those novel features believed characteristic of the invention. However, the invention itself as well as further objects and advantages thereof, will best be understood by reference to the following detailed description of a preferred embodiment taken in conjunction with the accompanying drawings, where like following reference characters identify like elements throughout the various figures, in which:
FIG. 1 illustrates partially in block diagram form and partially in schematic diagram form a keyboard scanning system in accordance with the present invention;
FIG. 2 shows a simplified block diagram of a microprocessor utilized in the keyboard scanning system of FIG. 1; and
FIGS. 3 and 3A show the sequence of operations in the microprocessor of FIG. 2 in providing for keyboard scanning and key engagement detection in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, there is shown in combination schematic and block diagram form a keyboard scanning system 10 in accordance with the present invention.
The keyboard scanning system 10 includes a microprocessor 12 for controlling system operation, a matrix-type keyboard 16 having a plurality of keys 17 for entering data into the system, and various other circuitry for implementing the various features of the invention as described below. Microprocessor 12 controls the keyboard scanning operation and interfaces with a central processing unit (CPU) 14 which exercises control over the system in which the keyboard scanning system 10 of the present invention is incorporated. CPU 14 typically would control the operation of a computer terminal as in the case of a word processor where data is entered via a keyboard 16 for presentation on a video display (not shown) and subsequent print-out in hard copy form. However, the present invention is not limited to use in a computer terminal, but has application in any system where data is entered via a keyboard under the control of a microprocessor. Various other features of the present invention include the generation of audio signals upon key selection and to indicate various operating modes of the system. The generation of these audio signals is described in detail below.
Microprocessor 12 is coupled to CPU 14 via a data bus 18 as well as a control bus 20. Data bus 18 includes a plurality of 3-state, bidirectional data bus lines by means of which CPU 14 reads the code of the pressed key of keyboard 16 from microprocessor 12, reads microprocessor 12 status information, and writes command words via the D0 through D7 pins of microprocessor 12. Various microprocessor control signals are provided via control bus 20. When CPU 14 addresses the microprocessor 12, the I/O port decoder (not shown) of CPU 14 asserts KEYBDSEL to the CS pin of microprocessor 12 for the activation thereof. The A0 address input provided to microprocessor 12 from CPU 14 indicates whether the byte transfer via the D0 through D7 pins is data (A0=0) or a command (A0=1) and is derived from the buffered address line BA0 from CPU 14. When the DBIN output from CPU 14 is asserted to the RD input pin of microprocessor 12, microprocessor 12 transfers its internal data to lines D0 through D7 and data from microprocessor 12 can then be loaded into the CPU's accumulator (not shown). When CPU 14 asserts the WR input to microprocessor 12, data provided by CPU 14 may be loaded into microprocessor 12. A RESET output from CPU 14 clears the microprocessor's status flip-flops and program counter (not shown) to 0 and initializes microprocessor 12 prior to the start of operation thereof. A crystal oscillator 50 provides a 6 MHz clocking signal to microprocessor 12 for proper operation of the circuits therein.
A plurality of bidirectional I/O lines 22 which are programmed as input lines to microprocessor 12 are coupled to a connector 32 for rows 0 through 7 of matrix keyboard 16. When a key (not shown) on keyboard 16 is selected, a signal from one of the column lines COL 0 through COL 15 is coupled to one of the row lines via column connector 34 in a conventional matrix switch manner. Microprocessor 12 notes which column is being strobed by checking an internal counter (not shown). By determining which row signal is low, microprocessor 12 determines which column was connected to which row when the key was pressed. From this information, microprocessor 12 then refers to a look-up table in an internal read only memory (ROM) and provides the appropriately coded signal to CPU 14 indicating which key on keyboard 16 has been selected. The T1 input pin is checked by microprocessor 12 when a key is selected to determine if the shift key (not shown) for providing capital letters is also pressed. If so, microprocessor 12 jumps to a routine in its operating program which translates the key pressed to its appropriate shifted code if it has one. Similarly, when a key is pressed, microprocessor 12 checks the T0 input line to determine if the control key (not shown) is selected. If the control key is selected, microprocessor 12 jumps to a routine that translates the key pressed to its appropriate control code, if it has one. Input pins T1 and T0 can be directly tested using conditional branch instructions by microprocessor 12. Each of the input lines 22 is coupled to a respective pull-up resistor for asserting the proper logic state to microprocessor 12. The pull-up resistors are generally shown in block 36.
A plurality of bidirectional I/O lines programmed as output lines 24 couple microprocessor 12 to column connector 34 of matrix keyboard 16 via decoders 28, 30. A 3-bit code output via lines P20, P21, and P22 is converted by decoders 28, 30 to one of eight outputs provided to column connector 34 and thence to a respective column of the matrix keyboard 16. The P23 output from microprocessor 12 determines which of decoders 28 or 30 is actuated by means of NOR gate 42 coupled to decoder 30. Thus, a low output from pin P23 of microprocessor 12 turns on decoder 28, while a high output provided from pin 23 to NAND gate 42 turns on decoder 30. In this manner, the three coded outputs from microcomputer pins P20, P21, and P22 are converted to one of sixteen outputs for the sequential scanning of the oolumn and row matrix of keyboard 16.
The combination of output lines P20 through P23 effectively converts decoders 28, 30 to a 4-line to 16-line decoder with microprocessor 12 pulsing these lines so as to cause a sequential transition in columns 0 through 7 followed by a sequential transition in columns 8 through 15, with the cycle continually repeated for updating key selection data. Decoders 28, 30 have open-collector outputs such that when a given key is deselected, the corresponding line will switch between a high impedance state and logic 0, rather than between a logic 1 and a logic 0. The P24 pin of microprocessor 12 is coupled to a bidirectional I/O line programmed as an output for asserting a KEYINT signal to CPU 14 for sending a keyboard interrupt to CPU 14 prior to placing data on data lines D0 through D7 to CPU 14.
Pin P27 of microprocessor 12 is coupled to a bidirectional I/O line programmed as an output for providing one input to OR gate 60 and one input to NOR gate 44. An output from pin P27 of microprocessor 12 indicates that a key closure has been detected and results in an output signal being provided to one input of OR gate 60. A P27 output from microprocessor 12 via OR gate 60 triggers multivibrator 62, resulting in a momentary high signal being provided to one input of AND gate 84 in peripheral drive circuit 80. The values of resistor 59 and capacitor 61 are selected to provide the desired duration of this signal A 1 KHz signal is provided from the output of oscillator 68 to AND gate 84.
The P27 output from microprocessor 12 is also NORed with the P21 output from microprocessor 12 in NOR gate 44. If both low inputs are provided to NOR gate 44, a high output is provided therefrom to one input of OR gate 64 which is coupled to the input of multivibrator 66. Triggering of multivibrator 66 results in a Q output therefrom for a predetermined duration established by the values of resistor 63 and capacitor 65. The output of multivibrator 66 is provided to one input of AND gate 82 of peripheral drive circuit 80. In addition, the values of resistor 59 and capacitor 61 and resistor 63 and capacitor 65 are selected such that multivibrator 62 outputs a pulse of relatively short duration and multivibrator 66 outputs a pulse of longer duration. Also providing inputs to AND gates 82, 84 of peripheral drive circuit 80 is oscillator circuit 68. Oscillator circuit 68 also provides a 1 KHz output in a preferred embodiment. AND gates 82, 84 are rendered conductive in response to the aforementioned inputs provided thereto for turning on NPN transistors 86, 88, respectively. The outputs from NPN transistors 86, 88 of peripheral drive circuit 80 are provided via current limiting resistor 89 and voltage limiting diode 90 to speaker 92. Thus, the time constant of one shot multivibrator 62 is selected to provide a relatively short period of a 1 KHz signal to speaker 92, while the output of multivibrator 66 provides a relatively long duration 1 KHz signal to speaker 92. The short 1 KHz pulse represents a click sounded upon selection of a key, while the longer 1 KHz pulse represents a beep upon key selection to provide an indication to the user of a special operating mode. For example, a beep sounded by speaker 92 may be desired when operating in a special mode to indicate selection of an illegal key in that mode. Thus, the P21 output of microprocessor 12 serves the dual purpose of providing a coded scan signal to keyboard 16 as well as an indication to speaker 92 of system operation in a special mode.
Referring to FIG. 2, there is shown in simplified block diagram form a microprocessor 12 used in a preferred embodiment of the present invention. An Intel 8741A microprocessor designed for use with a variety of 8-bit microcomputer systems and including a program memory, data memory, 8-bit CPU, I/O ports, timer/counter, and clock is used in a preferred embodiment of the present invention. Microprocessor 12 includes control logic 100 responsive to inputs received from CPU (not shown in FIG. 2) for providing coded instructions to instruction decoder 106 in generating commands for microprocessor execution. A timing circuit 102 responsive to XTAL 1 and XTAL 2 inputs from the external oscillator circuit (also not shown in FIG. 2) provides proper timing signals to control logic 100. Instruction decoder 106 deciphers the coded control inputs from the CPU and generates output commands used with various timing signals to control the functions of arithmetic logic unit (ALU) 108. ALU 108 in response to commands received from instruction decoder 106 performs various arithmetic and logic functions such as incrementing, decrementing, AND, OR, etc., and provides the results of these operations via the microprocessor's internal bus 126 to accumulator 110 for temporary storage therein. The contents of accumulator 110 are provided to data bus status register 112 which provides data to the data bus buffer 104. ALU 108 provides operating information to a flag circuit 114 for generating operating program flags reflecting predetermined status conditions and arithmetic functions.
The program memory 118 is a read only memory (ROM) which contains program instructions for controlling microprocessor 12 operation. A 16-bit program counter 120 monitors program instruction execution and insures proper sequencing of instructions output from ROM 118. The program stored in ROM 118 writes to or reads from the data memory 116 for transferring data to/from the data memory for carrying out the program instructions selected in ROM, or program memory, 118. A timer/event counter 128 receives program operating information from the microprocessor's internal bus 126 and provides timing information to conditional branch logic circuitry 130 to permit the operating program to make decisions and control its operation in response to the instructions read from program memory 118. I/O port 122 and I/O port 124 couple the internal bus 126 respectively to the P10 through P17 and P20 through P27 lines of microprocessor 12 and serve as a buffer for the signals provided from and to microprocessor 12 via the aforementioned pins, or lines. The configuration of microprocessor 12 as used in the present invention is conventional in design, does not form a part of the present invention, and will not therefore be described further herein.
Referring back to FIG. 1, microprocessor 12 may be reset via two key selected inputs from keyboard 16. These signals are CTRL and KBRST which are provided from keyboard 16 to NOR gate 46. In addition, the CTRL signal is provided to the T0 pin of microprocessor 12. The CTRL and KBRST signals from keyboard 16 go low upon selection of the keys causing NOR gate 46 to provide a high to NOR gate 48. The other input terminal of NOR gate 48 is coupled to neutral ground potential permitting NOR gate 48 to operate as an inverter with respect to the input signal provided thereto from NOR gate 46. The inverted output of NOR gate 48 is provided to inverter 52 via grounded capacitor 51 and resistor 55. The RC time constant associated with capacitor 51 and resistor 55 squares up the leading ledge of the output of NOR gate 48 and provides a signal time delay in providing a key debounce function to reduce the possibility of erroneous, or false, system reset. The output of inverter 52 is again inverted by inverter 54 in generating a KBDRESET signal which is provided to CPU 14 for resetting the entire keyboard scanning system 10. Inverter 54 is included to provide the proper logic level to CPU 14 for the resetting thereof. As explained, the input to NOR gate 48 is an active high signal while NOR gate 48 has a low active output. Therefore, a low active input is provided to inverter 52 and a high active input is output therefrom to inverter 54 for generating the KBDRESET for resetting the keyboard scanning system 10 via CPU 14.
Referring to FIGS. 3 and 3A, there is shown the steps involved in scanning the matrix keyboard 16 in order to detect the simultaneous engagement of two separate keys and the deselection of either key so as to provide a reliable means and method for detecting simultaneous key entry in accordance with the present invention. In accordance with conventional flow chart practices, in FIGS. 3 and 3A an eliptical symbol indicates an action or condition for action by microprocessor 12, a diamond symbol indicates a decision point in the program routine being carried out by microprocessor 12, and a rectangle represents the effect or resulting state following a decision. The flow diagram shown in FIGS. 3 and 3A represents the program stored in the ROM 118 of microprocessor 12 which receives control inputs from CPU 14 and data and control inputs from keyboard 16.
The operations described in FIGS. 3 and 3A will now be explained with respect to FIG. 2. Power is initially applied to microprocessor 12 at step 150 prior to initiation of keyboard scanning. Similarly, following a reset operation the program stored in the microcomputer's ROM 118 will begin operation at step 150 as shown in FIG. 3. Following microprocessor power up, the memory storage locations in its RAM, or data memory, 116 and other portions of the microprocessor 12 are initialized to predetermined conditions established by the code stored in the CPU's ROM 118 at step 152. Data transferred from CPU 14 to microprocessor 12 includes keyboard scanning operating instructions and constants. Instructions output by CPU 14 are decoded by instruction decoder 106 before being transmitted to the various microprocessor controlled elements. Control logic in the form of the microprocessor's arithmetic logic unit (ALU) 108 then implements these instructions. At step 154 the program determines whether the keyboard scanning system is in a normal scan mode or in an alternate keyboard scanning mode. For example, an alternate scanning mode may be used when the keyboard is used to provide inputs in playing a video game, whereas the normal scan mode is utilized in a word processing application. If the program determines that it is not in a normal scan mode, it proceeds to a routine for carrying out the selected special scan mode shown at point "D". If the program determines that it is still in a normal scan mode of operation, it proceeds to step 156 and implements a FIFO (First In First Out) routine for data memory 116 in microprocessor 12. Data memory 116 processes data provided thereto in a first in/first out manner. The program then executes a scan of the next column in sequence at step 158 looking for a selected key and determines whether any key is down at step 160. If no key is detected as selected, the program returns to point "A" and step 154 where a determination of whether the system is in the normal scan mode is made and the program continues as described earlier.
If a key is determined as engaged at step 160, the program decodes that key at step 162 by means of the decode portion of data memory 116 and provides this decoded information to the FIFO data memory 116. At step 166 this decoded key information is stored in a first location, designated a "last" key location, for subsequent use. A key debounce routine is then executed at step 168 to verify that a key has indeed been selected.
The microprocessor 12 then continues to scan keyboard 16 looking for the engagement, or selection, of any other key at step 170. If no other key is detected as selected, the program then checks to determine whether the "last" key is still down at step 172 or has been deselected. A key debounce routine is executed at step 176 if the earlier selected key has been deselected and the program branches to point "A" in order to determine whether the system is in the normal scan mode at step 154. If the last key detected is still engaged at step 172, the program then executes a process any repeat routine at step 177 to determine if the auto repeat function has been enabled for repeating the selection of the "last" key automatically or if the "repeat key" (not shown) on keyboard 116 has been selected. At step 180 the program updates the status of the modifier keys, e.g., shift key, and re-encodes the selected key and proceeds to point "B" to detect the engagement of any other key at step 180.
Upon the detection of the engagement of a second key at step 170, the program then decodes the selected key at step 171 and provides that coded key input to the FIFO data memory 116 at step 174, performs a key debounce routine at step 178 for insuring valid key engagement, and shifts the contents of the "last" key location in data memory 116 to a second, predetermined location therein designated the "first" key location at step 182. The program then stores the most recently selected, or new, key code in the first memory location in data memory 116 termed the "last" key location at step 184. The program at step 186 then determines whether the "first" key is still engaged, and if the "first" key has been deselected, a key debounce routine is performed at step 188 with the program returning to point "B" for detecting the selection of any other key at step 170.
If the "first" key detected is still engaged at step 186, the program then determines whether the "last" key is still down at step 190 and performs a branching function. If the "last" key is still down, the program again processes any repeat instruction at step 198, as previously explained, and updates the status of the modifier keys and re-encodes the selected "last" key in accordance with the modifier keys selected at step 200 and returns to point "C" in the program in order to detect when the "first" key has been deselected at step 186. If the "last" key is detected as deselected at step 190, the program renames the "first" key as the "last" key by shifting the coded contents of the second memory location in data memory 116 to the aforementioned first memory location therein. Thus, the keyboard scanning in accordance with the present invention is able to keep track of the relative order of selection of first and second keys and, in order to simplify the scanning operation and maintain the present invention as an economical approach offering high speed and accurate key selection detection, processes only the last two selected keys. It is only after one of these two keys has been deselected, that the program looks for a third selected key. Following the redesignating of the "first" as the "last" key at step 192, the program then updates the status of the modifier keys and re-encodes the selected key in accordance with this update at step 194, performs a key debounce routine at step 196, and returns to point "B" to detect the engagement of any other key at step 170.
There has thus been shown an improved keyboard scanning system and method in which only the last two selected keys and the order in which they were selected is detected and stored in memory. Engagement of a special mode key such as a capital letter or letter repeat key is asserted only with respect to the intended key even if both keys are selected at the same time. The present invention reduces the possibility of erroneous key detection while providing for the accurate and rapid detection of an engaged key in a matrix-type keyboard.
While particular embodiments of the invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects and, therefore, the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention. The matters set forth in the foregoing description and accompanying drawings is offered by way of illustration only and not as a limitation. The actual scope of the invention is intended to be defined in the following claims when viewed in their proper perspective based on the prior art.
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A multi-key keyboard is scanned at high speed in such a manner as to substantially reduce erroneous key entries caused by the simultaneous engagement of more than one key. A keyboard processor determines which key is down by sequential scanning of the keyboard, encodes the selected key and sends this code to a master processor, or CPU. A 2-key lockout scanning approach is employed wherein keyboard scanning stops when two keys are selected simultaneously. Scanning is resumed when either one or both of the first two keys are released. By limiting simultaneous key engagement detection to two keys, system complexity and cost are kept within reasonable limits while insuring against erroneous key entries. Detecting and storing the key engagement sequence permits a selected special function, e.g., automatic key repeat, to be applied to the last selected key rather than to an earlier selected, but simultaneously engaged, key.
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BACKGROUND OF THE INVENTION
[0001] The present invention is directed to a combination appliance for cooling/freezing and cooking a food item, and more specifically to a self-contained refrigerator/freezer and oven, for refrigerating/freezing and cooking food in the same enclosed chamber, which can be actuated by the operator from a variety of remote locations around the world through a public exchange computer communications system, the public switched telephone network or the Internet.
[0002] Many families today have two wage earners and as a consequence, there can be a significant delay when they both return from work before the evening meal can be prepared. Not only that, but sometimes their schedules change during the day so that the time when the evening meal is to be prepared must be changed.
[0003] There are a number of combination refrigeration systems and heating units known wherein the food is confined to the same space. U.S. Pat. No. 6,121,593, Mansbery et al., the contents of which are hereby incorporated by reference, is directed to a food heating and cooling unit which may be actuated from a remote location. However, U.S. Pat. No. 6,121,593 describes a refrigerator oven wherein the refrigerator is a thermoelectric heat pump and the oven is a microwave oven.
[0004] Conventional ovens, either gas or electric, offer the advantage of more traditional cooking processes which allow browning of a product and avoid the problems of accelerated and uneven cooking of some products (breads and chesses for instance) that arise with microwave cooking. Because the volume of the typical conventional oven is considerably larger than that of a microwave oven, a higher capacity cooling system is required than for the refrigerator oven with a microwave heating unit.
[0005] Thus the need exists for a combination refrigerator/freezer oven with a conventional oven and a cooling system with sufficient capacity to handle the cooling requirements of a conventional oven. Furthermore the need exists for a means for remote activation of the heating and cooling units.
BRIEF SUMMARY OF THE INVENTION
[0006] In view of the aforementioned needs, the invention contemplates a combination refrigerator/freezer and oven that provides for selective cooling and cooking of foods. The present invention further contemplates the combination refrigerator and oven is capable of actuation from a remote location. For ease of reference, the preferred embodiment of a refrigeration module will be discussed. However, it is understood that the invention is suitably comprised of a combination freezer and oven that provides selective freezing, thawing and cooking.
[0007] One aspect of the present invention contemplates a combination appliance for cooling and cooking a food item, comprising a frame, a door, a heat element, an inlet duct, a return duct, and a refrigeration module. The frame comprises a cooking chamber and a refrigeration module chamber, and the cooking chamber having an opening through which access to the interior of the cooking chamber is provided. The door moveably mounted to the frame for movement between an open position where the opening is uncovered and a closed position where the opening is covered. The heat element is disposed within the cooking chamber to selectively provide heat to the cooking chamber. The inlet duct extends between the refrigeration module chamber and the cooking chamber, and has an inlet in communication with the refrigeration module chamber and an outlet in communication with the cooling chamber. The return duct extends between the refrigeration module chamber and the cooking chamber, the return duct has an inlet in communication with the cooking chamber and an outlet in communication with the refrigeration module chamber. The refrigeration module comprises a compressor, condenser, evaporator, and base. The compressor, condenser, and evaporator are mounted on the base to form a module. An insulated housing covers the evaporator to thermally isolate the evaporator from the condenser. The insulated housing has an inlet and an outlet, which align with the outlet of the return duct and the inlet of the inlet duct, respectively, when the refrigeration module is mounted within the refrigeration module chamber, to thereby form a refrigerated air path between the evaporator and the cooking chamber.
[0008] When remote actuation is desired, the present invention contemplates a first means for controlling the operation of the heating element and the refrigeration-module, and a second means for sending and receiving data concerning the heating element and the refrigeration module to and from the remote location via either a telephone or the Internet, whereby an individual may evaluate data concerning the heating element and the refrigeration module received through the second means thus enabling the individual to direct and control the first means through the second means.
[0009] Another aspect of the present invention contemplates a combination appliance for freezing and cooking a food item, comprising a frame, a door, a heat element, an inlet duct, a return duct, and a refrigeration module. The frame comprises a cooking chamber and a freezer module chamber, and the cooking chamber having an opening through which access to the interior of the cooking chamber is provided. The door moveably mounted to the frame for movement between an open position where the opening is uncovered and a closed position where the opening is covered. The heat element is disposed within the cooking chamber to selectively provide heat to the cooking chamber. The inlet duct extends between the freezer module chamber and the cooking chamber, and has an inlet in communication with the freezer module chamber and an outlet in communication with the cooking chamber. The return duct extends between the freezer module chamber and the cooking chamber, the return duct has an inlet in communication with the cooking chamber and an outlet in communication with the refrigeration module chamber. The freezer module comprises a compressor, condenser, evaporator, and base. The compressor, condenser, and evaporator are mounted on the base to form a module. An insulated housing covers the evaporator to thermally isolate the evaporator from the condenser. The insulated housing has an inlet and an outlet, which align with the outlet of the return duct and the inlet of the inlet duct, respectively, when the freezing module is mounted within the refrigeration module chamber, to thereby form a refrigerated air path between the evaporator and the cooking chamber.
[0010] When remote actuation is desired, the present invention contemplates a first means for controlling the operation of the heating element and the freezer module, and a second means for sending and receiving data concerning the heating element and the freezer module to and from the remote location via either a telephone or the Internet, whereby an individual may evaluate data concerning the heating element and the freezer module received through the second means thus enabling the individual to direct and control the first means through the second means.
[0011] Another aspect of the present invention contemplates a time-bake cooking cycle for a refrigerated oven used to cook a food item. The refrigerated oven comprises a cooking chamber selectively closeable by a door, a heating element for heating the cooking chamber, a refrigeration unit for cooling the cooking chamber, a temperature sensor for sensing the temperature of the cooking chamber, a data input device for inputting user-selected cooking cycle parameters, and a controller. The controller operably coupling the heating element, refrigeration unit, temperature sensor, and the data input device to selectively actuate the heating element and the refrigeration unit in response to the sensed temperature and to implement the cooking cycle as defined by the cooking cycle parameters. The time-bake cooking cycle comprising a cool cycle and a bake cycle. In an alternate embodiment, the time-bake cooking cycle further comprises a warm cycle. During the cool cycle the temperature of the cooking chamber is maintained at a first predetermined temperature to prevent spoilage of the food item in the cooking chamber. The bake cycle following the cool cycle maintains the temperature of the cooking chamber at a temperature to cook the food item in the cooking chamber. The warm cycle is suitably configured to follow the bake cycle to maintain the temperature of the cooking chamber at a temperature suitable for serving the food item upon removal from the cooking chamber.
[0012] The time-bake cooking cycle may further comprise a second cool cycle initiated after one of the cook cycle or the warm cycle. The time-bake cooking cycle would typically include a data input cycle prior to the cool cycle wherein user-defined operating parameters are stored in the controller. The user-defined operating parameters comprise an End Time representing the time of day that the cooking of the food is to be completed and a Bake Time representing the length of time to cook the food.
[0013] Yet, another aspect of the present invention contemplates a time-bake cooking cycle for a freezer oven used to cook a food item. The freezer oven comprises a cooking chamber selectively closeable by a door, a heating element for heating the cooking chamber, a freezer unit for cooling the cooking chamber, a temperature sensor for sensing the temperature of the cooking chamber, a data input device for inputting user-selected cooking cycle parameters, and a controller. The controller operably coupling the heating element, freezer unit, temperature sensor, and the data input device to selectively actuate the heating element and the freezer unit in response to the sensed temperature and to implement the cooking cycle as defined by the cooking cycle parameters. The time-bake cooking cycle comprising a freeze cycle, a bake cycle, and a warm cycle. In an alternate embodiment, the time-bake cooking cycle comprises a freeze cycle, a bake cycle, and a warm cycle or cool cycle, or both. During the freeze cycle the temperature of the cooking chamber is maintained at a first predetermined temperature to prevent spoilage of the food item in the cooking chamber. The bake cycle following the freeze cycle maintains the temperature of the cooking chamber at a temperature to cook the food item in the cooking chamber. The warm cycle following the bake cycle maintains the temperature of the cooking chamber at a temperature suitable for serving the food item upon removal from the cooking chamber.
[0014] In another embodiment, the time-bake cooking cycle comprises a cool cycle initiated following the completion of one of the cook cycle or the warm cycle. The time-bake cooking cycle would typically include a data input cycle prior to the freeze cycle wherein user-defined operating parameters are stored in the controller. The user-defined operating parameters comprise an End Time representing the time of day that the cooking of the food is to be completed and a Bake Time representing the length of time to cook the food.
[0015] Still other aspects and advantages of the present invention will become readily apparent to those skilled in this art from the following description wherein there is shown and described a preferred embodiment of this invention, simply by way of illustration of one of the best modes best suited for to carry out the invention. As it will be realized, the invention is capable of other different embodiments and its several details are capable of modifications in various obvious aspects all without departing from the invention. Accordingly, the drawing and descriptions will be regarded as illustrative in nature and not as restrictive.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0016] The accompanying drawings incorporated in and forming a part of the specification, illustrates several aspects of the present invention, and together with the description serve to explain the principles of the invention. In the drawings:
[0017] FIG. 1 is a functional block diagram of combination cooling/freezing and cooking system for food, which may be actuated from a remote location;
[0018] FIG. 2 is a block diagram overview of the software included in the present invention;
[0019] FIG. 3 is a flow chart describing the initialization of the home appliances for remote access;
[0020] FIG. 4 is a flow chart describing the remotely located software used to communicate with the home appliances from a remote location;
[0021] FIG. 5 is a flow chart illustrating the selection of a particular home appliance for remote operation;
[0022] FIG. 6 is a flow chart describing management of the home appliances, which includes determining which home appliances will be available for possible remote access;
[0023] FIG. 7 is a flow chart illustrating the determination of food dishes that will be available for preparation in the home appliances from a remote location;
[0024] FIG. 8 is a flow chart describing how the home appliances operation buttons are accessed from a remote location;
[0025] FIG. 9 is a flow chart illustrating how a food dish is programmed for preparation in a home appliance from a remote location;
[0026] FIG. 10 is a flow chart describing the process for reproducing the information displayed by home appliance at a remote location;
[0027] FIG. 11 is an isometric view of a refrigerator oven;
[0028] FIG. 12 is a perspective view of a combination refrigerating and cooking system with a drawer containing the refrigeration module in the open position;
[0029] FIG. 13 is a perspective view of a combination refrigerating and cooking system with a door providing access to the cooking chamber in the open position; and
[0030] FIG. 14 is a block diagram of the components of the refrigeration module.
DETAILED DESCRIPTION OF INVENTION
[0031] Throughout this description, the preferred embodiment and examples shown should be considered as exemplars, rather than limitations, of the present invention. For ease of reference, the preferred embodiment of a refrigeration module will be discussed. However, it is understood that the invention is suitably comprised of a combination refrigerator/freezer and oven that provides selective refrigerating, freezing, thawing and cooking.
[0032] Referring now to FIG. 1 , the cooking and refrigeration chamber is indicated at 10 in dotted outline. Contained within the chamber is a refrigeration module 1 - 1 that is utilized for cooing the cavity 17 . Temperature control 14 is used to turn the refrigeration-module 11 on and off. Temperature sensor 15 is used by temperature control 14 to maintain a desired temperature.
[0033] The heat element 18 as shown is connected to the control relays 19 . Ordinarily, the heat element 18 may either be an electric resistive element or a gas burner, however other types of heat elements such as microwave, radiated heat elements, infra red, or any other heat source may also be utilized. As shown the heat element is controlled by control relays 19 . Temperature control 14 can be used to activate and deactivate control relays 19 . The type of control app lied is dependent upon the type of heat element used. The location of the heat element 18 is normally at the bottom of the cavity 17 . However, it can be located anywhere in the cavity. A second heat element (not shown) may also be placed at the top of the cavity 17 for broiling.
[0034] Referring now to FIGS. 11-13 there is shown a combination appliance 1100 . The combination appliance 1100 comprises a door 1102 which covers a cavity 17 that is used as a cooking chamber. A window 1104 enables a user to view the contents of the cooking chamber. The appliance 1100 further comprises vertical walls 1108 , a top surface 1110 and a control panel 1116 mounted on the top surface. Burners 1112 are also mounted on top surface 1110 . The burners 1112 may be gas, electrical, or other heating means well known in the art.
[0035] The control panel 1116 is used for obtaining input for operating the cooking chamber. Mounted on the control panel 1116 are control knobs 1114 which are used to control the burners. A display 1118 is mounted on the control panel 1116 and is used as a local control for the cooking chamber. The display would ordinarily comprise selectors 1120 , which commonly are either pushbuttons or touchscreen, and/or a dial selector 1122 which may be used for selecting a temperature for the cooking chamber or scrolling through menu choices.
[0036] Within the cavity 17 is the heat element 18 , an outlet 1134 duct and an inlet duct 1136 . The heat element 18 may be gas, electric, or any other heat source. As shown in FIG. 13 , the heating element is at the bottom of the cavity 17 . However, heat element 18 may be located anywhere in the cavity 17 . It is further contemplated that a second heat element (not shown) may be mounted at the top of the cavity 17 for broiling. As indicated by arrow 1132 , heat rises from heat element 18 .
[0037] Drawer 1106 is adapted to slide in and out to provide access to the refrigeration chamber 1160 containing the refrigeration module 11 , mounted on the bottom 1124 of the drawer 1106 . Referring to FIG. 14 with continued reference to FIGS. 11-13 , the refrigeration module 11 performs a refrigeration cycle to withdraw heat from cooking chamber so that the temperature in cavity 17 will be lower than the ambient temperature surrounding the appliance 1100 . The Refrigeration module 11 is a closed-loop system that uses a fluid, or refrigerant, to move heat from one place to another. Drawer 1106 is aligned such that when it is in a closed position, the ducts connecting inlet duct 1136 and outlet 1134 duct are aligned with the warm air inlet 1152 and cool air outlet 1154 of the thermally insulated evaporator housing 1128 .
[0038] The refrigeration module 11 comprises a compressor 1126 , condenser 1144 , an expansion valve 1146 and an evaporator 1142 within a thermally insulated housing 1128 . Tubing 1130 is used to connect the compressor 1126 to the condenser 1144 , the condenser 1144 to the expansion valve 1146 , the expansion valve 1146 to the evaporator 1142 , and the evaporator 1142 to the compressor 1126 and provides the path for the fluid, or refrigerant. Arrows 1148 indicate the direction of the fluid, or refrigerant, flow through the tubing 1130 .
[0039] In operation, cool, liquid refrigerant enters the evaporator 1142 . The refrigerant in evaporator 1142 absorbs heat from cavity 17 communicated from inlet duct 1136 to warm air inlet 1152 and changes state from a liquid to a vapor. The vapor refrigerant exits evaporator 1142 and moves into compressor 1126 . Compressor 1126 raises the pressure and temperature of the refrigerant so that the refrigerant will move through refrigeration module 11 . The increase in pressure causes the refrigerant to flow out of compressor 1126 and into condenser 1144 . Condenser 1144 releases heat from the refrigerant to the outside air. Refrigeration module 11 may include a condenser fan 16 ( FIG. 1 ) for facilitating the movement of heat away from condenser 1144 . The vapor refrigerant exits from condenser 1144 and goes to the expansion valve 1146 . At expansion valve 1146 , the pressure of the refrigerant is reduced and the refrigerant is cooled to the point where it returns to a liquid state. The cool, liquid refrigerant exits expansion valve 1146 and re-enters evaporator 1142 . Upon entering evaporator 1142 , the liquid refrigerant absorbs heat from warm air 1150 drawn into evaporator 11142 through warm air inlet 1152 . As warm air 1150 passes over evaporator 1142 , it gives up some of its heat to produce cool air 1156 which is recirculated by evaporator fan 16 ( FIG. 1 ) through cool air outlet 1158 and back into cavity 17 .
[0040] Referring now to FIG. 1 , the digital controller unit 20 comprises the following items computer 21 with microprocessor with random access memory and read only memory for control program storage and operation, visual alpha/numeric display 22 , and data/control entry keyboard 23 . Also included is the communications interface circuits 25 . It is understood that the communication interface is any suitable communication interface known in the art. Examples include but are not limited to power line communication protocols, Ethernet, and wireless interfaces.
[0041] In operation, the computer 21 executes a control program stored in electronic memory and by using input/output signals which enable the multiple functions of the digital controller unit 20 . These functions are 1) receiving operating commands and data from the data/control entry keyboard; 2) displaying cooking times and related information and providing visual operator feedback for keyboard data entries; 3) monitoring safety interlock switches such as the door as well as temperature sensors; 4) control signals to power control relays which in turn actuates the refrigeration module 11 or the heat element 18 ; 5) manage internal clock and timing functions as required; 6) responding to control requests submitted via digital control from remote locations.
[0042] The alpha/numeric display 22 informs the user of important information such as cooking time, operating mode and visual operator feedback of keyboard keys pressed.
[0043] Provision has also been included for the complex DISPLAY from the front of the refrigerated oven. This includes a remote display interface circuit board, which interfaces with the Display of the oven directly and relays the display contents at any point in time to the internal communication interface controller. The communication interface controller requests the display contents up to 10 times a second. The communication interface controller then packages up the display sequences and sends it out through the communication interface. The appliance server running on the home computer receives the display sequence through the communication interface operably coupled to the home computer and upon request relays this information on to the current programs running on the home computer or at the office.
[0044] The keyboard data control entry 23 is an array of electronic switches located at the front of the digital controlling unit. The switches are interfaced with the computer and provide the user a method of entering data and commands to the computer. Each switch enters specific information such as numeric values zero through nine; direct commands start/stop, etc.; automated macro commands designed to reduce user time and involvement (i.e., potato sets cooking time appropriate for cooking a potato, initiates the cooking process and stops the operation after the specified time). The front panel provides legend labels which denote the purpose of each keyboard button. This is typical of a state of the art oven.
[0045] The DC power supply 24 receives AC power from the electrical power distribution and produces all DC voltage and current required to operate the digital controlling unit. The communication interface 25 provides communication with remote control of four functional categories: temperature control, electrical power control, safety interlocks and remote control. An electronic temperature sensor (not shown) located in the cold air path is electronically interfaced to the computer. This allows the computer control algorithm stored in memory to measure the refrigerator temperature if the measured temperature is above an established set point or correction signal is sent to a control relay that energizes the refrigeration system. This is mutually exclusive of cooking activities of course.
[0046] The electronic power control at the communication interface 25 is provided to allow low voltage, low power logic signals from the personal computer 26 to energize or de-energize control relays that activate the cooking system or refrigeration system.
[0047] The software involved consists of three major parts. The first part is the appliance server which directly controls all of the appliances in a home. This is accomplished using the communication interface protocol which is generally found in home networks. The second part of the software portion of Applicant's invention is a Graphical User Interface (GUI) for easily controlling home appliances as well as managing the meals that are to be cooked. The third part of the software allows homeowners to control and monitor their appliances while away from the home through the GUI or from their favorite worldwide web browser. Many homes and small offices are being equipped with “Thin Servers”. These so called “Thin-Servers” are appliance-like-devices that control home computer/print networks, Internet connections, home lighting and intelligent appliances. The home computer or “Thin-Server” can be used to monitor and control the home appliances, including microwaves, ovens and refrigerators, as well as other appliances. The protocol used to control such an appliance from the home server is one that has been developed specifically for the home network communication interface. The communication interface protocol allows one to provide an abstract definition of say an appliance and be able to query it and perform operations on it. Communication interface can operate over many different types of networks, power lines, radio frequency, coaxial cable and twisted pair, as well as others. The Applicant's invention uses existing power lines in an existing home to communicate to the appliances. This avoids retrofitting a home with a new network. Applicant's invention uses object oriented methodologies in many ways. The system is written in an object oriented language. Second, the communication interface protocol is object oriented by design. Each communication interface device is considered an object with attributes that can be interrogated or changed directly via operations or methods. Lastly, the technology used to communicate with the home appliances from anywhere in the world is a remote interface means for selective control and monitoring of appliance via a remote disposed data terminal. The remote interface is any suitable remote interface known in the art. Essentially, this technology allows one to easily design objects (such as home appliances) in one's home. These objects can be directly manipulated from any computer around the world.
[0048] The use of the remote interface is an important aspect for the remote operation of the appliance. A remote interface object on the home server is built for each home appliance. These objects take requests from the software to control the appliance. The software could be located locally on the home server or could be remotely located at one's office in another state or country. This allows a homeowner to remotely monitor their home with unprecedented ease and ability. One can also use any worldwide web browser, including, but not limited to Microsoft Internet Explorer and Netscape Navigator/Communicator to monitor or control a home appliance. This is accomplished by using a version of Applicant's software which is written as a Java applet. This applet is launched within the browser and provides te means to communicate with remote interface objects on one's home server that controls the home appliances. The home appliances are controlled via software running on the home server. The home server must be able to communicate using the communication interface protocol via some network media. The communication media interface for communicating information between the oven and the home server is used. The communication media is any suitable communication medium known in the art, such as powerline, Ethernet, and wireless communication. The software on the home server that controls the home appliance is called the appliance server. This is a program that among other things understands communication interface. When started, the appliance server searches for all home appliances in the home. It does this by broadcasting a communication interface request on the communication media to which all communication interface compliant home appliances respond. Response includes its address on the network, the type, manufacturer and model of the appliances. The appliance server knows, based on the appliances manufacturer and model, how to control the appliance. After discovering all home appliances in the home, the appliance server then creates a remote interface object for each appliance. If the home appliances are powered on after the appliance server has started, the appliance broadcasts an announcement that is received by the appliance server. The appliance is then made available via a remote interface object.
[0049] The preferred remote interface is as follows.
SetClock (Integer Hours, Integer Minutes) GetStatus (Integer Status) StartCooling ( ) StopCooling ( ) SetCookTime (Integer Hours, Integer Minutes, Integer Seconds) SetTemperatureLevel (Integer Temp) GetTemperatureLevel (Integer Temp) Cancel ( ) Start ( ) ReadDisplay (String DisplayStr) SetSafeTemperatureLevel (Integer Temp)
[0061] This is the basic interface required to control any home appliance. Other interfaces can be provided based upon the type, manufacturer and model of a specific home appliance.
[0062] The remote interface objects representing home appliances wait for requests. Applicant's software GUI and Applicant's Java applet are two programs that communicate with the remote interface objects in order to control the appliances. These programs are referred to as remote interface clients. Once the client programs connect to these objects, they operate on them as if they were locally defined and created within the client program. The client programs can then use the object's interface to manage the remote appliance.
[0063] As far as safety is concerned, the remote interface object provides an interface for specifying a safe temperature level. If the temperature of the unit rises above this level, the remote interface object will tell the home appliance to shut down. The object will also notify all client programs that are connected to it that a high temperature condition has occurred. An object can also notify all connected clients if a home appliance has stopped responding to input.
[0064] The core of software system is the management/GUI software that allows the user to view each home appliance being controlled. Each appliance can be programmed to keep a dish cool until it is time to be cooked. Dishes can be defined by the user which spells out the steps to cook the dish and whether or not it needs to be kept cool before cooling.
[0065] A major feature of software is the ability to monitor and manage home appliances from remote locations. Applicant's software accomplishes this by providing an appliance server software that runs on the home server. This software is a remote interface server that spawns a remote interface appliance object for each home appliance that it discovers on the home network. These appliance objects continually monitor the real home appliance as well as wait for the GUI software to connect to it. The Applicant's software that connects the appliance objects is referred to as client software. The client software can be run at home on the home server or on another machine in the home. Remote interface objects are inherently distributed. This means that not only can any computer in the home manage home appliances through the remote interface appliance objects, but from any computer in the world, one can monitor and manage appliances in their home. The client software described earlier communicates with appliance objects residing on the home server. The client software is configured with the Internet address of the home server. This allows it to remotely communicate with the home server through the Internet. The client software communicates with the appliance objects through a well known port number. The client software transparently makes requests to the home objects which passes the requests along to the real appliance.
[0066] It is not necessary to have the menu management software installed in order to remotely monitor and manage home appliances in one's home. All it takes is a worldwide web browser, including but not limited to Microsoft Internet Explorer and Netscape Navigator/Communicator. The Applicant's software is also available in the form of a Java applet that can be run from the browser. Having the software available from a browser, users can use just about any type of computer operating system to remotely connect to their home and control home appliances. This gives people unprecedented access and control over their home while away.
[0067] Referring to FIG. 2 , a block diagram representation of the overall software included in the invention. Two major components of the software used by the invention are shown in FIG. 2 . The first software component runs on the home computer and has been titled Tonight's Menu Appliance Server Software 100 . The Tonight's Menu Appliance Server Software 100 can be attached to a communication media 150 via a variety of computer industry communication protocols. The present invention discloses a communication interface Subsystem protocol 120 to communicate with the home appliances 200 . The Tonight's Menu Appliance Server Software 100 receives information from the internet and translates this information into specific commands to operate the home appliances 200 .
[0068] After the Tonight's Menu Appliance Server Software 100 is started, it will initialize the communication interface Subsystem 120 and identify the various home appliances 200 that are connected to the communication media 150 and enable communication with the communication interface Subsystem 120 . The Tonight's Menu Appliance Server Software 100 will also create a remote interface appliance object 110 for each home appliance 200 that can communicate with the communication interface Subsystem 120 . The remote interface appliance objects 110 will allow the Tonight's Menu Client Software or Browser Software 50 to locate the remote interface appliance objects 110 through the Internet and communicate with the Tonight's Menu Appliance Server Software 100 .
[0069] Thus, a user on a remote computer running the Tonight's Menu Client Software 50 connected through the Internet through the remote interface appliance objects 110 to the Tonight's Menu Appliance Server Software 100 can communicate and operate home appliances 200 .
[0070] Referring to FIG. 3 , the Tonight's Menu Appliance Server Software 100 is brought on line in phases. First, all the Appliances 100 to be connected to the system have to be turned on. Second, the Tonight's Menu Appliance Server Software 100 has to be started. After the Tonight's Menu Appliance Server Software 100 is started, it will initialize the remote interface Subsystem 115 which broadcasts out on the communication media 150 ( FIG. 2 ) it's address on the network. The communication interface Subsystem 120 ( FIG. 2 ) acts as a network where every appliance 200 ( FIG. 2 ) is identified by an address that is available to anyone accessing the communication interface Subsystem 120 .
[0071] The Tonight's Menu Appliance Server Software 100 will create a remote interface appliance manager-object 125 which provides a well known object for managing the set of discovered appliances. The Tonight's Menu Appliance Server Software 100 will also create a remote interface food dish manager object 140 that provides a well known object for management of defined food dishes.
[0072] The user configures and selects what appliances 200 will be used to prepare the food dishes for the day. Once the user has selected the appliances 200 , a list of those appliances 200 will be contained in a initialization file. The Tonight's Menu Appliance-Server Software 100 will retrieve the list of configured appliances 155 and communicate with the configured appliances 200 to ascertain what type of appliance it is, whether a microwave or conventional oven, what model, what are its capabilities, etc. After this information has been obtained, the Tonight's Menu Appliance Server Software 100 will initialize the communication interface device on board each appliance 175 and create a remote interface appliance object for all the appliances 180 . The Tonight's Menu Appliance Server Software 100 initialization routines form the framework for communicating with the Tonight's Menu Client Software 50 .
[0073] Referring to FIG. 4 , the Tonight's Menu Appliance Software 50 contains the procedures for communicating with the Tonight's Menu Appliance Server Software 100 in diagramatic fashion. In the figure, the procedure is commenced with a remote interface subsystem initialization routine 51 . The remote interface Subsystem initialization routine 51 initializes an object management system, which allows the user to communicate between the Remote Appliance Object 45 and the remote interface appliance objects 110 located on the user's home computer.
[0074] The remote interface Subsystem Initialization Routine 51 will contact the remote interface Appliance Manager 52 on the Tonight's Menu Appliance Server Software 100 and obtain information regarding the various Appliances 200 connected to the Tonight's Menu Appliance Server Software 100 . Once the remote interface Subsystem Initialization Routine 51 has obtained a list of Appliances 200 connected to the Tonight's Menu Appliance Server Software 100 , the Tonight's Menu Client Software 50 Remote Appliance Objects 45 will bind to the Tonight's Menu Appliance Server Software's 100 remote interface Appliance Manager Object 53 .
[0075] In addition, the remote interface Subsystem Initialization Routine 51 will also contact the remote interface Dish Manager 54 on the Tonight's Menu Appliance Server Software 100 and obtain information regarding the various food dishes to be prepared. After the remote interface Subsystem Initialization Routine 51 has received the information regarding the food dishes, the Tonight's Menu Client Software's 50 will bind to the Tonight's Menu Appliance Server Software's 100 remote interface Dish Manager Object 55 . Upon completion of the binding process; the Tonight's Menu Client Software 50 will allow the user to Open An Appliance 300 , Manage An Appliance 400 or Manage Dishes 500 .
[0076] Looking to FIG. 5 , the Opening An Appliance Software 300 allows the user to access an Appliance 200 using Applicant's invention. The user will select the open appliance option from the file menu 310 . This will indicate to the Tonight's Menu Client Software 50 that the user wants to view or act upon a particular appliance. 200 that is managed by the Tonight's Menu Appliance Server Software 100 . At Block 320 , the Tonight's Menu Client Software 50 communicates with the Tonight's Menu Appliance Server Software 100 located on the home computer through the appliance manager remote interface object. A list of defined appliances 200 is retrieved from the appliance manager. This list is used to display a list of available appliances 330 .
[0077] When the user has selected an appliance to open, a user interface window is created 340 . This window will graphically represent the microwave or conventional oven that is being controlled. This includes the portrayal of keypad buttons as well as an Display of the appliance 200 . The selected remote interface object is then associated with the window representing the appliance 350 . Finally, the window is displayed in the Tonight's Menu Client Software 50 . This function also includes automatically updating the Display without the users need to interact.
[0078] FIG. 6 illustrates the various options a user can exercise regarding the management of appliances software 400 that is specified in block 410 to 470 . The list of appliances and the information about the appliances 200 is stored on the home computer. The Management of Appliances Software 400 allows the user to modify and maintain the information regarding the appliances 200 remotely. Block 410 shows the Management of Appliances Software 400 interrogating the remote interface Appliance Manager on the Tonight's Menu Appliance Server Software 100 for the list of appliances. After the remote interface Appliance Manager receives the list of all the remote interface appliance objects 110 , it will present the list in a list box and the user will have several options available. The options the user will have available pertaining to the list box includes being able to add an appliance 430 , modify an appliance 450 and delete an appliance 460 .
[0079] An appliance is added by sending a message to the remote interface Appliance Manager 52 requesting to add an appliance 430 . This message is a function call on the appliance and on the remote interface Appliance Manager 52 . The Tonight's Menu Appliance. Server Software 100 will create a remote interface Object and make it available for communication. Once that is complete, an empty remote interface Appliance Object 435 will be created and a dialogue box will appear on the Tonight's Menu Client Software 50 and prompt the user for new information regarding the capabilities of the appliance 440 . After the user enters the appliance information including the appliance's communication interface address on the home computer, this information is transmitted to the home computer and stored in the initialization file which will be retrieved the next time the Tonight's Menu Appliance Serve Software 100 is started.
[0080] The Modified Appliance 450 and the Delete Appliance 460 activities are contained in Blocks 430 through 470 . Block 450 shows where the decision is made whether to modify the appliance 200 , if the decision is yes, the user is prompted for new information regarding the appliance 440 . If the user makes the decision to delete an appliance 460 , the remote interface Appliance Object is removed 470 .
[0081] FIG. 7 , discloses the management of dishes software 500 flow chart which details the steps necessary for an appliance 200 to prepare a food dish. The dish manager remote interface object 510 is located on the home computer in order to centralize the management of the food dishes. The management of dishes software 500 allows the user to add a food dish 530 , modify food dishes 550 , modify cooking steps 570 or delete food dishes 580 .
[0082] Once the user is presented with a list of food dishes 520 , the user can choose to add a dish 530 and the program will create an empty remote interface dish object 540 . The software will prompt the user for new values of dish properties or cooking information 560 . This information would include a description of the food dish, comments regarding the food dish, list of cooking steps and whether the food dish should be kept cool prior to cooking. If the user selects the modify dish option 550 , the user will again be prompted for new values of dish properties 560 . At this point, the user can modify a variety of information regarding the food dish including the description of the food dish or the cooking steps.
[0083] Blocks 605 through 630 illustrate how to add a cooking step, modify a cooking step or delete a cooking step. A cooking step includes the cooking duration, the cooking time in hours, minutes and seconds, cooking temperature for conventional ovens and cooking levels for microwaves. If the user chooses to add a cooking step, the software will add a cooking step 605 after it presents the user with a list of the present cooking steps 600 . The software will create an empty remote interface step object 610 and prompt the user for new values of step properties 615 . The user will also be prompted for new values of step properties 615 , if the user selects the modify step 620 option. Furthermore, a cooking step can also be deleted 625 by removing the pertinent remote interface step object 630 .
[0084] Referring to FIG. 8 , the flow chart illustrates utilization of the Tonight's Menu Client Software 50 in combination with the Tonight's Menu Appliance Server Software 100 to operate a home appliance 200 from a remote location. After the user has executed the Opening an Appliance software 300 , the user can press a button on the remotely located user interface for the particular appliance 820 to be used. The software will analyze and determine the button code 830 and invoke the button press method on a remote appliance remote interface object 840 . Information regarding a particular button that was pressed by the user will be transmitted from the Tonight's Menu Client Software 50 to the Tonight's Menu Appliance Server Software 100 .
[0085] Once the Tonight's Menu Appliance Server Software 100 receives this information, the receive button code from remote interface object 850 will begin processing this data. The button information will be checked to ascertain whether it is a valid code 860 , and if not, an error message 870 will be sent to the user. If the button information is a valid code, the data will be translated into the appropriate communication interface packet and transmitted to the specific appliance 880 to be used. The Tonight's Menu Appliance Server Software 100 will notify the user that it has successfully received the user's remote button command.
[0086] FIG. 9 provides a flow chart describing how a user would program an appliance to prepare a food dish from a remote location 900 . Blocks 905 through 925 illustrate how the user would be presented with a list of dishes 905 to facilitate the selection of a dish to be cooked and be prompted to supply the software with a specific time when the food dish is to be ready 910 . Once the Tonight's Menu Client Software 50 has received the proposed finished times for the food dish 910 , the software will determine the appropriate start time 915 . The software will calculate whether the time required to prepare the meal is sufficient in order to complete the meal by the finish time selected by the user 920 . If there is insufficient time to prepare the dish before the finish time, the software will loop back and request the user to re-enter another dish finish time. However, if there is enough time to cook the dish 920 , the food dish information will be sent to the appliance server via the remote interface appliance server 925 .
[0087] The Tonight's Menu Appliance Server Software 100 will receive the food dish information via a remote interface appliance object 930 . After the Tonight's Menu Appliance Server Software 100 has received the dish information, the Tonight's Menu Appliance Server Software 100 , also performs a check to determine whether there is enough time to cook the dish 935 . If there is not sufficient time to cook the dish before the dish finish time, the Tonight's Menu Appliance Server Software 100 will return an error code to the user. If there is sufficient time to cook the dish, the Tonight's Menu Appliance Server Software 100 will start cooling the dish in the appliance 945 . The software will then determine the appropriate time to start cooking the dish in order to have it completed by the desired finish time.
[0088] The Tonight's Menu Appliance Server Software 100 will periodically check whether it is time to start cooking the dish 950 . If it is time to start-cooking the dish, the Tonight's Menu Appliance Server Software 100 will send the appropriate button press sequences to execute the predetermined cooking step 955 . The program will determine if the software has reached the last cooking step 960 . If the software has not reached the last cooking step, the program will loop back to the time to start cooking routine 950 in order to determine whether it is time to start the next cooking step. If the software has reached the last cooking step, then the software will provide the appliance 200 with instructions to keep the dish warm 970 .
[0089] FIG. 10 , shows the flow chart for the remotely-drawing the appliance display software 1000 . This flow chart illustrates how the appliance's 200 display screen is able to be reproduced for the user at a remote location. The Tonight's Menu Appliance Server Softwaare 100 uses a remote display interface circuit board (“RDIB”) that allows for a real time remote location acquisition and display of a microwave or conventional oven's display screen. The RDIB acquires and processes the display data and on demand transmits it to the communication interface adapter for eventual display at a remote location. A typical microwave or conventional oven will have a six position LED Display and there are sixteen segments in each position which the RDIB scans and captures the illuminated LED's on each of the six different positions for translation. The RDIB then translates the illuminated six different positions into a character or a number 1010 .
[0090] The RDB will buffer one (1) second worth of sequences of the display 1020 prior to translating the display information into a communication interface packet. Once the one (1) second buffer of display information is translated into a communication interface packet, this information is transmitted to the appliance server 1030 . After the communication interface packet is sent to the appliance server, the appliance server will buffer two (2) seconds of the display information 1040 prior to transmitting it to the Tonight's Menu Client Software 50 . The buffering of an additional second of display information will improve the transmission process of the display information to the Tonight's Menu Client Software 50 .
[0091] Once the Tonight's Menu Client Software has received the display information through the remote interface appliance objects 1050 , the software will determine the number of display sequences to show 1060 . The Tonight's Menu Client Software 50 will determine whether it has finished its display sequences 1070 . If not, the software loops back to the receive display information through the remote interface appliance object routine 1050 . If the Tonight's Menu is Client Software 50 has finished with the display sequences, it will paint the display screen of the specified appliance on the user's remote interface 1080 . The software will briefly delay the painting of the appliance's display information to imitate a display refresh process on an appliance 1090 . Finally, the programs will loop back to the finish with display-sequence 1070 in order to determine whether it has finished displaying all of the pertinent information.
[0092] It will be appreciated by one skilled in the art that the preceding description of remotely drawing the appliance display software, as shown in FIG. 10 , may be accomplished in a myriad of manners. The capture of the appliance display generally pertains to the retrofitting of an existing appliance. The person skilled in the art will understand that the method described herein may be incorporated into a new appliance. For example, a remote computer accesses the new appliance over any communications channel known in the art. The remote computer then interrogates the appliance for status information and updates. Upon receiving the request for a status update, the appliance may then collect or aggregate the current status information. Having collected the information requested by the remote computer, the appliance then transmits the information to the remote computer using any suitable communications channel. Thus the remote computer is not simply capturing the display of the appliance, but rather presenting to the user status information independent of the information currently be displayed on the appliance display.
[0093] The foregoing description of a preferred embodiment 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. Obvious modifications or variations are possible in light of the above teachings. The embodiment was chosen and described to provide the best illustration of the principles of the invention and its practical application to thereby enable one of the ordinary skill in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance to the breadth to which they are fairly, legally and equitably entitled.
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A self-contained refrigerator/freezer and oven, for refrigerating/freezing and cooking food in the same enclosed chamber, which can be actuated by the operator from a variety of remote locations around the world through a public exchange computer communications system, a public switched telephone network, or the internet. The oven has a heating element such as an electrical resistance heating element or a gas burner. A controller is in communication with the heating unit and the refrigeration/freezer unit. The controller activates the refrigeration/freezing unit when a cooling mode is desired, and activates the heating unit when a heating mode is desired.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to controls for accessories attached or mounted to vehicles and more specifically to a cab mounted control for controlling a high current power source for an electric motor which drives an accessory such as a spreader for sand or salt that is coupled to a vehicle.
2. Description of the Related Art
There are many devices that are coupled with a vehicle that require a separate motor to control and operate the device. For instance, a spreader is often mounted on a vehicle to aid in the deposition of granular material such as salt, seed, fertilizers, chemical agents, sand or the like onto a surface as the vehicle travels over it. The spreader is connected to a material supply bin, which is usually gravity fed. As the material falls through the spreader, its is distributed by an auger or similar driving device. The auger is powered by an electric motor which is controlled by the operator in the cab of the vehicle. The operator can start, stop and control the speed of the spreader by so controlling the motor. The speed of the spreader controls the distribution characteristics of the material being spread.
Traditionally, the electric motor requires a relatively high current power source to adequately drive the spreader. Therefore, the motor control circuitry employed must be able to handle such a high current load. Obviously, any type of circuitry capable of handling such a level of current is appropriate. Generally, the power control circuit is mounted in the cab of the vehicle. The operator then actuates a control which will turn on, turn off and vary the speed of the electric motor by varying the amount of current which ultimately reaches the motor.
While this arrangement provides all of the necessary control the operator may require, it also creates several areas of concern. In order to make such an arrangement functional, relatively heavy gauge wire must be run through the firewall of the vehicle and into the cab. In and of itself, this is a modification which many vehicle owners may be hesitant to make as a correspondingly large hole must be cut. Furthermore, the cab and spreader are usually located on opposite ends of the vehicle. As such, a long length of this heavy gauge wire must be utilized. This adds significantly to the cost of such a system. In order to locate the power control circuitry remotely from the motor and driver device, rather large and very expensive high current handling electrical plugs must be utilized, further increasing the overall cost. These plugs are used to couple the high current wire to a control box that contains the MOSFET and also to couple the wire to a junction with the electric motor. In addition, the length of the wire reduces the efficiency of the system due to the voltage drop-off encountered. Finally, the size of the wire makes it difficult to conceal. As such, the exposed wire is subject to abrasions and inadvertent cutting.
The most significant concern, however, is the relatively large amount of heat that is generated by a MOSFET (or similar component) located within the cab of a vehicle, when handling high current loads. The heat generated by the control circuitry represents a fire hazard and severely limits the design parameters available during installation. Typically, the cab mounted circuitry occupies almost 2 square feet of space. It is difficult to place such a large device within the cab of a vehicle because the heat produced will often adversely affect the surrounding components. A large number of the items within the cab are made of plastic and are thus subject to melt. Wiring proximate the control circuit can also be damaged by the heat and thus short circuit. This causes obvious mechanical/electrical problems and also creates a risk of fire. If the circuitry can be mounted in a location that does not affect components in the cab, it will prevent the operator from being able to fully utilize the cab. That is, anything brought into the cab must be carefully placed to avoid contact with the control circuit.
As such, the heat generated by previous power control circuits is of significant concern. There has been no way to minimize this heat generation as those components which can handle the required current levels must necessarily dissipate this heat in some manner. Presently, such systems must simply be installed within the cab of the vehicle, in a location which hopefully minimizes the exposure of sensitive elements to the high levels of heat generated. The heat is simply allowed to dissipate into the surrounding air. Such installation presumes that the airflow within the cab will be sufficient to prevent the control circuitry from overheating. This is often incorrect, and as a result, the control circuitry may be prone to overheating, thus amplifying the above described concerns. Since the space inside the cabs of vehicles is so limited, the placement of the control is extremely problematic. As a result, vehicle owners must risk serious damage to their vehicles and forego the use of significant amounts of space within the cab in order to simply control an attachment which is mounted on the vehicle.
Therefore, there exists a need to provide an accessory control unit for high current drawing vehicle accessories that is electrically efficient and thermally isolated.
SUMMARY OF THE INVENTION
The present invention places all the high current switching circuitry within the accessory at or near the electric motor. A low current control line is run from the cab of the vehicle to the switching circuitry, thus giving the operator full control over the electric motor without having the physically intrusive high current wires inside the cab of the vehicle. Since the power is brought directly to the motor, as opposed to a long control line run, the system is more efficient.
Locating the switching circuitry within the accessory prevents the heat generated by the circuitry from posing any hazard within the cab of the vehicle. In addition, the circuitry can be directly connected to the casing of the electric motor. Generally, the casing is an aluminum shell, which acts as a heat sink to the switching circuitry. The circuitry can be placed on the inside of the motor casing to conserve space. Alternatively, the circuitry can be mounted to the outside of the motor casing, or even adjacent to it, thus allowing the present system to be more easily retrofit into existing devices.
In one embodiment of the present invention, a MOSFET is used to control the high current flow to the electric motor. The MOSFET is mounted on the inner wall of the motor casing. A low current control within the cab actuates the MOSFET, which in turn controls the flow of current to the electric motor. In a preferred embodiment, a photovoltaic isolator is used to control the MOSFET. The photovoltaic isolator includes a variable LED and a photovoltaic generator. The intensity of the LED is varied by the cab control. The LED is located proximate to the photovoltaic generator that is coupled to the gate of the MOSFET. As the intensity of the light emitted by the LED increases, the photovoltaic generator increases the voltage at the gate, thus controlling the MOSFET in a known way. Alternatively, the MOSFET may be controlled directly through the actuation of a variable resistor or similar element, which directly controls the voltage generated at the gate.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram representing the control system of the present invention coupled with a vehicle.
FIG. 2 is schematic drawing of the control system with the circuitry mounted within the housing of an electric motor (shown in cross section).
FIG. 3 is a circuit diagram of the control system of the present invention utilizing a photovoltaic controller.
FIG. 4 is a circuit diagram of the control system of the present invention utilizing a variable resistor.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 illustrates the control system 10 as it is coupled with a vehicle 14 and an accessory. The vehicle 14 is representative of any type of vehicle to which a powered material handler, such as spreader 20 , may be attached. The vehicle 14 can range from a small personal vehicle, such as a pickup truck, to a larger commercial vehicle such as a dump truck used by road servicing crews. A housing 12 containing the accessory is coupled to the vehicle 14 . This connection is represented by coupling 18 . The housing 12 could be mounted directly to the vehicle as either a permanent or removable attachment or could simply be pulled behind as a trailer. Within the housing 12 is the actual spreader 20 . The spreader 20 includes some form of material handling device, such as an auger and is attached to a material supply container (either within the spreader 20 or within the vehicle 14 ). An electric motor 22 is mounted within the spreader 20 and has a drive shaft 34 (FIG. 2) which is coupled to the material handling device. A high current switching circuit, such as MOSFET 24 , is mounted on the electric motor 22 .
A control 26 is mounted within the cab 16 of the vehicle 14 . The control 26 is electrically connected to MOSFET 24 with a relatively thin, low current control line 28 . The control 26 allows an operator to turn the electric motor 22 on, off and vary its speed by controlling the MOSFET 24 , which in turns controls the amount of current supplied to the motor 22 .
FIG. 2 schematically illustrates the control system 10 of the present invention in its most preferred form. High amperage current is supplied to the electric motor 22 by an alternator 38 (or similar power supply). Current is ultimately delivered to the coils 32 of the electric motor 22 , which in turn causes the drive shaft 34 to rotate and deliver motive force to the actual spreader itself. The positive feed of the alternator 38 is coupled to the positive terminal 36 of the MOSFET 24 . The MOSFET 24 is of sufficient capacity to handle the high current load. In a preferred embodiment, the MOSFET 24 has a 100 Amp capacity. The positive output of MOSFET 24 is coupled, via positive lead 42 , through junction 40 to the motor coil 32 . The MOSFET 24 is flushly mounted to an inner side of the aluminum motor housing 30 , which acts as a heat sink for the MOSFET 24 . The positive terminal 36 of the MOSFET 24 extends through the motor housing 30 . Alternatively, the MOSFET could be mounted to the outer surface of the electric motor 22 . This makes installation easier and allows this system to be retrofit into existing devices. Control 26 receives power from a low current power supply 44 . The control 26 is coupled to the MOSFET 24 via control line 28 . As the control 26 is varied, the amount of current that flows from the alternator 38 , through MOSFET 24 and ultimately to the coils 32 is correspondingly varied. while it is preferable to mount the MOSFET 24 to an inner surface of the motor 22 , it is to be understood that the present invention contemplates locating the MOSFET 24 (or equivalent circuitry) anywhere proximate the electric motor 22 . That is, MOSFET 24 can be mounted on an outer surface of the motor 22 or on a structure located proximate to the motor 22 , so long as the efficiency of the circuit is maintained, heat generation is controlled, and the cab controls are connected remotely via a low current control line.
FIG. 3 is a circuit diagram illustrating one way of controlling electric motor 22 using a photovoltaic isolator. The photovoltaic isolator includes LED 46 and photovoltaic generator 48 . One example of such a photovoltaic isolator is that produced by International Rectifier, Series PVI, particularly the PVI 1050 or the PVI 5100. Control 26 serves to control the amount of current reaching LED 46 . As such, the control 26 will turn on, turn off and vary the intensity of LED 46 . As is known, LED 46 will only require a minimal current supply. The LED 46 is located proximate to a photovoltaic generator 48 . As the LED 46 varies in intensity, the photovoltaic generator 48 causes a corresponding variance in the voltage applied to the gate of the MOSFET 24 . By controlling the voltage applied to the gate, the amount of current which flows from the voltage source 50 (such as alternator 38 ) to the electric motor 22 is also controlled. The combination of the LED 46 and the photovoltaic generator 48 also act as an isolator to physically separate the low current control line from the high current switching circuit.
Alternatively, as shown in FIG. 4, a variable resistor 52 may be substituted for the LED 46 /photovoltaic controller 48 combination. The variable resistor 52 is actuated directly by the controller 26 , and varies the amount of low amperage current passing to ground. This may be accomplished in any of the known ways, such as employing a rheostat, a potentiometer, or the like. Once again, by varying the amount of voltage applied to the gate of the MOSFET 24 , the amount of current flowing from the voltage source 50 to the electric motor 22 is correspondingly varied.
While the above embodiments have been shown and described to include a MOSFET, the present invention contemplates the use of any type of high current switching circuitry. That is, by locating the switching circuitry close to the motor, and away from the cab, and remotely controlling the circuitry from the cab, the problems associated with any of these switching arrangements are minimized.
Those skilled in the art will further appreciate that the present invention may be embodied in other specific forms without departing from the spirit or central attributes thereof. In that the foregoing description of the present invention discloses only exemplary embodiments thereof, it is to be understood that other variations are contemplated as being within the scope of the present invention. Accordingly, the present invention is not limited in the particular embodiments which have been described in detail therein. Rather, reference should be made to the appended claims as indicative of the scope and content of the present invention.
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The present invention is a control system for a vehicle that utilizes a powered attachment such as a material spreader. Such a device requires the use of a high current drawing motor, which in turn requires the ability to control the flow of high amperage current. The high current switching circuitry is mounted on or near the electric motor to prevent the heat generated by the circuitry from posing any type of hazard. A low current control is placed within the cab of the vehicle and serves to remotely control the switching circuitry.
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This application is a division, of application Ser. No. 480,980, filed Mar. 31, 1983, now U.S. Pat. No. 4,506,731.
BACKGROUND OF THE INVENTION
The present invention relates to formation testing of a producing formation in an oil or gas well. Formation testing helps determine the potential productivity of a subsurface formation intersected by a well bore. The testing procedure requires the opening of a section of the well bore adjacent the formation to atmospheric or reduced pressure. A "testing string" comprising a string of drill pipe having incorporated therein a tester valve and one or more packers is lowered into the well bore, which may be cased or open hole, with the tester valve closed to prevent entry of well bore fluids into the string. Two packers may be employed if it is necessary to isolate the formation to be tested from the well bore below it. At the desired level, the packer or packers are set to isolate the formation to be tested, and the formation is then exposed to reduced pressure in the empty pipe string by opening the tester valve. The initial ability of the formation to produce fluid is thereby determined, and the tester valve is subsequently closed after a predetermined time period to test the rate of pressure buildup in the formation. This sequence may be repeated several times. At the end of the test, the tester valve is closed, pressure across the packer or packers is equalized, after which they are unset, and the testing string removed from the well. Formation pressures and in some instances other parameters, are recorded by one or more combination measuring and recording devices included in the testing string below the tester valve.
Several prior art methods of measuring downhole parameters are known in the art. The most common utilizes one or more combination measuring and recording devices placed in housings incorporated in the testing string. These devices are activated prior to the string being run into the well, and their proper operation or accuracy cannnot, as a result, be determined until the testing string is pulled from the well bore. Another more recently developed device of the prior art employs a wireline with an actuator sub at the bottom thereof to latch into a measuring device incorporated in the string, whereby a real time readout of the formation parameters measured is obtained at the surface. However, there is again the disadvantage of not being able to replace a faulty or inoperative measuring device without pulling the entire testing string, as well as the possibility that the wireline connection or the wireline itself may short out during the test, a common occurrence due to the hostile environment in the well bore and the long duration of the tests which often extend to several days. A third type of device employed to measure downhole parameters is a so-called "bomb hanger," such as is available from Otis Engineering Corporation of Dallas, Tex., whereby an instrument may be run into the well at the end of a wireline on the bomb hanger and locked into a collar recess on the interior of a pipe string, and retrieved in the same manner. This device, however, does not provide an absolutely positive indication that the instrument is locked in where desired, and also creates a significant flow obstruction when placed in the pipe string. In addition, the relatively large diameter of the bomb hanger precludes it from being run below any reduced diameter portion in a pipe string, such as in a testing string below a ball type tester valve, in close proximity to the formation.
SUMMARY OF THE INVENTION
In contrast to the prior art, the present invention comprises a method and apparatus whereby downhole measuring and recording devices may be placed and retrieved at will by wireline, even below a ball type tester valve in a testing string. The apparatus comprises a gauge receptacle means which may be incorporated in a testing string or any other pipe string, including substantially coaxial tubular inner and outer housing, the inner housing positioned by support rings having longitudinal apertures therethrough. The inner housing has a landing nipple profile cut therein, whereby a locking mandrel as known in the art having a gauge holder having a measuring and recording instrument therein (hereinafter referred to as a "gauge") and secured thereto may be run into the pipe string on a running tool as known in the art at the end of a wireline and locked into the inner housing. The wireline is then retracted from the well bore until such time as the operator desires to retrieve the gauge holder, at which time the wireline is run into the well bore with a pulling tool as known in the art and the locking mandrel with attached gauge holder is retrieved.
Of course, more than one gauge receptacle means may be incorporated into a pipe string, so that redundancy of gauges may be effected or multiple well bore parameters measured by different gauges.
BRIEF DESCRIPTION OF THE DRAWINGS
The method and apparatus of the present invention will be more fully understood by reference to the following detailed description of the preferred embodiment, taken in conjunction with the accompanying drawings, wherein:
FIGS. 1A-1D are a vertical half-section elevation of the apparatus of the gauge receptacle means of the present invention with locking, mandrel and landing and gauge holder in place.
FIG. 2 is a full sectional view taken across FIG. 1A at 2--2, showing the configuration of the support rings employed in the gauge receptacle means of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIGS. 1A-1D, gauge receptacle means 10 is shown incorporated in a pipe string 6 above and 8 below. The pipe string will be in a well bore, not shown, and may or may not be a part of a "testing string," as previously defined.
Gauge receptacle means 10 of substantially cylindrical and uniform outer diameter comprises an upper adapter 12 which engages pipe string 6 at threads 14. Upper adapter 12 has substantially the same diameter bore 16 at its upper end as that of pipe string 6. Below upper bore 16, the bore enlarges in oblique annular walled steps to intermediate bore 18 and lower bore 20. The lower end of upper adapter 12 comprises annular wall 22.
Upper case 30 is threaded to upper adapter 12 at 26, O-ring 28 effecting a fluid-tight seal therebetween. Case 30 possesses a substantially uniform diameter inner bore defined by bore wall 32, which extends substantially from its top to its bottom (as shown in FIGS. 1A-1D), where it engages middle case 40 at threaded area 34, O-ring 36 creating a fluid-tight seal therebetween.
Middle case 40 possesses an upper extension 42 of slightly less exterior diameter than the interior diameter of bore wall 32, ending at its upper extent in annular wall 44. Below threaded area 34, the exterior of middle case steps radially outward to substantially the same exterior diameter as upper case 30. The interior of middle case 40 is defined by bore wall 46 leading by an oblique annular step to constricted bore wall 48, which communicates radially outward via another oblique annular step with bore wall 50. Bore wall 50 extends to the bottom of middle case 40, where it terminates at a radial annular step 52, leading laterally to recessed bore wall 54.
Lower case 60 is secured to middle case 40 at threaded area 56, O-ring 58 creating a fluid-tight seal therebetween. Like middle case 40, lower case 60 possesses an upper extension 62, which is of slightly less exterior diameter than the interior diameter of recessed bore wall 54, ending at its upper extent in annular wall 64. Below threaded area 56, the exterior of lower case 60 steps radially outward to substantially the same exterior diameter as middle case 40. The interior of lower case 60 is defined by bore wall 66 leading by an oblique annular step to constricted bore wall 68, which communicates radially outward via another oblique annular step with bore wall 70. Bore wall 70 extends to the bottom of lower case 60, where it terminates at a radial annular step 72, leading laterally to recessed bore wall 74.
Lower adapter 80 is secured to lower case 60 at threaded area 76, O-ring 78 creating a fluid-tight seal therebetween. Like middle case 40 and lower case 60, lower adapter 80 possesses an upper extension 82 of slightly lesser exterior diameter than the interior diameter recessed bore wall 74, and terminates in an annular wall 84 at its upper extent. Below threaded area 76 and O-ring 78, lower adapter 80 steps radially outward to an exterior diameter substantially the same as that of the rest of gauge receptacle means 10. The interior of lower adapter 80 is defined by upper bore wall 82, which extends via an oblique annular step to constricted bore wall 84, which in turn terminates at an oblique annular step in exit bore wall 86, of substantially the same diameter as that of pipe string 8 to which it is threaded at 88. Upper adapter 12, upper case 30, middle case 40, lower case 60 and lower adapter 80 together comprise substantially tubular outer housing 90 of gauge receptacle means 10.
Inside outer housing 90 are an inner housing and a plurality of support rings disposed therebetween. At the top of gauge receptacle means 10, top support ring 100 having a plurality of longitudinal apertures 102 therethrough extends radially outward to abut bore wall 32 and annular wall 22. FIG. 2 shows the configuration of apertures 102, separated by integral radially extending legs 104 which extend between outer shell 106 and inner adapter 108.
Inner adapter 108 is threaded to tubular landing nipple 110 and 112. Landing nipple 110 has a substantially uniform exterior 114, which extends from its upper to its lower end. The interior of landing nipple 110 comprises entry bore wall 116, which necks down to landing bore 118 having annular landing grooves 120, 122 and 124 therein. These grooves may be preferably configured substantially identically to a "Type R" Otis Landing Nipple produced by Otis Engineering Corporation of Dallas, Tex., or may be of other landing nipple configuration as is known in the art. Below grooves 120, 122 and 124 the interior of landing nipple 110 flares slightly to exit bore 126.
Landing nipple 110 is threaded at 128 to flow tube assembly 130, which comprises middle support ring 132 and flow tube 134. Middle support ring 132 is similar in configuration to top support ring 100, having apertures 136 therethrough and an outer shell and an inner adapter (unnumbered) with integral radially extending legs therebetween. Flow tube 134 is welded to ring 132 at 138, and possesses a substantially uniform cylindrical exterior 140 and a substantially uniform interior defined by flow bore wall 142. The outer edge of the lower end of flow tube 34 is beveled as shown at 144.
Flow tube 134 extends downward from middle support ring 132 through first and second substantially identical lower support rings 150 and 160. Support ring 150 has longitudinal apertures 152 therethrough and integral radial legs extending between inner shell 154 and outer shell 156. Support ring 160 possesses longitudinal apertures 162 and integral radial legs extending between inner shell 164 and outer shell 166. Ring 150 is maintained in longitudinal position between step 52 of middle case 40 and annular wall 64 of lower case 60, which ring 160 is maintained in longitudinal position by step 72 of lower case 60, and annular wall 84 of lower adapter 80.
Top support ring 100, landing nipple 110, flow tube assembly 130 and lower support rings 150 and 160 comprise inner housing 170. The substantially annular passage between inner housing 170 and outer housing 90, created by support rings 100, 132, 150 and 160 of inner housing 170, is hereinafter referenced by numeral 180.
Referring again to FIGS. 1A-1D, locking mandrel 190 is shown in position, locked into landing nipple 110. Locking mandrel 190 as shown is an Otis "Type R" Locking Mandrel produced by Otis Engineering Corporation of Dallas, Tex. and is the preferred locking mandrel to use with the landing nipple configuration of choice. However, other locking mandrels known in the art may be employed, such as the Otis "Type X," with a suitably configured landing nipple, or landing nipples and locking mandrels manufactured by other companies and in use in the industry. Locking mandrel 190 comprises fishing neck 192 at its top end, having annular recess 193 on its interior, with annular shoulder 191 thereabove and annular shoulder 195 therebelow. Below fishing neck 192 on the exterior of locking mandrel 190 is dog case 194 of cylindrical configuration, dog case 194 having a plurality of sets of longitudinal spring retainer apertures 196, spring expansion slots 198 and dog recesses 200 substantially evenly spaced about the circumference thereof. Dog case 194 is secured to mandrel case 202 at threads 201. Mandrel case 202 extends upward at 204 inside of dog case 194 to the edge of annular shoulder 195, extension 204 having at least one relief aperture 206 therein near its lower extent. Below extension 204, mandrel case 202 has a shear pin aperture 208 through the wall thereof leading from its interior 210 to its exterior. Annular packing 212 is disposed on annular undercut 214 on the exterior of mandrel case 202. As may be seen in FIG. 1B, packing 212 creates a seal between locking mandrel 190 and landing nipple 110 when locking mandrel 190 is in the position shown.
Double acting springs 220 are disposed in spring expansion slots 198, the upper radially outwardly bent ends 222 thereof being retained in retainer apertures 196. Double acting springs 220 each have two substantially straight sections 224 and 226 oriented at substantially the same acute angle to the axis of locking mandrel 190, and laterally offset by oblique section 228, the purpose of which will be explained in conjunction with the operation of the present invention.
Locking dogs 230 are disposed in dog recesses 200, and each comprise three keys 232, 234 and 236, of substantially matching configuration to annular grooves 120, 122 and 124 of landing nipple 110. Key 234 has aperture 238 cut thereinto, lip 240 protruding upwardly from key 236 thereinto. The lower ends 229 of springs 220 extend into apertures 238 and over lips 240.
Tubular expander mandrel 250, secured to fishing neck 192 at threads 252 (shortened in FIG. 1A for convenience) extends downward between dog case 194 and mandrel case 202 under spring retainer apertures 196, expansion slots 198, to substantially near the bottom of dog recesses 200, proximate relief aperture 206. Annular shoulder 254 projects radially outwardly from the bottom of expansion mandrel 250.
Connector 260 connects locking mandrel 190 to shock absorber 270 at threads 262 and 264, respectively. Shock absorber 270, is not essential to the operation of the present invention, but is preferably employed to cushion any shocks experienced by a gauge in gauge holder 280 carried by locking mandrel 190. Shock absorber 270 preferably comprises a "Type LO" spring type double acting shock absorber produced by Otis Engineering Corporation, in order to cushion both upward and downward shocks.
Shock absorber 270 is connected at threads 272 to top bumper holder 282 of gauge holder 280. Bumper holder 282 is connected to tubular gauge housing 290 at threads 284. Gauge housing 290 has a plurality of apertures 292 and 294 about its circumference, to expose gauge chamber 296 to well bore conditions. Elastomeric top bumper 300 is disposed in gauge housing 290 adjacent top bumper holder 282, maintained in position by bolt 302.
Nose 310 is threaded to the bottom of gauge receptacle 290 at threads 298. Nose 310 has a lower frustoconical exterior 312, and lateral ports 314 leading to central passage 316 which extends upward into gauge chamber 296 through hollow bolt 320 which maintains lower bumper 330, preferably of an elastomeric material, in place.
OPERATION OF THE PREFERRED EMBODIMENT
Gauge receptacle means 10 is incorporated in a pipe string run into a well bore, for purposes of illustration and not by way of limitation, in a testing string with a ball type tester valve above it and at least one packer below it. For example and not by way of limitation, the tester valve may be a Halliburton FUL-FLO® HYDROSPRING® tester, or a Halliburton APR®N tester, both produced by Halliburton Services of Duncan, Okla. and described on pages 4003-4005 of Halliburton Services Sales and Service Catalog Number 41. Both of these tools employ a rotating ball with a central bore therethrough as a valve element to open and close the testing string thereabove to formation fluid. The packer may comprise a Halliburton RTTS Hook Wall Packer, described on page 3997 of the previously referred to Halliburton Services Sales and Service Catalog Number 41, or a Halliburton NR Expanding Shoe Well Packer Assembly, described on page 3998 of the same catalog. The RTTS Hook Wall Packer would be employed for testing in a cased hole, while the NR Expanding Shoe Well Packer Assembly would be used in an open hole test. Of course, there would be additional components in the testing string, all of them well known to one of ordinary skill in the art, such as a slip joint, a circulating valve, an hydraulic bypass, a safety joint, an hydraulic jar, a choke, etc. However, these tools are not associated with the operation of the present invention nor germaine to an understanding of its advantages over the prior art, and have therefore not been illustrated and will not be discussed further.
Returning again to the operation of the present invention, the testing string is run into the well bore with the tester valve closed, and the packer set by manipulation of the string when the level of the formation to be tested is released (of course, if the test operator wished to isolate the formation to be tested from well bore both above and below, two packers would be employed). As the gauge receptacle means 10 is run into the well on the string, locking mandrel 190 with its associated gauge holder 280 may or may not be locked into landing nipple 110. For purposes of illustration it is assumed that it is in place as the testing string is run into the well bore.
After the packer or packers are set, the ball type tester valve is opened by string manipulation or application of pressure to the well bore annulus (depending on the type of tester employed) and the formation is allowed to flow therethrough into the test string. After a period of time determined by the operator, the tester valve is closed again, and formation pressure permitted to build. During the test, the temperature and pressure of the flowing well fluid is measured with respect to time by a suitable gauge in gauge chamber 296, such as the Geophysical Research Corporation EMR 502/EPG 520 memory gauge system. The gauge is held in position and cushioned by bumpers 300 and 330. Of course, the bumpers are configured to hold the desired gauge, and may be of any suitable configuration. Of course, other parameters such as resistivity or density of well bore fluid could be measured or a sample of fluid taken with a suitable instrument in gauge chamber 296. The pressure and temperature in the well bore is transmitted through the well fluid to the gauge through apertures 292 and 294 in gauge holder 290, and lateral ports 314 and central passage 316 in nose 310.
After the well has been flowed and closed in again one or more times, the operator may wish to retrieve the gauge in gauge chamber 296 to review test data and ensure the well bore parameters of concern are properly measured before pulling the entire testing string. Alternatively, the operator may wish to treat the formation with a treatment known in the art, for example, acidizing or fracturing, and then retest the formation to ascertain the success of the treatment by running the gauge into the testing string again on wireline. Furthermore, the operator may in some instances wish to retrieve the gauge, perforate another formation below the upper packer, and re-test the well with both formations flowing.
To pull the locking mandrel 190, shock absorber 270 and gauge holder 280, an appropriate pulling tool is run into the well on a wireline and the tester valve is opened to permit passage thereof. For pulling of the preferred embodiment locking mandrel 190, an Otis "Type GR" wireline pulling tool is employed. To use the Type GR Pulling Tool, it is lowered into the string through the open tester valve until it enters the dog chamber 189 defined by recess 193 at the top of locking mandrel 190. An upward pull on the wireline shears a pin in the pulling tool, causing locking dogs therein to expand outwardly and engage the walls of recess 193, whereupon the wireline is continued to be pulled upward, the pulling tool locking dogs being held in recess 193 by contact with top shoulder 191, expander mandrel 250 being pulled upward in the annular area between mandrel case 202 and dog case 194, so that annular shoulder 254 of expander mandrel 250 moves upwardly from the position shown in FIG. 1B to a position under oblique sections 228 of double acting springs 220, thereby retracting locking dogs 230 from landing nipple 110 due to the radially inward force applied by lower ends 229 of springs 220 to lips 240 on locking dogs 230. The locking mandrel 190 with shock absorber 270 and gauge holder 280 are then pulled from the well bore on the wireline, the tester valve closed after passage therethrough of the locking mandrel 190 with shock absorber 270 and gauge holder 280, and data is taken from the gauge in gauge chamber 280 by means known in the art. For purposes of illustration only, it is assumed that the operator wishes to treat the formation tested, and re-test the formation after treatment to ascertain if production of well fluid has been enhanced, and if so, to what degree. A second gauge or the same gauge cleared of data is then placed in gauge chamber 296 of gauge holder 280, and locking mandrel 190 is placed on the end of a suitable wireline running tool, such as an Otis "Type R" Wireline Running Tool, as used in the petroleum industry, and run down through the tester valve, which is opened to allow passage of the wireline, to gauge receptacle 10. The running tool holds the locking dogs 230 of the lock mandrel 190 in a retracted position until it is lowered through landing nipple 110 of gauge receptacle means 10. The running tool is then pulled upward into landing nipple 110, locating dogs on the running tool catch on the bottom of landing bore 118 of landing nipple 110, requiring a significant force on the wireline to pull the running tool up through landing nipple 110. This force is transmitted through the locating dogs to the locking dogs 230 of the locking mandrel 190 which are expanded as the running tool and locking mandrel 190 are pulled through the landing nipple. The running tool and locking mandrel are then lowered back into the landing nipple, where the radially flat bottom edges on keys 232 and 234 engage the radially flat bottom surface of grooves 120 and 122. A downward jarring action on the running tool shears a first shear pin in the running tool and allows the expander mandrel 250 to be driven behind the locking dogs 230, securing locking mandrel 190 to landing nipple 110. At the same time, retainer dogs on the running tool which have engaged recess 193 in locking mandrel 190 are retracted. An upward strain on the wireline indicates that locking mandrel 190 is set. A sudden upward pull, which produces an upward jarring action, then shears a second shear pin securing locking mandrel 190 to the running tool. Shear pin aperture 208 is the point of engagement of the shear pin with locking mandrel 190. With the new gauge in place in gauge chamber 296 in gauge holder 280, the test may be repeated and the locking mandrel/shock absorber/gauge holder assemblies retrieved once again if desired, to ensure that proper data has been obtained before pulling the testing string.
Otis Engineering Corporation wireline running tools and pulling tools and an Otis lock mandrel and landing nipple configuration have hereby been employed for purposes of illustration; it should be understood that this example is not intended to limit the invention or the tools which may be used in conjunction therewith, as any suitable tools of this type effecting equivalent results may be employed. Moreover, the foregoing example wherein the locking mandrel and associated gauge holder were initially run into the well bore with the testing string is only illustrative and not intended to so restrict the method of the present invention.
While the method and apparatus of the present invention have been disclosed in terms of a preferred embodiment, it will be readily apparent to one of ordinary skill in the art that certain additions, deletions and modifications to the present invention may be made without departing from the spirit and scope of the claimed invention. For example, more than one gauge holder may be run on a single locking mandrel; several gauge receptacle means may be placed in a testing string to receive a like number of locking mandrels and gauge holders; the gauge receptacle means is not limited to use with a testing string, but may be run in any suitable pipe string; treating or perforating operations may be run with the gauge receptacle means in place.
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The present invention comprises a method and apparatus for placement and retrieval of gauges employed to measure temperature, pressure and other parameters in a well bore. The apparatus comprises a gauge receptacle means incorporated in a pipe string including a substantially tubular outer housing having a substantially tubular inner housing substantially coaxially therein, the inner housing being supported in the outer housing by a plurality of support rings having longitudinally extending apertures therethrough. The inner housing has a landing nipple profile cut therein, whereby a locking mandrel having a gauge holder secured thereto may be run into the pipe string on a wireline, and locked into the inner housing after which the wireline may be retracted. The locking mandrel may also be subsequently unlocked and retrieved with the gauge holder by wireline.
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[0001] There are no related patent applications.
[0002] This application did not receive any federal research and/or development funding.
TECHNICAL FIELD
[0003] Generally, the present invention relates to a safety device used in training firefighters and other damage control personnel. More specifically, the invention is a strap device that attaches to a hose nozzle and prevents a bale of the hose nozzle from being inadvertently opened during training exercises. The strap device comprises a plurality of loops arranged around a handle of the nozzle, the nozzle body and the bale to prevent fire fighting material from being discharged from the nozzle. One or more of the loops may include a fastener means that quickly detaches to decouple the loop from the nozzle part about which it is arranged. The device may also comprise a visual indicator, such as a flag, that is attached to the device to indicate that it has been visually inspected during a training exercise.
BACKGROUND OF THE INVENTION
[0004] Damage control and firefighting personnel periodically perform training operations to train for fighting fires. During these training operations, the personnel practice deploying firefighting equipment, such as hose gear and nozzles. In the modern Navy, all sailors are trained in damage control and firefighting operations.
[0005] During these training exercises, problems arise when personnel inadvertently open a bale on a nozzle to allow water, foam, or other firefighting agent to flow from the hose nozzle. Currently, many naval personnel use bungee cords, or other such elastic bands, wrapped around the firefighting nozzle during training exercises to prevent inadvertently opening it. Industrial sized paper clips with attached rags are typically utilized to indicate that a hose crew has been inspected. Other problems arise when these bungee cords and paper clips break, are lost, or fall off during the training exercise.
[0006] The instant invention overcomes the problems associated with the aforementioned prior art by providing a safety device that prevents the bale from the hose nozzle from being inadvertently opened. A visual indicator device is also provided for assisting inspectors in verifying that a hose crew has been inspected and passed the inspection. Moreover, the safety device may be easily removed by disengaging a detachable loop from the bale. The bale may be operated and the safety device is removed from the hose nozzle.
SUMMARY OF THE INVENTION
[0007] A nozzle safety training device includes a plurality of straps, preferably two, arranged around a hose nozzle to prevent the bale from being inadvertently opened during training exercises. An agent test satisfactory indicator is arranged on the device for simulating an agent being expelled from the nozzle during damage control training. The indicator may be a flag of a specific color fastened at an end of the device. For example, a green indictor may simulate salt water agent or a white flag may mean an aqueous filming agent.
[0008] The device is preferably formed from a plurality of cloth strips or webbing and preferably includes permanent stitching that fastens the cloth strips together. One of the strips of webbing includes a fastener, preferably of hook and loop material, that forms a dis-engageable or detachable loop which fastens to a bale of a hose nozzle for securing it in a closed or off position. Another loop of material or webbing is arranged at an opposite end of the device for fastening the device to a handle of the hose nozzle. The nozzle includes a flow end that passes through a further loop of material to secure the device to the body of the nozzle.
[0009] It is an object of the invention to provide a nozzle safety training strap device that prevents the bale of a nozzle, on which the device has been deployed, from being inadvertently opened during a training exercise.
[0010] It is another object of the invention to teach a safety training device that is an agent test satisfactory indicator that shows when a hose crew has passed an inspection.
[0011] It is a further object of the invention to provide a safety training device for use in training exercises. The safety training device includes a pair of loops that are connected together via at least one strap. The first loop surrounds a handle on the nozzle handle and the second loop surrounds the body of the nozzle. A strip of material extends from one side of the second loop to the other side to pass across the end of the nozzle from which water or fire fighting agent is expelled or discharged. A third loop includes a fastener and is detachable to allow the third loop to be easily and quickly fastened or coupled to the bale to prevent the nozzle from being accidentally actuated during training exercises. However, the bale third loop may be decoupled from the bale by pulling a loose end to disengage the fastener.
[0012] It is another object of the invention to teach a safety training device that is made from common materials such as strips of cloth or webbing that are stitched to create a pair of permanent loops of material for attaching the device to a hose nozzle. A fastener is included for creating a loop that surrounds the bale to prevent it from being inadvertently actuated during a training exercise. In a preferred embodiment, two strips of webbing are used. A permanent loop is formed at one end of a longer strip of webbing via stitching. The second end of the longer strip includes a fastener such as hook and loop material that forms a non-permanent loop. A fastener is also provided at the tip of the second end for securing a visual indicator thererto. The shorter strip of webbing is formed into a circular loop and fastened to the longer strip between the first and second ends. Permanent stitching preferably secures the circular loop to the longer strip.
[0013] The above and further objects, details and advantages of the invention will become apparent from the following detailed description, when read in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a perspective view of the instant invention.
[0015] FIG. 2A is a perspective view of the instant invention affixed to a nozzle that is in a closed position. FIG. 2B is perspective view of the instant invention affixed to a nozzle that is in the open position.
[0016] FIG. 3 is a perspective view of the invention on a nozzle and including a visual indicator attached to the device indicating that the hose crew has been inspected.
[0017] FIG. 4A is a prior art nozzle in the closed position. FIG. 4B is a prior art nozzle in the open position.
DETAILED DESCRIPTION OF THE INVENTION
[0018] The embodiments of the invention and the various features and advantageous details thereof are more fully explained with reference to the non-limiting embodiments and examples that are described and/or illustrated in the accompanying drawings and set forth in the following description. It should be noted that the features illustrated in the drawings are not necessarily drawn to scale, and the features of one embodiment may be employed with the other embodiments as the skilled artisan recognizes, even if not explicitly stated herein. Descriptions of well-known components and techniques may be omitted to avoid obscuring the invention. The examples used herein are intended merely to facilitate an understanding of ways in which the invention may be practiced and to further enable those skilled in the art to practice the invention. Accordingly, the examples and embodiments set forth herein should not be construed as limiting the scope of the invention, which is defined by the appended claims. Moreover, it is noted that like reference numerals represent similar parts throughout the several views of the drawings.
[0019] In a preferred embodiment of the invention, as shown in FIG. 1 , the device 1 includes a first strip of material 10 having two ends 10 A and 10 B . The first strip of material 10 is formed into a first loop 12 via permanent stitching 25 at a first end 10 A thereof. The handle 103 of the nozzle 100 is inserted into the first loop 12 of material 10 . The second end 10 B of the first strip of material 10 includes a fastener 29 , having complementary portions 29 A and 29 B that arranged on respective portions of material 10 , as shown in FIG. 2B . These complementary portions 29 A, 29 B engage one another to create a dis-engageable loop 13 that fastens about the bale 105 of the hose nozzle 100 . The second end 10 B of the first strip of material 10 is tugged on to detach the dis-engageable loop 13 from the bale 105 . A second strip of shorter material 15 is formed in a loop 16 . The flow end 101 of the hose nozzle 100 passes through this loop 16 and into a basket end 17 of the device 1 that includes a basket comprising the loop 16 and a basket strip of material 14 that is formed to partially encapsulate flow end 101 . The second strip of material 15 is fastened in two places to the first strip of material 10 via permanent stitching 25 using a square pattern as shown. Fastener element 29 B is preferably attached on a top end of the material 10 where it overlaps the loop 16 . A second set of permanent stitching 25 is provided along a bottom of the loop 16 to secure it to the first strip of material 10 . The region of material between these permanent stitching 25 comprises strip of material 14 which encapsulates a portion of flow end 101 . As indicated by the drawings, one of the complementary portions 29 A, 29 B of the fastener 29 is arranged near or atop the area of permanent stitching that couples the first 10 and second 15 strips of materials together. The strips of material may be a nylon webbing, cloth or other such durable material that can be fastened with permanent stitching.
[0020] As indicated, FIG. 1 shows a safety training device 1 that preferably includes a pair of strips of webbing 10 , 15 that are formed to include a basket 17 which comprises the loop 16 formed from a shorter strip of material 15 and strip 14 of a longer strip of webbing 10 . The flow end 101 of hose nozzle 100 rests within this basket 17 when the hose nozzle 100 is being inspected or when not in use. An indicator flag 40 , as shown in FIG. 3 , may be included on the second end 10 B of the first strip of webbing. The indicator flag includes a complementary strip of fastening material that fastens to fastener strip 30 A.
[0021] Strip fastener 30 A is arranged at the second end 10 B of first strip of webbing 10 . This end 10 B is pulled upwards to separate fastener 29 into complementary portions 29 A and 29 B. These complementary portions 29 A, 29 B are permanently fastened to the same face of the material 10 via stitching 25 . When mated together, the fastener 29 creates loop 13 that secures about bale 105 to prevent it from being opened, as shown in FIG. 2A .
[0022] Permanent stitching 25 that secures complementary fastener 29 B to one face of material 10 also preferably secures material 10 to material 15 . That is, one half of fastener 29 is arranged directly above where one of material 10 , 15 overlaps the other and is permanently stitched together. Permanent stitching 25 is also provide on a bottom of the loop 16 to secure materials 10 , 15 together. Another loop 12 is formed at a first end of the material 10 , as shown.
[0023] As can be understood by FIG. 2A , which is a perspective view of the instant invention affixed to a nozzle that is in a closed position, the device 1 is arranged around a hose nozzle 100 . In this instance, the handle 103 is passed through loop 12 . Discharge end 101 passes through loop 16 and into basket 17 . The second end 10 B of material 10 is passed through an opening 102 of the bale 105 . The complementary strips 29 A, 29 B of fastener 29 are brought together to create the detachable loop 13 around bale 105 . This loop 13 prevents bale 105 from being inadvertently opened. Loop 13 is disengaged by tugging on end 10 B to decouple complementary strips 29 A, 29 B from one another, as shown in FIG. 2B . Bale 105 may be pulled rearward to allow fire retardant to flow from discharge end 101 . As can be understood from FIG. 2B , discharge material will cause basket 17 to be removed from discharge end 101 . The operator can then slip loop 12 downward and away from handle 103 .
[0024] FIG. 3 is a perspective view of the invention 1 on a nozzle 100 and including a visual indicator 40 attached to the device 1 indicating that the hose crew has been inspected. In this instance, the visual indicator 40 includes a complementary fastener strip 30 B (not shown) that mates with fastener strip 30 A to couple the visual indicator 40 to the second end 10 B of material 10 . Visual indicator 40 may be provided in a variety of colors. The visual indicator is used as an agent test satisfactory indicator and is arranged on the device for simulating an agent being expelled from the nozzle during damage control training. The visual indicator may be a flag of a specific color fastened at an end of the device. For example, a green indictor may simulate salt water agent or a white flag may mean an aqueous filming agent. Other identification indicia may be provided on each visual indicator.
[0025] FIG. 4A is a prior art nozzle in the closed position. FIG. 4B is a prior art nozzle in the open position. In FIG. 4B , the nozzle 100 includes a discharge end 101 that discharges fire retardant material (not shown) when the bale 105 is forced rearward away from the discharge end 101 . A hose end 104 is coupled to a hose that provides pressurized fire retardant that flows through nozzle 100 . In FIG. 4A , the bale 105 is shown in the open position to correspond with FIG. 2A when the device 1 is typically installed on the hose nozzle 100 . The body of the nozzle includes that part of the nozzle to which the bale 105 and the handle 103 attach. A valve is arranged within the body to be closed when the bale 105 is in a defined position such as the forward position shown when the nozzle is in the closed position.
[0026] While the invention has been described with respect to preferred embodiments, 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 limiting sense. From the above disclosure of the general principles of the present invention and the preceding detailed description, those skilled in the art will readily comprehend the various modifications to which the present invention is susceptible. Therefore, the scope of the invention should be limited only by the following claims and equivalents thereof.
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A safety device includes a first loop arranged around a handle of a nozzle. A second loop is arranged around a body of the nozzle and adjoins the first loop via a first strip of material. A second strip of material extends across the second loop. A first strip of material includes a fastener for creating a third loop that prevents a bale of the nozzle from being opened. The safety device may include a visual indicator arranged at a free end of the first strip of material for indicating that a firefighting crew maintaining the nozzle has passed inspection and the type of agent the fire hose expels.
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[0001] This application is a continuation of U.S. Ser. No. 10/427,426 filed on Apr. 30, 2003, which is a continuation of U.S. Ser. No. 09/843,103 (now U.S. Ser. No. 6,558,432) filed on Apr. 25, 2001, which is a continuation-in-part of U.S. Ser. No. 09/419,345 (now U.S. Ser. No. 6,355,072) filed on Oct. 15, 1999. Each of the foregoing applications is hereby incorporated by reference herein.
BACKGROUND
[0002] 1. Field of the Invention
[0003] The present invention relates generally to cleaning systems, and more specifically to substrate cleaning systems, such as textile cleaning systems, utilizing an organic cleaning solvent and a pressurized fluid solvent.
[0004] 2. Related Art
[0005] A variety of methods and systems are known for cleaning substrates such as textiles, as well as other flexible, precision, delicate, or porous structures that are sensitive to soluble and insoluble contaminants. These known methods and systems typically use water, perchloroethylene, petroleum, and other solvents that are liquid at or substantially near atmospheric pressure and room temperature for cleaning the substrate.
[0006] Such conventional methods and systems generally have been considered satisfactory for their intended purpose. Recently, however, the desirability of employing these conventional methods and systems has been questioned due to environmental, hygienic, occupational hazard, and waste disposal concerns, among other things. For example, perchloroethylene frequently is used as a solvent to clean delicate substrates, such as textiles, in a process referred to as “dry cleaning.” Some locales require that the use and disposal of this solvent be regulated by environmental agencies, even when only trace amounts of this solvent are to be introduced into waste streams.
[0007] Furthermore, there are significant regulatory burdens placed on solvents such as perchloroethylene by agencies such as the EPA, OSHA and DOT. Such regulation results in increased costs to the user, which, in turn, are passed to the ultimate consumer. For example, filters that have been used in conventional perchloroethylene dry cleaning systems must be disposed of in accordance with hazardous waste or other environmental regulations. Certain other solvents used in dry cleaning, such as hydrocarbon solvents, are extremely flammable, resulting in greater occupational hazards to the user and increased costs to control their use.
[0008] In addition, textiles that have been cleaned using conventional cleaning methods are typically dried by circulating hot air through the textiles as they are tumbled in a drum. The solvent must have a relatively high vapor pressure and low boiling point to be used effectively in a system utilizing hot air drying. The heat used in drying may permanently set some stains in the textiles. Furthermore, the drying cycle adds significant time to the overall processing time. During the conventional drying process, moisture adsorbed on the textile fibers is often removed in addition to the solvent. This often results in the development of undesirable static electricity and shrinkage in the garments. Also, the textiles are subject to greater wear due to the need to tumble the textiles in hot air for a relatively long time. Conventional drying methods are inefficient and often leave excess residual solvent in the textiles, particularly in heavy textiles, components constructed of multiple fabric layers, and structural components of garments such as shoulder pads. This may result in unpleasant odors and, in extreme cases, may cause irritation to the skin of the wearer. In addition to being time consuming and of limited efficiency, conventional drying results in significant loss of cleaning solvent in the form of fugitive solvent vapor. The heating required to evaporate combustible solvents in a conventional drying process increases the risk of fire and/or explosions. In many cases, heating the solvent will necessitate explosion-proof components and other expensive safety devices to minimize the risk of fire and explosions. Finally, conventional hot air drying is an energy intensive process that results in relatively high utility costs and accelerated equipment wear.
[0009] Traditional cleaning systems may utilize distillation in conjunction with filtration and adsorption to remove soils dissolved and suspended in the cleaning solvent. The filters and adsorptive materials become saturated with solvent, therefore, disposal of some filter waste is regulated by state or federal laws. Solvent evaporation especially during the drying cycle is one of the main sources of solvent loss in conventional systems. Reducing solvent loss improves the environmental and economic aspects of cleaning substrates using cleaning solvents. It is therefore advantageous to provide a method and system for cleaning substrates that utilizes a solvent having less adverse attributes than those solvents currently used and reduces solvent losses.
[0010] As an alternative to conventional cleaning solvents, pressurized fluid solvents or densified fluid solvents have been used for cleaning various substrates, wherein densified fluids are widely understood to encompass gases that are pressurized to either subcritical or supercritical conditions so as to achieve a liquid or a supercritical fluid having a density approaching that of a liquid. In particular, some patents have disclosed the use of a solvent such as carbon dioxide that is maintained in a liquid state or either a subcritical or supercritical condition for cleaning such substrates as textiles, as well as other flexible, precision, delicate, or porous structures that are sensitive to soluble and insoluble contaminants.
[0011] For example, U.S. Pat. No. 5,279,615 discloses a process for cleaning textiles using densified carbon dioxide in combination with a non-polar cleaning adjunct. The preferred adjuncts are paraffin oils such as mineral oil or petrolatum. These substances are a mixture of alkanes including a portion of which are C 16 or higher hydrocarbons. The process uses a heterogeneous cleaning system formed by the combination of the adjunct which is applied to the textile prior to or substantially at the same time as the application of the densified fluid. According to the data disclosed in U.S. Pat. No. 5,279,615, the cleaning adjunct is not as effective at removing soil from fabric as conventional cleaning solvents or as the solvents described for use in the present invention as disclosed below.
[0012] U.S. Pat. No. 5,316,591 discloses a process for cleaning substrates using liquid carbon dioxide or other liquefied gases below their critical temperature. The focus of this patent is on the use of any one of a number of means to effect cavitation to enhance the cleaning performance of the liquid carbon dioxide. In all of the disclosed embodiments, densified carbon dioxide is the cleaning medium. This patent does not describe the use of a solvent other than the liquefied gas for cleaning substrates. While the combination of ultrasonic cavitation and liquid carbon dioxide may be well suited to processing complex hardware and substrates containing extremely hazardous contaminants, this process is too costly for the regular cleaning of textile substrates. Furthermore, the use of ultrasonic cavitation is less effective for removing contaminants from textiles than it is for removing contaminants from hard surfaces.
[0013] U.S. Pat. No. 5,377,705, issued to Smith et al., discloses a system designed to clean parts utilizing supercritical carbon dioxide and an environmentally friendly co-solvent. Parts to be cleaned are placed in a cleaning vessel along with the co-solvent. After adding super critical carbon dioxide, mechanical agitation is applied via sonication or brushing. Loosened contaminants are then flushed from the cleaning vessel using additional carbon dioxide. Use of this system in the cleaning of textiles is neither suggested nor disclosed. Furthermore, use of this system for the cleaning of textiles would result in redeposition of loosened soil and damage to some fabrics.
[0014] U.S. Pat. No. 5,417,768, issued to Smith et al., discloses a process for precision cleaning of a work piece using a multi-solvent system in which one of the solvents is liquid or supercritical carbon dioxide. The process results in minimal mixing of the solvents and incorporates ultrasonic cavitation in such a way as to prevent the ultrasonic transducers from coming in contact with cleaning solvents that could degrade the piezoelectric transducers. Use of this system in the cleaning of textiles is neither suggested nor disclosed. In fact, its use in cleaning textiles would result in redeposition of loosened soil and damage to some fabrics.
[0015] U.S. Pat. No. 5,888,250 discloses the use of a binary azeotrope comprised of propylene glycol tertiary butyl ether and water as an environmentally attractive replacement for perchlorethylene in dry cleaning and degreasing processes. While the use of propylene glycol tertiary butyl ether is attractive from an environmental regulatory point of view, its use as disclosed in this invention is in a conventional dry cleaning process using conventional dry cleaning equipment and a conventional evaporative hot air drying cycle. As a result, it has many of the same disadvantages as conventional dry cleaning processes described above.
[0016] U.S. Pat. No. 6,200,352 discloses a process for cleaning substrates in a cleaning mixture comprising carbon dioxide, water, surfactant, and organic co-solvent. This process uses carbon dioxide as the primary cleaning media with the other components included to enhance the overall cleaning effectiveness of the process. There is no suggestion of a separate, low pressure cleaning step followed by the use of densified fluid to remove the cleaning solvent. As a result, this process has many of the same cost and cleaning performance disadvantages of other liquid carbon dioxide cleaning processes. Additional patents have been issued to the assignee of U.S. Pat. No. 6,200,352 covering related subject matter. All of these patents disclose processes in which liquid carbon dioxide is the cleaning solvent. Consequently, these processes have the same cost and cleaning performance disadvantages.
[0017] Several of the pressurized fluid solvent cleaning methods described in the above patents may lead to recontamination of the substrate and degradation of efficiency because the contaminated solvent is not continuously purified or removed from the system. Furthermore, pressurized fluid solvent alone is not as effective at removing some types of soil as are conventional cleaning solvents. Consequently, pressurized fluid solvent cleaning methods require individual treatment of stains and heavily soiled areas of textiles, which is a labor-intensive process. Furthermore, systems that utilize pressurized fluid solvents for cleaning are more expensive and complex to manufacture and maintain than conventional cleaning systems. Finally, few if any conventional surfactants can be used effectively in pressurized fluid solvents. The surfactants and additives that can be used in pressurized fluid solvent cleaning systems are much more expensive than those used in conventional cleaning systems.
[0018] There thus remains a need for an efficient and economic method and system for cleaning substrates that incorporates the benefits of prior systems, and minimizes the difficulties encountered with each. There also remains a need for a method and system in which the hot air drying time is eliminated, or at least reduced, thereby reducing the wear on the substrate and preventing stains from being permanently set on the substrate.
SUMMARY
[0019] In the present invention, certain types of organic solvents, such as terpenes, halohydrocarbons, certain glycol ethers, polyols, ethers, esters of glycol ethers, esters of fatty acids and other long chain carboxylic acids, fatty alcohols and other long-chain alcohols, short-chain alcohols, polar aprotic solvents, siloxanes, hydrofluoroethers, dibasic esters, and aliphatic hydrocarbons solvents or similar solvents or mixtures of such solvents are used in cleaning substrates. Any type of organic solvent that falls within the chemical formulae disclosed hereinafter may be used to clean substrates. However, unlike conventional cleaning systems, in the present invention, a conventional drying cycle is not performed. Instead, the system utilizes the solubility of the organic solvent in pressurized fluid solvents, as well as the physical properties of pressurized fluid solvents, to dry the substrate being cleaned.
[0020] As used herein, the term “pressurized fluid solvent” refers to both pressurized liquid solvents and densified fluid solvents. The term “pressurized liquid solvent” as used herein refers to solvents that are preferably liquid at between approximately 600 and 1050 pounds per square inch and between approximately 5 and 30 degrees Celsius, but are gas at atmospheric pressure and room temperature. The term “densified fluid solvent” as used herein refers to a gas or gas mixture that is compressed to either subcritical or supercritical conditions so as to achieve either a liquid or a supercritical fluid having density approaching that of a liquid. Preferably, the pressurized fluid solvent used in the present invention is an inorganic substance such as carbon dioxide, xenon, nitrous oxide, or sulfur hexafluoride. Most preferably, the pressurized fluid solvent is densified carbon dioxide.
[0021] The substrates are cleaned in a perforated drum within a vessel in a cleaning cycle using an organic solvent. A perforated drum is preferred to allow for free interchange of solvent between the drum and vessel as well as to transport soil from the substrates to the filter. After substrates have been cleaned in the perforated drum, the organic solvent is extracted from the substrates by rotating the cleaning drum at high speed within the cleaning vessel in the same way conventional solvents are extracted from substrates in conventional cleaning machines. However, instead of proceeding to a conventional evaporative hot air drying cycle, the substrates are immersed in pressurized fluid solvent to extract the residual organic solvent from the substrates. This is possible because the organic solvent is soluble in the pressurized fluid solvent. After the substrates are immersed in pressurized fluid solvent, the pressurized fluid solvent is transferred from the drum. Finally, the vessel is de-pressurized to atmospheric pressure to evaporate any remaining pressurized fluid solvent, yielding clean, solvent-free substrates.
[0022] The solvents used in the present invention tend to be soluble in pressurized fluid solvents such as supercritical or subcritical carbon dioxide so that a conventional hot air drying cycle is not necessary. The types of solvents used in conventional cleaning systems must have reasonably high vapor pressures and low boiling points because they must be removed from the substrates by evaporation in a stream of hot air. However, solvents that have a high vapor pressure and a low boiling point generally also have a low flash point. From a safety standpoint, organic solvents used in cleaning substrates should have a flash point that is as high as possible, or preferably, it should have no flash point. By eliminating the conventional hot air evaporative drying process, a wide range of solvents can be used in the present invention that have much lower evaporation rates, higher boiling points and higher flash points than those used in conventional cleaning systems. For situations where the desired solvent has a relatively low flash point, the elimination of the hot air evaporative drying cycle significantly increases the level of safety with respect to fire and explosions.
[0023] Thus, the cleaning system described herein utilizes solvents that are less regulated and less combustible, and that efficiently remove different soil types typically deposited on textiles through normal use. The cleaning system reduces solvent consumption and waste generation as compared to conventional dry cleaning systems. Machine and operating costs are reduced as compared to currently used pressurized fluid solvent systems, and conventional additives may be used in the cleaning system.
[0024] Furthermore, one of the main sources of solvent loss from conventional dry cleaning systems, which occurs in the evaporative hot air drying step, is eliminated altogether. Because the conventional evaporative hot air drying process is eliminated, there are no heat set stains on the substrates, risk of fire and/or explosion is reduced, the total cycle time is reduced, and residual solvent in the substrates is substantially reduced or eliminated. Substrates are also subject to less wear, less static electricity build-up and less shrinkage because there is no need to tumble the substrates in a stream of hot air to dry them.
[0025] While systems according to the present invention utilizing pressurized fluid solvent to remove organic solvent can be constructed as wholly new systems, existing conventional solvent systems can also be converted to utilize the present invention. An existing conventional solvent system can be used to clean substrates with organic solvent, and an additional pressurized chamber for drying substrates with pressurized fluid solvent can be added to the existing system.
[0026] Therefore, according to the present invention, textiles to be cleaned are placed in a cleaning drum within a cleaning vessel, adding an organic solvent to the cleaning vessel, cleaning the textiles with the organic solvent, removing a portion of the organic solvent from the cleaning vessel, rotating the cleaning drum to extract a portion of the organic solvent from the textiles, placing the textiles into a drying drum within a pressurizable drying vessel, adding a pressurized fluid solvent to the drying vessel, removing a portion of the pressurized fluid solvent from the drying vessel, rotating the drying drum to extract a portion of the pressurized fluid solvent from the textiles, depressurizing the drying vessel to remove the remainder of the pressurized fluid solvent by evaporation, and removing the textiles from the depressurized vessel.
[0027] These and other features and advantages of the invention will be apparent upon consideration of the following detailed description of the presently preferred embodiment of the invention, taken in conjunction with the claims and appended drawings, as well as will be learned by practice of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] FIG. 1 is a block diagram of a cleaning system utilizing separate vessels for cleaning and drying.
[0029] FIG. 2 is a block diagram of a cleaning system utilizing a single vessel for cleaning and drying.
DETAILED DESCRIPTION
[0030] Reference will now be made in detail to embodiments of the invention, examples of which are illustrated in the accompanying drawings. The steps of each method for cleaning and drying a substrate will be described in conjunction with the detailed description of the system.
[0031] The methods and systems presented herein may be used for cleaning a variety of substrates. The present invention is particularly suited for cleaning substrates such as textiles, as well as other flexible, precision, delicate, or porous structures that are sensitive to soluble and insoluble contaminants. The term “textile” is inclusive of, but not limited to, woven or non-woven materials, as well as articles made therefrom. Textiles include, but are not limited to, fabrics, articles of clothing, protective covers, carpets, upholstery, furniture and window treatments. For purposes of explanation and illustration, and not limitation, exemplary embodiments of a system for cleaning textiles in accordance with the invention are shown in FIGS. 1 and 2 .
[0032] As noted above, the pressurized fluid solvent used in the present invention is either a pressurized liquid solvent or a densified fluid solvent. Although a variety of solvents may be used, it is preferred that an inorganic substance such as carbon dioxide, xenon, nitrous oxide, or sulfur hexafluoride, be used as the pressurized fluid solvent. For cost and environmental reasons, liquid, supercritical, or subcritical carbon dioxide is the preferred pressurized fluid solvent.
[0033] Furthermore, to maintain the pressurized fluid solvent in the appropriate fluid state, the internal temperature and pressure of the system must be appropriately controlled relative to the critical temperature and pressure of the pressurized fluid solvent. For example, the critical temperature and pressure of carbon dioxide is approximately 31 degrees Celsius and approximately 73 atmospheres, respectively. The temperature may be established and regulated in a conventional manner, such as by using a heat exchanger in combination with a thermocouple or similar regulator to control temperature. Likewise, pressurization of the system may be performed using a pressure regulator and a pump and/or compressor in combination with a pressure gauge. These components are conventional and are not shown in FIGS. 1 and 2 as placement and operation of these components are known in the art.
[0034] The system temperature and pressure may be monitored and controlled either manually, or by a conventional automated controller (which may include, for example, an appropriately programmed computer or appropriately constructed microchip) that receives signals from the thermocouple and pressure gauge, and then sends corresponding signals to the heat exchanger and pump and/or compressor, respectively. Unless otherwise noted, the temperature and pressure is appropriately maintained throughout the system during operation. As such, elements contained within the system are constructed of sufficient size and material to withstand the temperature, pressure, and flow parameters required for operation, and may be selected from, or designed using, any of a variety of presently available high pressure hardware.
[0035] In the present invention, the preferred organic solvent should have a flash point of greater than 100 F to allow for increased safety and less governmental regulation, have a low evaporation rate to minimize fugitive emissions, be able to remove soils consisting of insoluble particulate soils and solvent soluble oils and greases, and prevent or reduce redeposition of soil onto the textiles being cleaned.
[0036] Preferably, the organic solvents suitable for use in the present invention include any of the following alone or in combination. A description of the chemical formulae of the organic solvents that can be used in the cleaning processes of the invention follows. As used herein, elemental designations are the same as used by one of skill in the relevant art. For example, as used herein, H designates hydrogen, O designates oxygen, C designates carbon, S designates sulfur, CH 3 designates methyl, CH 2 CH 3 designates ethyl, and so forth. R is a variable that designates a chemical structure as described further herein.
[0037] In one embodiment of the invention, the organic solvent of the invention is composed, at least in part, of a chemical having the following general chemical structure:
C a X j H k O z
wherein: a=5n and 1≦n≦3; each X is independently F, Cl, Br or I; 0≦z≦4; 0≦j, k≦10; and 0≦(j+k)≦10n.
[0044] In another embodiment of the invention, the organic solvent of the invention is composed, at least in part, of a chemical having the following general chemical structure:
C n X j H k
wherein: 1≦n≦20; each X is independently F, Cl, Br or I; 0≦j; k<2n+2; and 2n−4≦(j+k)≦2n+2.
[0051] In another embodiment of the invention, the organic solvent of the invention is composed, at least in part, of a chemical having the one of the following general chemical structures:
R iv =C j H u X v ; R ii =C k H y X z or benzyl, phenyl, partially or fully fluorinated benzyl or phenyl; 0≦u, v≦2j+1; 0≦(u+v)≦2j+1; 0≦y, z≦2k+1; 0≦(y+z)≦2k+1; 0≦u, v, y, z≦37; R 1-4 and R 9-12 are independently C m H n X p ,
where 0≦m≦2; 0≦(n+p)≦5; and n+p=2m+1;
R 5-8 and R 13-16 are independently C a H b X d ,
wherein a is 0 or 1; 0≦(b+d)≦3; and b+d=2a+1; and
each X is independently F, Cl, Br or I. or
R iv =C j H u X v ; R ii =C k H y X z or benzyl, phenyl, partially or fully fluorinated benzyl or phenyl; j and k each equal 0 independently or 14−3(x+y+z)≦j, k≦22−3(x+y+z) and 14−3(x+y+z)≦(j+k)≦22−3(x+y+z); 0≦X, y, z≦1; 0≦(x+y+z)≦3; 0≦u, v, y, z≦37; 0≦(u+v)≦2j+1; 0≦(y+z)≦2k+1; R 1-3 and R 7-9 are independently C m H n X p ,
wherein 0≦m≦2; 0≦(n+p)≦5; and n+p=2m+1;
R 4-6 and R 10-12 are independently C a H b X d ,
wherein a is 0 or 1; 0≦(b+d)≦3; and b+d=2a+1;and
each X is independently F, Cl, Br or I.
[0088] In another embodiment of the invention, the organic solvent of the invention is composed, at least in part, of a chemical having the following general chemical structure:
C n H j X k (OH) r
wherein: each X is independently F, Cl, Br or I; 1≦n≦20; 0≦r≦4; 0≦j, k≦2n+2−r; and 2n−4−r≦(j+k)≦2n+2−r.
[0095] In another embodiment of the invention, the organic solvent of the invention is composed, at least in part, of a chemical having the following general chemical structure:
C n H j X k O b
wherein: each X is independently F, Cl, Br or I; 2≦n≦20; 0≦j, k≦2n+2; 2n−4≦(j+k)≦2n+2; and 1≦b≦6.
[0102] In another embodiment of the invention, the organic solvent of the invention is composed, at least in part, of a chemical having the one of the following general chemical structures:
R v =C j H u X v ; R ii =C k H a X b ; 15≦j, k≦32−3(w+x+y+z); 15≦j+k≦32−3(w+x+y+z); 0≦u, v≦2j+1; 0≦a; b≦2k+1; 2j−7≦(u+v)≦2j+1; 2k−7≦(y+z)≦2k+1; and R 1-4 and R 9-12 are independently C m H n X p ,
wherein 0≦m≦2; 0≦(n+p)≦5;and n+p=2m+1;
R 5-8 and R 13-16 are independently C a H b X d ,
wherein a is 0 or 1; 0≦(b+d)≦3; and b+d=2a+1; and
each X is independently F, Cl, Br or I.
or
R iv =C j H u X v ; R v =C j H u X v ; R ii =C k H a X b ; 15≦j, k≦32−3(w+x+y+z); 15j+k≦32−3(w+x+y+z); 0≦u, v≦2j+1; 0≦a; b≦2k+1; 2j−7≦(u+v)≦2j+1; 2 k−7≦(y+z)≦2k+1; and R 1-4 and R 9-12 are independently C m H n X p ,
wherein 0≦m≦2; 0≦(n+p)≦5; and n+p=2m+1; R 5-8 and R 13-16 are independently C a H b X d , wherein a is 0 or 1; 0≦(b+d)≦3; and b+d=2a+1; and
each X is independently F, Cl, Br or I.
[0141] In another embodiment of the invention, the organic solvent of the invention is composed, at least in part, of a chemical having the following general chemical structure:
C n (CO 2 ) m H a X b
wherein: each X is independently F, Cl, Br or I; 2≦n≦21; 1≦m≦3; 0≦a; b≦2n+2; and 2n−2≦(a+b)≦2n+z.
[0149] In another embodiment of the invention, the organic solvent of the invention is composed, at least in part, of a chemical having the one of the following general chemical structures:
C n (CO 3 ) m H a X b
wherein: each X is independently F, Cl, Br or I; 2≦n≦18; m=1 0≦a; b≦2n+2; and 2n−4≦(a+b)≦2n+z. or
wherein:
1≦j≦6
R 1 =C j H a X b
0≦a; b≦2j+1; and
2j−7≦(a+b)≦2j+1;
R 2 =C k H d X e 1≦k≦6; 0≦d; e≦2k+1; and
d+e=2k+1;
R 3 =C m H e X f 1≦m≦6; 0≦e; f≦2m+1; and e+f=2m+1; and
each X is independently F, Cl, Br or I. or
SO e C n H j X k
wherein: each X is independently F, Cl, Br or I; 1≦e≦2; 2≦n≦8; 0≦j; k≦2a+1; and 2n≦(j+k)≦2n+1
or
C n H y N a O b
wherein: 1≦n≦10; 1≦a; b≦2 and a=b; and 2n−1≦y≦2n+1.
[0189] In another embodiment of the invention, the organic solvent of the invention is composed, at least in part, of a chemical having the one of the following general chemical structures:
wherein: each R equals C a X y H z independently; each X is independently F, Cl, Br or I; 1≦a≦3;and 0≦y, z≦2a+1 and y+z=2a+1.
or
wherein: 2≦n≦4; each R equals C a H y X z independently; each X is independently F, Cl, Br or I; 1≦a≦3 0≦y; z≦2a+1 and y+z=2a+1.
[0202] Referring now to FIG. 1 , a block diagram of a cleaning system having separate vessels for cleaning and drying textiles is shown. The cleaning system 100 generally comprises a cleaning machine 102 having a cleaning vessel 110 operatively connected to, via one or more motor activated shafts (not shown), a perforated rotatable cleaning drum or wheel 112 within the cleaning vessel 110 with an inlet 114 to the cleaning vessel 110 and an outlet 116 from the cleaning vessel 110 through which cleaning fluids can pass. A drying machine 104 has a drying vessel 120 capable of being pressurized. The pressurizable drying vessel 120 is operatively connected to, via one or more motor activated shafts (not shown), a perforated rotatable drying drum or wheel 122 within the drying vessel 120 with an inlet 124 to the drying vessel 120 and an outlet 126 from the drying vessel 120 through which pressurized fluid solvent can pass. The cleaning vessel 110 and the drying vessel 120 can either be parts of the same machine, or they can comprise separate machines. Furthermore, both the cleaning and drying steps of this invention can be performed in the same vessel, as is described with respect to FIG. 2 below.
[0203] An organic solvent tank 130 holds any suitable organic solvent, as previously described, to be introduced to the cleaning vessel 110 through the inlet 114 . A pressurized fluid solvent tank 132 holds pressurized fluid solvent to be added to the pressurizable drying vessel 120 through the inlet 124 . Filtration assembly 140 contains one or more filters that continuously remove contaminants from the organic solvent from the cleaning vessel 110 as cleaning occurs.
[0204] The components of the cleaning system 100 are connected with lines 150 - 156 , which transfer organic solvents and vaporized and pressurized fluid solvents between components of the system. The term “line” as used herein is understood to refer to a piping network or similar conduit capable of conveying fluid and, for certain purposes, is capable of being pressurized. The transfer of the organic solvents and vaporized and pressurized fluid solvents through the lines 150 - 156 is directed by valves 170 - 176 and pumps 190 - 193 . While pumps 190 - 193 are shown in the described embodiment, any method of transferring liquid and/or vapor between components can be used, such as adding pressure to the component using a compressor to force the liquid and/or vapor from the component.
[0205] The textiles are cleaned with an organic solvent such as those previously described or mixtures thereof. The textiles may also be cleaned with a combination of organic solvent and pressurized fluid solvent, and this combination may be in varying proportions from about 50% by weight to 100% by weight of organic solvent and 0% by weight to 50% by weight of pressurized fluid solvent. In the cleaning process, the textiles are first sorted as necessary to place the textiles into groups suitable to be cleaned together. The textiles may then be spot treated as necessary to remove any stains that may not be removed during the cleaning process. The textiles are then placed into the cleaning drum 112 of the cleaning system 100 . It is preferred that the cleaning drum 112 be perforated to allow for free interchange of solvent between the cleaning drum 112 and the cleaning vessel 110 as well as to transport soil from the textiles to the filtration assembly 140 .
[0206] After the textiles are placed in the cleaning drum 112 , an organic solvent contained in the organic solvent tank 130 is added to the cleaning vessel 110 via line 152 by opening valve 171 , closing valves 170 , 172 , 173 and 174 , and activating pump 190 to pump organic solvent through the inlet 114 of the cleaning vessel 110 . The organic solvent may contain one or more co-solvents, water, detergents, or other additives to enhance the cleaning capability of the cleaning system 100 . Alternatively, one or more additives may be added directly to the cleaning vessel 110 . Pressurized fluid solvent may also be added to the cleaning vessel 110 along with the organic solvent to enhance cleaning. Pressurized fluid solvent can be added to the cleaning vessel 110 via line 154 by opening valve 174 , closing valves 170 , 171 , 172 , 173 , and 175 , and activating pump 192 to pump pressurized fluid solvent through the inlet 114 of the cleaning vessel 110 . Of course, if pressurized fluid solvent is included in the cleaning cycle, the cleaning vessel 110 will need to be pressurized in the same manner as the drying vessel 120 , as discussed below.
[0207] When a sufficient amount of the organic solvent, or combination of organic solvent and pressurized fluid solvent, is added to the cleaning vessel 110 , the motor (not shown) is activated and the perforated cleaning drum 112 is agitated and/or rotated within cleaning vessel 110 . During this phase, the organic solvent is continuously cycled through the filtration assembly 140 by opening valves 170 and 172 , closing valves 171 , 173 and 174 , and activating pump 191 . Filtration assembly 140 may include one or more fine mesh filters to remove particulate contaminants from the organic solvent passing therethrough and may alternatively or in addition include one or more absorptive or adsorptive filters to remove water, dyes and other dissolved contaminants from the organic solvent. Exemplary configurations for filter assemblies that can be used to remove contaminants from either the organic solvent or the pressurized fluid solvent are described more fully in U.S. application Ser. No. 08/994,583 incorporated herein by reference. As a result, the organic solvent is pumped through outlet 116 , valve 172 , line 151 , filter assembly 140 , line 150 , valve 170 and re-enters the cleaning vessel 110 via inlet 114 . This cycling advantageously removes contaminants, including particulate contaminants and/or soluble contaminants, from the organic solvent and reintroduces filtered organic solvent to the cleaning vessel 110 and agitating or rotating cleaning drum 112 . Through this process, contaminants are removed from the textiles. Of course, in the event the cleaning vessel 110 is pressurized, this recirculation system will be maintained at the same pressure/temperature levels as those in cleaning vessel 110 .
[0208] After sufficient time has passed so that the desired level of contaminants is removed from the textiles and organic solvent, the organic solvent is removed from the cleaning drum 112 and cleaning vessel 110 by opening valve 173 , closing valves 170 , 171 , 172 and 174 , and activating pump 191 to pump the organic solvent through outlet 116 via line 153 . The cleaning drum 112 is then rotated at a high speed, such as 400 - 800 rpm, to further remove organic solvent from the textiles. The cleaning drum 112 is preferably perforated so that, when the textiles are rotated in the cleaning drum 112 at a high speed, the organic solvent can drain from the cleaning drum 112 . Any organic solvent removed from the textiles by rotating the cleaning drum 112 at high speed is also removed IS from the cleaning drum 112 in the manner described above. After the organic solvent is removed from the cleaning drum 112 , it can either be discarded or recovered and decontaminated for reuse using solvent recovery systems known in the art. Furthermore, multiple cleaning cycles can be used if desired, with each cleaning cycle using the same organic solvent or different organic solvents. If multiple cleaning cycles are used, each cleaning cycle can occur in the same cleaning vessel, or a separate cleaning vessel can be used for each cleaning cycle.
[0209] After a desired amount of the organic solvent is removed from the textiles by rotating the cleaning drum 112 at high speed, the textiles are moved from the cleaning drum 112 to the drying drum 122 within the drying vessel 120 in the same manner textiles are moved between machines in conventional cleaning systems. In an alternate embodiment, a single drum can be used in both the cleaning cycle and the drying cycle, so that, rather than transferring the textiles between the cleaning drum 112 and the drying drum 122 , a single drum containing the textiles is transferred between the cleaning vessel 110 and the drying vessel 120 . If the cleaning vessel 110 is pressurized during the cleaning cycle, it must be depressurized before the textiles are removed. Once the textiles have been placed in the drying drum 122 , pressurized fluid solvent, such as that contained in the carbon dioxide tank 132 , is added to the drying vessel 120 via lines 154 and 155 by opening valve 175 , closing valves 174 and 176 , and activating pump 192 to pump pressurized fluid solvent through the inlet 124 of the drying vessel 120 via lines 154 and 155 . When pressurized fluid solvent is added to the drying vessel 120 , the organic solvent remaining on the textiles dissolves in the pressurized fluid solvent.
[0210] After a sufficient amount of pressurized fluid solvent is added so that the desired level of organic solvent has been dissolved, the pressurized fluid solvent and organic solvent combination is removed from the drying vessel 120 , and therefore also from the drying drum 122 , by opening valve 176 , closing valve 175 and activating pump 193 to pump the pressurized fluid solvent and organic solvent combination through outlet 126 via line 156 . If desired, this process may be repeated to remove additional organic solvent. The drying drum 122 is then rotated at a high speed, such as 150 - 800 rpm, to further remove the pressurized fluid solvent and organic solvent combination from the textiles. The drying drum 122 is preferably perforated so that, when the textiles are rotated in the drying drum 122 at a high speed, the pressurized fluid solvent and organic solvent combination can drain from the drying drum 122 . Any pressurized fluid solvent and organic solvent combination removed from the textiles by spinning the drying drum 122 at high speed is also pumped from the drying vessel 120 in the manner described above. After the pressurized fluid solvent and organic solvent combination is removed from the drying vessel 120 , it can either be discarded or separated and recovered for reuse with solvent recovery systems known in the art. Note that, while preferred, it is not necessary to include a high speed spin cycle to remove pressurized fluid solvent from the textiles.
[0211] After a desired amount of the pressurized fluid solvent is removed from the textiles by rotating the drying drum 122 , the drying vessel 120 is depressurized over a period of about 5 - 15 minutes. The depressurization of the drying vessel 120 vaporizes any remaining pressurized fluid solvent, leaving dry, solvent-free textiles in the drying drum 122 . The pressurized fluid solvent that has been vaporized is then removed from the drying vessel 120 by opening valve 176 , closing valve 175 , and activating pump 193 . As a result, the vaporized pressurized fluid solvent is pumped through the outlet 126 , line 156 and valve 176 , where it can then either be vented to the atmosphere or recovered and recompressed for reuse.
[0212] While the cleaning system 100 has been described as a complete system, an existing conventional dry cleaning system may be converted for use in accordance with the present invention. To convert a conventional dry cleaning system, the organic solvent described above is used to clean textiles in the conventional system. A separate pressurized vessel is added to the conventional system for drying the textiles with pressurized fluid solvent. Thus, the conventional system is converted for use with a pressurized fluid solvent. For example, the system in FIG. 1 could represent such a converted system, wherein the components of the cleaning machine 102 are conventional, and the pressurized fluid solvent tank 132 is not in communication with the cleaning vessel 100 . In such a situation, the drying machine 104 is the add-on part of the conventional cleaning machine.
[0213] Furthermore, while the system shown in FIG. 1 comprises a single cleaning vessel, multiple cleaning vessels could be used, so that the textiles are subjected to multiple cleaning steps, with each cleaning step carried out in a different cleaning vessel using the same or different organic solvents in each step. The description of the single cleaning vessel is merely for purposes of description and should not be construed as limiting the scope of the invention.
[0214] Referring now to FIG. 2 , a block diagram of an alternate embodiment of the present invention, a cleaning system having a single chamber for cleaning and drying the textiles, is shown. The cleaning system 200 generally comprises a cleaning machine having a pressurizable vessel 210 . The vessel 210 is operatively connected to, via one or more motor activated shafts (not shown), a perforated rotatable drum or wheel 212 within the vessel 210 with an inlet 214 to the vessel 210 and an outlet 216 from the vessel 210 through which dry cleaning fluids can pass.
[0215] An organic solvent tank 220 holds any suitable organic solvent, such as those described above, to be introduced to the vessel 210 through the inlet 214 . A pressurized fluid solvent tank 222 holds pressurized fluid solvent to be added to the vessel 210 through the inlet 214 . Filtration assembly 224 contains one or more filters that continuously remove contaminants from the organic solvent from the vessel 210 and drum 212 as cleaning occurs.
[0216] The components of the cleaning system 200 are connected with lines 230 - 234 that transfer organic solvents and vaporized and pressurized fluid solvent between components of the system. The term “line” as used herein is understood to refer to a piping network or similar conduit capable of conveying fluid and, for certain purposes, is capable of being pressurized. The transfer of the organic solvents and vaporized and pressurized fluid solvent through the lines 230 - 234 is directed by valves 250 - 254 and pumps 240 - 242 . While pumps 240 - 242 are shown in the described embodiment, any method of transferring liquid and/or vapor between components can be used, such as adding pressure to the component using a compressor to force the liquid and/or vapor from the component.
[0217] The textiles are cleaned with an organic solvent such as those previously described. The textiles may also be cleaned with a combination of organic solvent and pressurized fluid solvent, and this combination may be in varying proportions of 50-100% by weight organic solvent and 0-50% by weight pressurized fluid solvent. In the cleaning process, the textiles are first sorted as necessary to place the textiles into groups suitable to be cleaned together. The textiles may then be spot treated as necessary to remove any stains that may not be removed during the cleaning process. The textiles are then placed into the drum 212 within the vessel 210 of the cleaning system 200 . It is preferred that the drum 212 be perforated to allow for free interchange of solvent between the drum 212 and the vessel 210 as well as to transport soil from the textiles to the filtration assembly 224 .
[0218] After the textiles are placed in the drum 212 , an organic solvent contained in the organic solvent tank 220 is added to the vessel 210 via line 231 by opening valve 251 , closing valves 250 , 252 , 253 and 254 , and activating pump 242 to pump organic solvent through the inlet 214 of the vessel 210 . The organic solvent may contain one or more co-solvents, detergents, water, or other additives to enhance the cleaning capability of the cleaning system 200 or other additives to impart other desirable attributes to the articles being treated. Alternatively, one or more additives may be added directly to the vessel. Pressurized fluid solvent may also be added to the vessel 210 along with the organic solvent to enhance cleaning. The pressurized fluid solvent is added to the vessel 210 via line 230 by opening valve 250 , closing valves 251 , 252 , 253 and 254 , and activating pump 240 to pump the pressurized fluid solvent through the inlet 214 of the vessel 210 .
[0219] When the desired amount of the organic solvent, or combination of organic solvent and pressurized fluid solvent as described above, is added to the vessel 210 , the motor (not shown) is activated and the drum 212 is agitated and/or rotated. During this phase, the organic solvent, as well as pressurized fluid solvent if used in combination, is continuously cycled through the filtration assembly 224 by opening valves 252 and 253 , closing valves 250 , 251 and 254 , and activating pump 241 . Filtration assembly 224 may include one or more fine mesh filters to remove particulate contaminants from the organic solvent and pressurized fluid solvent passing therethrough and may alternatively or in addition include one or more absorptive or adsorptive filters to remove water, dyes, and other dissolved contaminants from the organic solvent. Exemplary configurations for filter assemblies that can be used to remove contaminants from either the organic solvent or the pressurized fluid solvent are described more fully in U.S. application Ser. No. 08/994,583 incorporated herein by reference. As a result, the organic solvent is pumped through outlet 216 , valve 253 , line 233 , filter assembly 224 , line 232 , valve 252 and reenters the vessel 210 via inlet 214 . This cycling advantageously removes contaminants, including particulate contaminants and/or soluble contaminants, from the organic solvent and pressurized fluid solvent and reintroduces filtered solvent to the vessel 210 . Through this process, contaminants are removed from the textiles.
[0220] After sufficient time has passed so that the desired level of contaminants is removed from the textiles and solvents, the organic solvent is removed from the vessel 210 and drum 212 by opening valve 254 , closing valves 250 , 251 , 252 and 253 , and activating pump 241 to pump the organic solvent through outlet 216 and line 234 . If pressurized fluid solvent is used in combination with organic solvent, it may be necessary to first separate the pressurized fluid solvent from the organic solvent. The organic solvent can then either be discarded or, preferably, contaminants may be removed from the organic solvent and the organic solvent recovered for further use. Contaminants may be removed from the organic solvent with solvent recovery systems known in the art. The drum 212 is then rotated at a high speed, such as 150-800 rpm, to further remove organic solvent from the textiles. The drum 212 is preferably perforated so that, when the textiles are rotated in the drum 212 at a high speed, the organic solvent can drain from the cleaning drum 212 . Any organic solvent removed from the textiles by rotating the drum 212 at high speed can also either be discarded or recovered for further use.
[0221] After a desired amount of organic solvent is removed from the textiles by rotating the drum 212 , pressurized fluid solvent contained in the pressurized fluid tank 222 is added to the vessel 210 by opening valve 250 , closing valves 251 , 252 , 253 and 254 , and activating pump 240 to pump pressurized fluid solvent through the inlet 214 of the pressurizable vessel 210 via line 230 . When pressurized fluid solvent is added to the vessel 210 , organic solvent remaining on the textiles dissolves in the pressurized fluid solvent.
[0222] After a sufficient amount of pressurized fluid solvent is added so that the desired level of organic solvent has been dissolved, the pressurized fluid solvent and organic solvent combination is removed from the vessel 210 by opening valve 254 , closing valves 250 , 251 , 252 and 253 , and activating pump 241 to pump the pressurized fluid solvent and organic solvent combination through outlet 216 and line 234 . Note that pump 241 may actually require two pumps, one for pumping the low pressure organic solvent in the cleaning cycle and one for pumping the pressurized fluid solvent in the drying cycle.
[0223] The pressurized fluid solvent and organic solvent combination can then either be discarded or the combination may be separated and the organic solvent and pressurized fluid solvent separately recovered for further use. The drum 212 is then rotated at a high speed, such as 150-350 rpm, to further remove pressurized fluid solvent and organic solvent combination from the textiles. Any pressurized fluid solvent and organic solvent combination removed from the textiles by spinning the drum 212 at high speed can also either be discarded or retained for further use. Note that, while preferred, it is not necessary to include a high speed spin cycle to remove pressurized fluid solvent from the textiles.
[0224] After a desired amount of the pressurized fluid solvent is removed from the textiles by rotating the drum 212 , the vessel 210 is depressurized over a period of about 5-15 minutes. The depressurization of the vessel 210 vaporizes the pressurized fluid solvent, leaving dry, solvent-free textiles in the drum 212 . The pressurized fluid solvent that has been vaporized is then removed from the vessel 210 by opening valve 254 , closing valves 250 , 251 , 252 and 253 , and activating pump 241 to pump the vaporized pressurized fluid solvent through outlet 216 and line 234 . Note that while a single pump is shown as pump 241 , separate pumps may be necessary to pump organic solvent, pressurized fluid solvent and pressurized fluid solvent vapors, at pump 241 . The remaining vaporized pressurized fluid solvent can then either be vented into the atmosphere or compressed back into pressurized fluid solvent for further use.
[0225] As discussed above, terpenes, halohydrocarbons, certain glycol ethers, polyols, ethers, esters of glycol ethers, esters of fatty acids and other long chain carboxylic acids, fatty alcohols and other long-chain alcohols, short-chain alcohols, polar aprotic solvents, siloxanes, hydrofluoroethers, dibasic esters, and aliphatic hydrocarbons solvents or similar solvents or mixtures of such solvents are organic solvents that can be used in the present invention, as shown in the test results below. Table 1 shows results of detergency testing for each of a number of solvents that may be suitable for use in the present invention. Table 2 shows results of testing of drying and extraction of those solvents using densified carbon dioxide.
[0226] Detergency tests were performed using a number of different solvents without detergents, co-solvents, or other additives. The solvents selected for testing include organic solvents and liquid carbon dioxide. Two aspects of detergency were investigated—soil removal and soil redeposition. The former refers to the ability of a solvent to remove soil from a substrate while the latter refers to the ability of a solvent to prevent soil from being redeposited on a substrate during the cleaning process. Wascherei Forschungs Institute, Krefeld Germany (“WFK”) standard soiled swatches that have been stained with a range of insoluble materials and WFK white cotton swatches, both obtained from TESTFABRICS, Inc., were used to evaluate soil removal and soil redeposition, respectively.
[0227] Soil removal and redeposition for each solvent was quantified using the Delta Whiteness Index. This method entails measuring the Whiteness Index of each swatch before and after processing. The Delta Whiteness Index is calculated by subtracting the Whiteness Index of the swatch before processing from the Whiteness Index of the swatch after processing. The Whiteness Index is a function of the light reflectance of the swatch and in this application is an indication of the amount of soil on the swatch. More soil results in a lower light reflectance and Whiteness Index for the swatch. The Whiteness indices were measured using a reflectometer manufactured by Hunter Laboratories.
[0228] Organic solvent testing was carried out in a Launder-Ometer while the densified carbon dioxide testing was carried out in a Parr Bomb. After measuring their Whiteness Indices, two WFK standard soil swatches and two WFK white cotton swatches were placed in a Launder-Ometer cup with 25 stainless steel ball bearings and 150 mL of the solvent of interest. The cup was then sealed, placed in the Launder-Ometer and agitated for a specified length of time. Afterwards, the swatches were removed and placed in a Parr Bomb equipped with a mesh basket. Approximately 1.5 liters of liquid carbon dioxide between 5° C. and 25° C. and 570 psig and 830 psig was transferred to the Parr Bomb. After several minutes the Parr Bomb was vented and the dry swatches removed and allowed to reach room temperature. Testing of densified carbon dioxide was carried out in the same manner but test swatches were treated for 20 minutes. During this time the liquid carbon dioxide was stirred using an agitator mounted on the inside cover of the Parr bomb. The Whiteness Index of the processed swatches was determined using the reflectometer. The two Delta Whiteness Indices obtained for each pair of swatches were averaged. The results are presented in Table 1.
[0229] Because the Delta Whiteness Index is calculated by subtracting the Whiteness Index of a swatch before processing from the Whiteness Index value after processing, a positive Delta Whiteness Index indicates that there was an increase in Whiteness Index as a result of processing. In practical terms, this means that soil was removed during processing. In fact, the higher the Delta Whiteness Value, the more soil was removed from the swatch during processing. Each of the organic solvents tested exhibited soil removal capabilities. The WFK white cotton swatches exhibited a decrease in Delta Whiteness Indices indicating that the soil was deposited on the swatches during the cleaning process. Therefore, a “less negative” Delta Whiteness Index suggests that less soil was redeposited.
TABLE 1 Delta Whiteness Values Insoluble Insoluble Cleaning Soil Soil Solvent Time (min.) Removal Redeposition Liquid carbon dioxide (neat) 20 3.36 −1.23 Pine oil 12 8.49 −6.84 d-limonene 12 10.6 −9.2 1,1-2 trichlorotrifluoroethane 12 11.7 −14.46 N-propyl bromide 12 11.18 −9.45 Perfluorohexane 12 2.09 −3.42 triethylene glycol mono-oleyl 12 10.54* −1.86* ether (Volpo 3) ∀-phenyl-ω-hydroxy-poly 12 1.54** −13.6** (oxy-1,2-ethanediyl) Hexylene glycol 12 6.9 −1.4 Tetraethylene glycol dimethyl 12 10.08 −4.94 ether Ethylene glycol diacetate 12 6.29 −3.39 Decyl acetates (Exxate 1000) 12 11.69 −8.6 Tridecyl acetates (Exxate 12 11.24 −4.86 1300) Soy methyl esters (SoyGold 12 5.81 −7.71 1100) 2-ethylhexanol 12 12.6 −3.4 Propylene carbonate 12 2.99 −1.82 Dimethylsulfoxide 12 5.84 −0.22 Dimethylformamide 12 7.24 −10.09 Isoparaffins (DF-2000) 12 11.23 −5.95 Dimethyl glutarate 12 9.04 −1.23 *After two extraction cycles **After three extraction cycles.
[0230] To evaluate the ability of densified carbon dioxide to extract organic solvent from a substrate, WFK white cotton swatches were used. One swatch was weighed dry and then immersed in an organic solvent sample. Excess solvent was removed from the swatch using a ringer manufactured by Atlas Electric Devices Company. The damp swatch was re-weighed to determine the amount of solvent retained in the fabric. After placing the damp swatch in a Parr Bomb densified carbon dioxide was transferred to the Parr Bomb. The temperature and pressure of the densified carbon dioxide for all of the trials ranged from 5° C. to 20° C. and from 570 psig-830 psig. After five minutes the Parr Bomb was vented and the swatch removed. The swatch was next subjected to Soxhlet extraction using methylene chloride for a minimum of two hours. This apparatus enables the swatch to be continuously extracted to remove the organic solvent from the swatch. After determining the concentration of the organic solvent in the extract using gas chromatography, the amount of organic solvent remaining on the swatch after exposure to densified carbon dioxide was calculated by multiplying the concentration of the organic solvent in the extract by the volume of the extract. A different swatch was used for each of the tests. The results of these tests are included in Table 2. As the results indicate, the extraction process using densified carbon dioxide is extremely effective.
TABLE 2 Percentage by Weight Weight of Solvent on of Solvent Test Swatch (grams) Removed Before After from Solvent Extraction Extraction Swatch Pine oil 7.8 0.1835 97.66% d-Limonene 5.8 0.0014 99.98% 1,1,2-Trichlorotrifluoroethane 1.4 0.0005 99.96% n-Propyl bromide 2.8 <0.447 >84% Perfluorohexane 1.0 0.0006 99.94% Triethylene glycol monooleyl 0.8 0.1824 77.88% ether (7) ∀-phenyl-ω-hydroxy- 16.0 5.7 64.5% poly(oxy 1,2-ethanediyl); (Ethylan HB4) Hexylene glycol 4.9 0.3481 92.87% Tetraethylene glycol dimethyl ether 5.2 .1310 97.48% Ethylene glycol diacetate 5.3 0.0418 99.21% Decyl acetate (2) 2.4 0.0015 99.94% Tridecyl acetate (1) 4.8 0.0605 98.75% Soy methyl esters (8) 4.9 0.0720 98.54% 2-Ethylhexanol 0.5 0.0599 99.09% Propylene carbonate 6.6 0.0599 99.09% Dimethyl sulfoxide 3.3 0.5643 82.69% Dimethylformamide 3.0 0.0635 97.88% Octamethylcyclooctasiloxane/ 5.5 0.0017 99.97% Decamethylcyclopentasiloxane (4) 1-Methoxynonofluorobutane (6) 0.7 not ˜100% detected Isoparaffins (5) 4.3 0.0019 99.96% Dimethyl glutarate (3)‡ 5.8 0.0090 99.85% Notes on Table 3: (1) Exxate 1300 (Exxon); (2) Exxate 1000 (Exxon); (3) DBE-5 (DuPont); (4) SF1204 (General Electric Silicones); (5) DF-2000 (Exxon); (6) HFE-7100 (3M); (7) Volpo 3 (Croda); (8) Soy Gold 1100 (AG Environmental Products)
[0231] It is to be understood that a wide range of changes and modifications to the embodiments described above will be apparent to those skilled in the art and are contemplated. It is, therefore, intended that the foregoing detailed description be regarded as illustrative rather than limiting, and that it be understood that it is the following claims, including all equivalents, that are intended to define the spirit and scope of the invention.
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A cleaning system that utilizes an organic cleaning solvent and pressurized fluid solvent is disclosed. The system has no conventional evaporative hot air drying cycle. Instead, the system utilizes the solubility of the organic solvent in pressurized fluid solvent as well as the physical properties of pressurized fluid solvent. After an organic solvent cleaning cycle, the solvent is extracted from the textiles at high speed in a rotating drum in the same way conventional solvents are extracted from textiles in conventional evaporative hot air dry cleaning machines. Instead of proceeding to a conventional drying cycle, the extracted textiles are then immersed in pressurized fluid solvent to extract the residual organic solvent from the textiles. This is possible because the organic solvent is soluble in pressurized fluid solvent. After the textiles are immersed in pressurized fluid solvent, pressurized fluid solvent is pumped from the drum. Finally, the drum is de-pressurized to atmospheric pressure to evaporate any remaining pressurized fluid solvent, yielding clean, solvent free textiles. The organic solvent is preferably selected from terpenes, halohydrocarbons, certain glycol ethers, polyols, ethers, esters of glycol ethers, esters of fatty acids and other long chain carboxylic acids, fatty alcohols and other long-chain alcohols, short-chain alcohols, polar aprotic solvents, siloxanes, hydrofluoroethers, dibasic esters, and aliphatic hydrocarbons solvents or similar solvents or mixtures of such solvents and the pressurized fluid solvent is preferably densified carbon dioxide.
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RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/933,183 filed Jun. 5, 2007.
BACKGROUND
[0002] The invention is directed to expandable casing packing element systems for use in oil and gas wells and, in particular, expandable casing packing element systems having extrudable sealing elements for sealing open-hole wells.
[0003] Expandable casing having a sealing element such as a packer have been used to seal the annulus of open-hole wells. In operation, after the well is drilled into the earth formation, the expandable casing is run into the well. The expandable casing has disposed on it, or as part of the expandable casing string, a sealing device such as a packer. The packer is designed to divide the well by sealing against the well formation, thereby isolating a lower portion of the well from an upper portion of the well.
[0004] After the expandable casing is run into the desired location in the well, a cone or other device can be transported through the bore of the expandable casing. As the cone, such as a swage, travels downward, the expandable casing is expanded by the cone. The expansion of the expandable casing causes the sealing device to contact the formation and separate the open-hole well into at least two isolated regions, one above the sealing device and one below the sealing device.
[0005] The expandable casing and sealing devices disclosed herein include components that, to the inventors' knowledge, are novel and non-obvious from previous expandable casing and sealing devices.
SUMMARY OF INVENTION
[0006] Broadly, the expandable casing packing element systems disclosed herein include an expandable casing member having a sealing device comprising a sealing element disposed between at least two retainer rings. In one embodiment, both retainer rings have flat cross-sections and the sealing element is forced radially outward by the expansion of the expandable casing against the two retainer rings such that the sealing element protrudes outwardly beyond the retainer rings and engages the wall of the a wellbore in three locations. The wellbore may be an opened-hole wellbore or a cased wellbore. In another embodiment, both of the two retainer rings include flares that extend outwardly from the body of the expandable casing to which they are attached. As the expandable casing is expanded, the flares are forced inward to compress the sealing element which is then extruded radially outward through a gap between the two retainer rings to engage and seal off the wellbore.
[0007] Also disclosed is a method comprising the steps of: (a) running an expandable casing string having a packing element system attached thereto into a wellbore defined by an inner wall surface, the packing element system having a sealing element and at least two retainer rings, at one of the at least two retainer rings overlapping the sealing element; (b) applying a radial load to expand the expandable casing, causing the sealing element to be extruded outwardly by at least one of the at least two retainer rings applying an inward force to the sealing element; and (c) continuing to apply the radial load causing the sealing element to move radially outward into sealing engagement with the inner wall surface of the wellbore. In one particular embodiment, the wellbore is cased. In another specific embodiment, the wellbore is an opened-hole wellbore.
BRIEF DESCRIPTION OF DRAWINGS
[0008] FIG. 1 is a cross-sectional view of one embodiment of an expandable casing having a sealing device, FIG. 1 showing the expandable casing as it is being expanded from its run-in position to its expanded or set position.
[0009] FIG. 2 is a cross-sectional view of another specific embodiment of an expandable casing having a sealing device, FIG. 2 showing the expandable casing in its run-in position.
[0010] FIG. 3 is a cross-sectional view of the expandable casing shown in FIG. 2 shown in its expanded or set position.
[0011] While the invention will be described in connection with the preferred embodiments, it will be understood that it is not intended to limit the invention to that embodiment. On the contrary, it is intended to cover all alternatives, modifications, and equivalents, as may be included within the spirit and scope of the invention as defined by the appended claims.
DETAILED DESCRIPTION OF INVENTION
[0012] Referring now to FIG. 1 , in one specific embodiment, expandable casing 30 is disposed within well 20 that has been drilled into formation 26 . Well 20 is defined by well inner wall surface 22 . Expandable casing 30 has upper end 32 , lower end 34 , bore 36 defined by inner wall surface 38 , outer wall surface 39 , and axis 40 . Expandable casing 30 includes run-in diameter 42 , set diameter 44 , and transitional diameter 46 . Run-in diameter 42 is less than set diameter 44 and transitional diameter 46 illustrates the location of a cone (not shown) or other device used to expand expandable casing 30 from the run-in diameter 42 to the set diameter 44 . Although a cone is described as being used to expand expandable casing 30 from the run-in diameter 42 to the set diameter 44 , it is to be understood that any device or method known to persons of ordinary skill in the art may be used to expand expandable casing 30 .
[0013] As illustrated in FIG. 1 , disposed on outer wall surface 39 of expandable casing 30 are upper sealing device 50 and lower sealing device 60 . In this embodiment, upper sealing device 50 is identical to lower sealing device 60 except that upper sealing device 50 is shown in the set position and lower sealing device 60 is shown in the run-in position. It is to be understood, however, that expandable casing 30 may have only one sealing device 50 , 60 , or more than two sealing devices 50 , 60 . For convenience, both upper and lower sealing devices 50 , 60 will be discussed in greater detail with reference to like numerals.
[0014] Sealing devices 50 , 60 include annular deformable sealing elements 51 having upper ends 52 and lower ends 54 , upper retainer ring 56 , and lower retainer ring 58 . Sealing element 51 is a deformable element formed from an deformable material so that radial outward movement of sealing element 51 away from axis 40 and into upper and lower retainer rings 56 , 58 causes sealing element 51 to extrude into sealing contact with inner wall surface 22 of well 20 . Suitable materials for forming sealing element 51 include, but are not limited to, elastomers, rubbers, polymers, or thermoplastics.
[0015] Additionally, sealing element 51 may have any shape desired or necessary to provide the requisite compression, deformation, or “extrusion” to form the seal with inner wall surface 22 of well 20 . As shown in FIG. 1 , in this specific embodiment, sealing element 51 is formed in the shape of a sleeve having a thicker center portion as compared to upper and lower ends 52 , 54 . This thicker portion is disposed between upper and lower retainer rings 56 , 58 and, as shown with reference to sealing device 60 , has an outer diameter that is equal to the outer diameter of both upper and lower retainer rings 56 , 58 when in the run-in position. It is to be understood, however, that sealing element 51 may have an outer diameter that is less than the outer diameter of one or both of upper or lower retainer rings 56 , 58 when in its run-in position or it may have an outer diameter that is greater than the outer diameter of one or both upper or lower retainer rings 56 , 58 when in its run-in position.
[0016] Further, in the embodiment shown in FIG. 1 , upper and lower ends 52 , 54 are shown protruding above and below upper and lower retainer rings 56 , 58 ; however, upper and lower ends 52 , 54 are not required to protrude above and below upper and lower retainer rings in this manner.
[0017] Sealing element 51 is maintained against outer wall surface 39 of expandable casing 30 using any device or method known to persons of ordinary skill in the art. For example, sealing element 51 may be chemically bonded to outer wall surface 39 . Alternatively, sealing element 51 can be maintained solely by upper and lower retainer rings 56 , 58 .
[0018] Upper retainer rings 56 and lower retainer rings 58 are expandable members disposed around the outer diameter of sealing element 51 and, thus, can maintain or assist in maintaining sealing element 51 along outer wall surface 39 . In this embodiment both upper retainer ring 56 and lower retainer ring 58 have a relatively flat vertical cross-section parallel or substantially parallel to the axial length of the expandable casing 30 . As additionally shown in FIG. 1 , both upper and lower retainer rings 56 , 58 have an axial length greater than their width so that the inner diameter surface area of both upper and lower retainer rings 56 , 58 are in contact with sealing element 51 to facilitate extrusion of sealing element 51 during expansion of expandable casing 30 .
[0019] Although the shape of upper and lower retainer rings 56 , 58 are discussed with reference to FIG. 1 , it is to be understood that upper and lower retainer rings 56 , 58 may have any shape desired or necessary to provide the necessary force against sealing element 51 during expansion of expandable casing 30 so that sealing element 51 is extruded to seal against inner wall surface 22 of well 20 .
[0020] Further, upper and lower retainer rings 56 , 58 may be formed from any material known to persons of ordinary skill in the art. For example, one or both of upper and lower retainer rings 56 , 58 may be formed from stiffer elastomers, polymers, or metals such as steel.
[0021] After expandable casing 30 is properly located within well 20 , a cone (not shown) or other expanding device is run through bore 36 of expandable casing 30 . As the cone travels downward, i.e., downhole, expandable casing 30 is forced radially outward from axis 40 . In so doing, run-in diameter 42 is radially expanded to transition diameter 46 and ultimately to set diameter 44 . As a result of the radial expansion of expandable casing 30 , sealing element 51 is forced into upper and lower retainer rings 56 , 58 . Although upper and lower retainer rings 56 , 58 are radially expandable, they are formed from a material that is stronger, i.e., more resistance to expansion, compared to the material used to form sealing element 51 . As a result, as expandable casing 30 is expanded, sealing material 51 is compressed, deformed, or extruded in between outer wall surface 39 of expandable casing and the inner wall surfaces of upper and lower retainer rings 56 , 58 defined by the inner diameters of upper and lower retainer rings 56 , 58 . Due to the compression of sealing element 51 between outer wall surface 39 of expandable casing 30 and the inner wall surfaces of upper and lower retainer rings 56 , 58 , the center portion of sealing element 51 is extruded outwardly in between upper and lower retainer rings 56 , 58 ; upper end 52 of sealing element 51 is extruded outwardly above upper retainer ring 56 ; and lower end 54 of sealing element 51 is extruded outwardly below lower retainer ring 58 until all three portions of sealing element 51 form a seal against inner wall surface 22 of well 20 . The distance between the outer diameter of upper and lower retainer rings 56 , 58 and inner wall surface 22 of well 20 is referred to as the extrusion gap.
[0022] Referring now to FIGS. 2-3 , in another embodiment, expandable casing 130 has upper end 132 , lower end 134 , bore 136 defined by inner wall surface 138 , outer wall surface 139 , and axis 140 . Expandable casing 30 includes run-in diameter defined by run-in radius 142 ( FIG. 2 ) and set diameter defined by set radius 144 ( FIG. 3 ). Run-in radius 142 and, thus, the run-in diameter, is less than set radius 144 and, thus, the set diameter. Expandable casing 130 is radially expanded using a cone (not shown) or other device used to expand expandable casing 130 from the run-in diameter defined by run-in radius 142 to the set diameter defined by set radius 144 in the same manner as the embodiment discussed above with respect to FIG. 1 .
[0023] As illustrated in FIG. 2 , expandable casing 130 is in the run-in position. Disposed on outer wall surface 139 of expandable casing 130 is sealing device 150 . Although only a single sealing device 150 is shown, it is to be understood that more than one sealing device may be disposed on outer wall surface 139 of expandable casing 130 .
[0024] Sealing device 150 includes annular sealing element 151 , upper retainer ring 156 and lower retainer ring 158 . Annular sealing element 151 is a deformable element formed from a deformable material such as those discussed above with respect to sealing element 51 . In this embodiment, sealing element 151 has a trapezoid section such that the inner surface of sealing element 151 has a longer axial length along outer wall surface 139 than the axial length of the outer surface defined by the outer diameter of sealing element 151 .
[0025] Upper retainer ring 156 has upper flare portion 157 and lower retainer ring 158 has lower flare portion 159 thereby forming a cavity between upper retainer ring 156 and lower retainer ring 158 with a gap between the lowermost end of upper retainer ring 156 and the uppermost end of lower retainer ring 158 . Sealing element 151 is disposed within the cavity. In one specific embodiment, sealing element 151 is maintained along outer wall surface 139 through any device or method known to persons of ordinary skill in the art, such as through chemical bonding or by upper and lower retainer rings 156 , 158 .
[0026] As with the embodiment shown in FIG. 1 , upper and lower retainer rings 156 , 158 may be formed from any material known to persons of ordinary skill in the art. For example, one or both of upper and lower retainer rings 156 , 158 may be formed from stiffer elastomers, polymers, or metals such as steel.
[0027] Upper flare portion 157 and lower flare portion 159 may have any shape or angle relative to the remaining vertical portions of upper and lower flare portions. For example, upper and lower flare portions 157 , 159 may be at an angle in a range greater than 0 degrees and less than 90 degrees relative to the vertical portions of upper and lower flare portions 157 , 159 . Additionally, the angle at which upper flare portion 157 intersects the remaining portion of upper retainer ring may be different from the angle at which lower flare portion 159 intersects the remaining portion of lower retainer ring 158 . In one specific embodiment, both of these angles are within the range from 30 degrees to 60 degrees so that sufficient inward force can be applied to sealing element 151 during expansion of expandable casing 130 to extrude sealing element 151 through the gap between the lowermost and uppermost ends of upper retainer ring 156 and lower retainer ring 158 , respectively. In the embodiment shown in FIGS. 2-3 , upper and lower flare portions 157 , 159 are reciprocally shaped to receive sealing element 151 so that a portion of both upper and lower flare portions 157 , 159 contact sealing element 151 during run-in.
[0028] Upper and lower retainer rings 156 , 158 can be secured to outer wall surface 139 through any device or method known to persons of ordinary skill in the art. For example, upper and lower retainer rings 156 , 158 may be welded or epoxied to outer wall surface 139 . Alternatively, upper and lower retainer rings 156 , 158 may be secured or formed integral with an expandable mandrel (not shown) that is then secured such as through threads to an expandable casing string.
[0029] As shown in FIG. 2 , sealing element 151 of sealing device 150 is in its run-in position such that it does not protrude outwardly from outer wall surface 139 past upper or lower retainer rings 156 , 158 . It is to be understood that although sealing element 151 is shown as having an outer diameter equal to the outer diameters of upper and lower retainer rings 156 , 158 , sealing element 151 may have either an outer diameter that is less than the outer diameter of one or both of upper or lower retainer rings 156 , 158 when in its run-in position, or an outer diameter that is greater than the outer diameter of one or both of upper or lower retainer rings 156 , 158 when in its run-in position.
[0030] After expandable casing 130 is properly located within well (not shown), a cone (not shown) or other expanding device is run through bore 136 of expandable casing 130 . As the cone travels downward, i.e., downhole, expandable casing 130 is forced radially outward from axis 140 . In so doing, the run-in diameter illustrated by run-in radius 142 is radially expanded to a transition diameter (not shown) and ultimately to set diameter illustrated by set radius 144 ( FIG. 3 ). As a result of the radial expansion of expandable casing 130 , sealing element 151 is forced into upper and lower flare portions 157 , 159 of upper and lower retainer rings 156 , 158 . As with upper and lower retainer rings 56 , 58 , upper and lower retainer rings 156 , 158 are radially expandable; however, they are formed from a material that is stronger, i.e., has more resistance to expansion, compared to the material used to form sealing element 151 . As a result, as expandable casing 130 is expanded, upper and lower flare portions 157 , 159 bend inward toward axis 140 as expandable casing 130 expands and, thus, compress, deform, or extrude sealing element 151 within the cavity in between outer wall surface 139 of expandable casing 130 and upper and lower flare portions 157 , 159 . In other words, upper flare portion 157 and lower flare portion 159 become more straightened in line with the remaining portions of upper retainer ring 156 and lower retainer ring 158 , respectively, so that sealing element 151 is forced radially outward.
[0031] Due to the compression of sealing element 151 between outer wall surface 139 of expandable casing 130 and the upper and lower flare portions 157 , 159 , sealing element 151 is extruded outwardly from the cavity through the gap located between the lowermost end of upper retainer ring 156 and the upper most end of lower retainer ring 158 until sealing element 151 forms a seal against the inner wall surface of the well. This distance between the outermost diameters of upper and lower retainer rings 156 , 158 and the inner wall surface of the well is referred to as the extrusion gap.
[0032] It is to be understood that the invention is not limited to the exact details of construction, operation, exact materials, or embodiments shown and described, as modifications and equivalents will be apparent to one skilled in the art. For example, the sealing devices may be disposed on an expandable mandrel that is placed within an expandable casing string. Additionally, the expandable casing may have one or more sealing devices 50 or 60 together with one or more sealing devices 150 . Moreover, a spacer may be disposed in between outer wall surface 39 of expandable casing 30 and the inner diameter of sealing element 151 to assist in extrusion of sealing element 151 during expansion of expandable casing 130 . Further, the inner diameter of upper retainer ring 56 is not required to be equal to the inner diameter of lower retainer ring 58 . Likewise, the shape of upper flare portion 157 is not required to be the same shape as lower flare portion 159 . Additionally, the expandable casing 30 , 130 may be disposed in a cased wellbore as opposed to an open-hole wellbore. Thus, the term “wellbore” as used herein includes a cased wellbore as well as an opened-hole wellbore. Accordingly, the invention is therefore to be limited only by the scope of the appended claims.
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The expandable casing packing element systems for cased and open-hole wellbores include an expandable casing member having a sealing device comprising a sealing element disposed between at least two retainer rings. In one embodiment, both retainer rings have flat cross-sections and the sealing element is forced radially outward by the expansion of the expandable casing against the two retainer rings such that the sealing element protrudes outwardly beyond the retainer rings and engages the wall of a wellbore in three locations. In another embodiment, both of the two retainer rings include flares that extend outwardly from the body of the expandable casing to which they are attached. As the expandable casing is expanded, the flares are forced inward to compress the sealing element which is then extruded radially outward through a gap between the two retainer rings to engage and seal off the wellbore.
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BACKGROUND OF THE INVENTION
[0001] This invention relates to a wheeled walker that can be used as a transport chair for the disabled and to a novel braking system for wheeled apparatus.
[0002] Many persons, by reason of age or disability have difficulty in walking without a walking aid. Wheeled walkers are widely used by many such persons to assist in mobility. A wheeled walker typically has a frame mounted on four wheels and a pair of rearwardly extending handle bars which the user can grip for support while walking. The user positions himself between the handle bars behind the walker and pushes the walker forward. The wheels permit the user to roll the walker smoothly over the ground thereby avoiding the laborious action of picking up and moving a non-wheeled walker in step-by-step fashion. The handle bars can be fitted with brake levers that when squeezed by the user, actuate some form of wheel braking mechanism.
[0003] Wheeled walkers are routinely equipped with a seating surface that permits the user to rest in the sitting position. The seating surface is usually positioned transversely between the handle bars within the wheel base of the walker to offer a stable platform for sitting. In order to use the seating surface, the user must turn around and sit down in the rearward facing direction, opposite to the normal direction of travel, with his feet resting on the ground. The braking mechanism can be fitted with a locking mechanism to maintain braking engagement with the wheels to prevent the walker from rolling while the user is sitting.
[0004] While the provision of a seat to permit the user to rest is a useful feature, it often occurs that the user is too tired to continue walking and requires the assistance of a care-giver continue travel. Conventional wheeled walkers are not adapted to support a seated user and be pushed by a care-giver. In particular, because the user is seated in a rearward facing position between the handlebars, there is very little space between the user and the care-giver, making it difficult for the care-giver to take walking steps without interfering with the feet of the user. Moreover, there is no dedicated means on conventional walkers to support the feet of the user while in the sitting position with the result that the feet are usually dragged across the ground or propped up on a frame member in an unnatural position.
[0005] There have been a number of attempts to provide a wheeled apparatus that is useful as a self-propelled walker and also as a care-giver propelled transport chair.
[0006] U.S. Pat. No. 5,451,193 discloses a combined wheelchair and walker. In the normal walking position, the seating surface is pivoted up rearwardly toward the seat back to provide space between the handlebars for the user to walk. The user walks in a forward direction pulling the walker behind him. When the user wishes to sit, the seating surface can be flipped down. There is no provision to permit the walker to be pushed by a care-giver. Indeed, the patent discloses that a third party must pull the seated user backwards by pulling on the seat back.
[0007] U.S. Pat. No. 5,451,193 discloses a combination wheelchair and walker. While the user or the care-giver can push the apparatus from behind as a conventional walker or transport chair, in order to assume the seated position, the user must walk around to the front of the apparatus, which manoeuvre can be difficult for a physically challenged person.
[0008] U.S. Pat. No. 5,605,345 discloses a wheeled apparatus for use both as a walker and a wheelchair. The design has rearward facing handle bars to permit the apparatus to be used as a wheeled walker. The design also has a bidirectional seating arrangement. When the seat is placed in the rearward facing position, it permits the person using the device as a walker to rest in a seated position by turning around and sitting down in the rearward facing direction with his feet resting on the ground. When the seat is placed in the forward facing position, the apparatus can be used as a conventional wheelchair. The wheelchair design is conventional in that it has large rear wheels with hand-rings that permit the wheelchair to be propelled by the occupant or rearward facing handles to permit the wheelchair to be pushed by a care-giver.
[0009] While the design disclosed in U.S. Pat. No. 5,605,345 offers significant advantages, it is not well adapted for use as a walker. Because it is based on a conventional wheelchair design, it is heavy and bulky, making it difficult to manoeuvre in confined locations. Furthermore, the bi-directional seating arrangement uses a frame mounted link arrangement which cannot be practicably adapted to a light walker design. Because the seat back is pivoted to the seat base, the vertical rise of the seat back is limited and accordingly offers only lower back support. Furthermore, when positioned in the walker mode, the seat back obscures the user's view of the ground directly in front of the walker.
[0010] Conventional walkers have been equipped with handle bar mounted braking system actuators that permit the user to manually apply braking force when walking or to lock the brakes to permit the user to safely assume a seated position. For example, one such system is disclosed in U.S. Pat. No. 5,279,180 and relates to a cable braking system. The actuating mechanism uses a connecting lever to pull the cable when the brake lever is raised to a braking position or depressed to a locked position.
[0011] Thus, there remains a need for a walking aid that offers all of the functionality of a conventional wheeled walker and can be readily converted for use as a transport chair.
[0012] Cable type braking systems are commonly used on walkers which have height adjustable handle bars. In such a case, the flexible cable accommodates the variable length between the brake handle actuator and the wheel mounted braking element. However, cable type braking mechanisms have a number of deficiencies. In particular, the cables require rather precise and periodic adjustment to maintain effective braking action. Moreover, because the cables are routed from the brake handle actuator to the wheels outside of the frame and require some slack to accommodate height adjustability, the resulting loop or bight in the cable is prone to catching or snagging on other objects, a deficiency which is particularly problematic in the case of a folding style walker that is transported in the trunk of a car.
[0013] Thus, there remains a need for a brake actuating system which avoids the problems associated with cable based systems.
SUMMARY OF THE INVENTION
[0014] The present invention provides a wheeled walking aid that functions as a conventional walker, but is adapted to also be used as a transport chair. The present invention also provides for a novel braking system in which the brake actuating linkage is internal of structural members, and is length adjustable.
[0015] In accordance with the present invention, there is provided a convertible walker/transport chair apparatus, comprising a frame having a longitudinal axis in the forward and rearward directions, a pair of front wheels evenly spaced on either side of said longitudinal axis along a front transverse axis and rotatably mounted at the lower ends of a pair of upwardly extending front leg members, a pair of rear wheels evenly spaced on either side of said longitudinal axis along a rear transverse axis and rotatably mounted at the lower ends of a pair of upwardly extending rear leg members, a horizontal seating surface transversely disposed at the upper ends of said front and rear leg members, a pair of handle bar members slidably received for telescopic movement within the upper ends of said rear leg members and projecting upwardly and rearwardly of said seating surface, a pair of push handle assemblies, each of said assemblies disposed at the upper end of said handle bar member, a backrest connection member projecting forwardly from the upper end of each said handle bar members, a generally arcuate shaped backrest disposed transversely between said backrest connection members, pivotal attachment means disposed substantially in vertical alignment over the longitudinal mid-point of said seating surface for connecting said backrest to said connection members, said pivotal attachment means permitting said backrest to be pivoted between a first position in which said backrest extends in a generally horizontal forward projecting position adapted to support a rearward facing seated user's back when in the walker configuration and a second position in which said backrest extends in a generally horizontal rearward projecting position adapted to support a forward facing seated user's back when in the transport chair configuration, and stop means for selectively retaining said backrest in said first or second position. The backrest connection members are preferably connected to said push handle assemblies and is a strap formed of a flexible plastic material with said attachment means integrally moulded at the ends thereof. In a preferred embodiment, the walker/transport chair includes a cross-bar member extending transversely between the lower ends of said front leg members, the cross-bar member having a central portion thereof that is disposed substantially in vertical alignment with the front edge of the seating surface. The cross-bar may include integrally moulded end fittings extending forward of the lower end of said forward leg members, and wherein each of said front wheels is rotatably mounted in a caster type fork assembly having a vertically disposed mounting shaft, said mounting shaft being rotatably received in said end fitting.
[0016] In a preferred embodiment, the walker/transport chair may include a footrest member mounted for pivotal movement between a stowed position transversely disposed between said front leg members and a deployed position projecting forward of the lower ends of said front leg members for supporting a forward facing seated user's feet when in the transport chair configuration.
[0017] In accordance with another aspect of the invention, there is provided an apparatus for actuating a brake of a wheeled vehicle comprising a housing, a brake lever having a forward end retained in said housing and a handle projecting from the rear of said housing, and manually operable between a neutral position, a raised brake actuating position and a depressed brake locking position, said brake lever having a first pivot means and a first abutment surface located near the forward end of said brake lever, and a second pivot means and a second abutment surface located intermediate the forward end and the handle of said brake lever; whereby when said handle is raised from said neutral position to said brake actuating position said brake lever pivots about said first pivot means and said second abutment surface is moved to a raised position and when said handle is depressed from said neutral position to said brake locking position said brake lever pivots about said second pivot means and said first abutment surface is moved to a raised position, a brake actuating slide member retained in said housing having a third abutment surface in opposed relation with said first abutment surface whereby said upward movement thereof moves said slide upward along said axis and having a fourth abutment surface in opposed relation with said second abutment surface whereby said upward movement thereof moves said slide upward along said axis.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] [0018]FIG. 1 is a front right perspective view of the walker/transport chair of the present invention with the back rest in the walker position;
[0019] [0019]FIG. 2 is a right side view of the walker/transport chair of the present invention with the back rest in the walker position;
[0020] [0020]FIG. 3 is a plan view of the walker/transport chair of the present invention with the back rest in the walker position;
[0021] [0021]FIG. 4 is a right side view of the walker/transport chair of the present invention with the back rest in the transport chair position;
[0022] [0022]FIG. 5 is a plan view of the walker/transport chair of the present invention with the back rest in the transport chair position;
[0023] [0023]FIG. 6 is a right side view of the back rest extension arm;
[0024] [0024]FIG. 7 is a left side view the back rest extension arm;
[0025] [0025]FIG. 8 is a perspective view showing the manner in which the backrest is connected to the extension arms;
[0026] [0026]FIG. 9 is a front view of the cross-bar member;
[0027] [0027]FIG. 10 is a top plan view of the cross-bar member;
[0028] [0028]FIG. 11 is a right side view in partial section of the cross-bar member connection details;
[0029] [0029]FIG. 12 is a side view of the inside of the right brake housing half;
[0030] [0030]FIG. 13 is a side view of the inside of the left brake housing half;
[0031] [0031]FIG. 14 is a left side view of the brake actuator slide;
[0032] [0032]FIG. 15 is a rear view of the brake actuator slide;
[0033] [0033]FIG. 16 is a right side view of the brake actuator slide;
[0034] [0034]FIG. 17 is a side view of the inside of the right brake housing half showing the position of the brake actuator slide;
[0035] [0035]FIG. 18 is a left side view of the brake lever;
[0036] [0036]FIG. 19 is a right side view of the brake lever;
[0037] [0037]FIG. 20 is a side view of the inside of the left brake housing half showing the brake lever in the neutral position;
[0038] [0038]FIG. 21 is a side view of the inside of the left brake housing half showing the brake lever in the depressed brake locking position;
[0039] [0039]FIG. 22 is a side view of the inside of the left brake housing half showing the brake lever and the brake actuator slide in the neutral position;
[0040] [0040]FIG. 23 is a side view of the inside of the left brake housing half showing the brake lever and the brake actuator slide in the raised brake actuating position;
[0041] [0041]FIG. 24 is a side view of the inside of the left brake housing half showing the brake lever in the depressed brake locking position;
[0042] [0042]FIG. 25 is a right side view in partial section of the internal brake actuating mechanism of the present invention;
[0043] [0043]FIG. 26 is a perspective view of the brake wire clamp;
[0044] [0044]FIG. 27 is a right side view, in partial section showing the brake shoe connection details;
[0045] [0045]FIG. 28 is a perspective view of the brake shoe;
[0046] [0046]FIG. 29 is a side view of the brake shoe showing the position of the friction member;
[0047] [0047]FIG. 30 is a perspective view of the friction member.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0048] Referring to FIGS. 1 to 3 , there is shown a perspective view of walker/transport chair 10 in the walker configuration. Walker/transport chair 10 has a pair of forward leg members 12 , a pair or rearward leg members 16 , and a U-shaped transverse seat support member 20 . Front leg members 12 are fixedly secured at their upper ends to front leg brackets 22 and rear leg members 16 are fixedly attached at their upper ends to rear leg brackets 26 . Front leg brackets 22 are pivotally attached to rear leg brackets 26 at pivot pins 30 . In the open or operative position shown in FIGS. 1 to 3 , abutment surfaces 32 at the upper ends of front leg brackets 22 engage the forward lower edge of seat support member 20 when forward leg members 12 are in the open and weight bearing position. Front leg brackets 22 permit the front leg members 12 to be folded toward rear leg members 16 in order to collapse walker/transport chair 10 into a more compact configuration, for example for placement in the trunk of a car.
[0049] Walker/transport chair 10 is locked in the open position by means of lock rod 73 which engages projections 75 on front leg brackets 22 . Handle 77 is rotatably mounted about transverse seat support member 20 for moving lock rod 73 out of engagement with projections 75 . Handle opening 36 is provided in seating surface 34 to provide easy access to handle 77 .
[0050] Seating surface 34 is horizontally supported at its forward edge 90 by transverse seat support member 20 and provides a stable seating platform. Seating surface 34 is pivotally attached to transverse seat support member 20 such that it can be flipped to a vertical position by pulling up on rear edge 71 . This position is particularly useful when the user wishes to move as far forward as possible, for example when reaching ahead of the walker/transport chair to remove objects from a cupboard.
[0051] Front leg members 12 are stabilized by cross-bar member 68 which extends horizontally between front leg members 12 and is fixedly secured to the bottom ends of front leg members 12 at end fittings 40 . Front wheels 38 are mounted on front fork assemblies having a vertical axle shaft carried in a bearing assembly (not shown) in each end fitting 46 for rotation about the vertical axis to permit front wheels 38 to caster for ease of steering walker/transport chair 10 .
[0052] Rear wheels 42 are carried at the lower ends of rear leg members 16 on rear fork assemblies 44 . Rear fork assemblies 44 are fixedly connected to the lower ends of rear leg members 16 .
[0053] Push handle assemblies 50 are fixedly attached to the upper ends of telescopic tubes 52 which are slidably received in rear leg members 16 . The height of push handle assemblies 50 can be adjusted by extending or retracting telescopic tubes 52 in rear leg members 16 . Telescopic tubes 52 have a series of through holes at uniform spacings along their length through which thumb screws 54 can be selectively inserted to fix push handle assemblies 50 at the desired height.
[0054] Push handle assemblies 50 comprise handgrips 60 , handle housings 62 and brake levers 64 . Brake levers 64 are operatively connected to brake shoes 66 by length adjustable rod assemblies housed within telescopic tubes 52 and rear leg members 16 . Movement of brake levers 64 will cause brake shoes 66 to move into braking engagement with the tread of rear wheels 42 thereby arresting rolling motion.
[0055] When walker/transport chair 10 is in the walker configuration as shown in FIGS. 1 to 3 , the user positions himself behind walker/transport chair 10 , and between push handle assemblies 50 facing the forward direction. In order to function as an effective walker, it is desirable that the geometry of the walker be such that the user can position himself far enough forward that his centre of gravity is vertically aligned over handgrips 60 . This will permit the user to support a substantial portion of his weight on handgrips 60 when desirable to reduce the weight on the feet. In order to ensure stability of the walker when a substantial vertical load is placed on handgrips 60 , the handgrips must be positioned forward of the point of ground contact of rear wheels 42 . Moreover, in order to facilitate walking, there must be sufficient room in front of the user to permit him to extend his feet forward in a natural walking gait without interfering with tile walker structure, and in particular with the seating surface. Accordingly, the position of seating surface 34 is biased to the front of walker/transport chair 10 such that its rear edge 71 is forward of handgrips 60 . In addition, seating surface 34 can be flipped to a vertical position about transverse seat support member 20 as described above. This will provide the user with additional space to move forward between push handle assemblies 50 if desired.
[0056] When the user wishes to rest, he simply turns around between push handle assemblies 50 , using liandgrips 60 for support if required, and sits down on seating surface 34 , with his feet on the ground. Backrest 70 is provided to support the user's back while seated on walker/transport chair 10 . Backrest 70 is attached to extension arms 72 which are fixed at their rearward ends to push handle assemblies 50 .
[0057] [0057]FIGS. 6, 7 and 8 show the details of extension arms 72 and the manner in which backrest 70 is attached to extension arms 72 . Extension arms 72 each have an inward facing partannular recess 96 with a central cylindrical bore 98 formed therethrough. Backrest 70 has formed therein two mounting points 100 and 102 for attachment to extension arm 72 . Mounting point 100 can be used as the point of attachment for a larger user whereas mounting point 102 effectively shortens the length of backrest 72 for a smaller user. The configuration of mounting points 100 and 102 is identical and will be described with reference to point 102 which is visible in FIG. 8.
[0058] Backrest 70 is formed of a flexible plastic material and at each end has a connection piece 80 . Backrest 70 and connection piece 80 can be unitarily moulded of a suitable plastic material that has sufficient flexibility in the central back-supporting area to conform to and support a user's back and sufficient mechanical strength to function as a connection piece. In the alternative, backrest 70 and connection piece 80 can be separate components joined together. Moreover, backrest 70 can be formed of a rigid material such as aluminum if a non-flexible backstrap type backrest is desired. Connection piece 80 has all outwardly projecting key type lug 82 and a central bore 84 formed therethrough. Part-annular recess 96 in extension arm 72 is sized to fit over and closely receive key type lug 82 on backrest 70 with the cylindrical bores 84 and 98 axially aligned. A suitable bolt (not shown) with a smooth shank passes through cylindrical bores 84 and 98 and is fastened with a captive nut (not shown) located in hex-head recess 86 in connection piece 80 . In this manner, backrest 70 is pivotally connected to extension arms 72 .
[0059] Stop lug 104 projects inwardly of recess 96 in extension arm 72 . Abutment surface 106 on stop lug 104 limits forward rotation of backrest 70 by contacting key type lug 82 in connection piece 80 and maintains backrest 70 in the forward facing horizontal position. Similarly, abutment surface 108 limits rotation of backrest 70 by contacting key type lug 82 in connection piece 80 and maintains backrest 70 in the rearward facing horizontal position. This arrangement permits backrest 70 to be manually flipped from the forwardly extending position shown in FIGS. 1 to 3 for use in the walker mode, to the rearwardly facing position, shown in FIGS. 4 and 5 for use in the transport chair mode.
[0060] When walker/transport chair 10 is in the transport chair configuration, the user or a care-giver flips backrest 70 to the rearward extending position as shown in FIGS. 4 and 5. The user positions himself in front of and facing away from walker/transport chair 10 and sits down on seating surface 34 with his back against backrest 70 . Footrest 72 is then folded from the stowed position shown in FIGS. 2 and 3 to the deployed position shown in FIGS. 4 and 5. The user rests his heels on footrest tray 76 and in that position can be comfortably propelled by the care-giver in the transport chair mode. (Footrest 72 has been omitted from FIG. 1 to show greater detail of cross-bar 68 ). The forward facing seated position is not only useful when the apparatus is being propelled by a care-giver in the transport chair mode, but also permits the apparatus to be positioned close to a table, for example when eating a meal. Conventional walkers in which the user is seated in the rearward facing position are not well suited to this application because the rearward projecting handgrips and the rear wheels limit how close the walker can be placed, while the seating surface is typically positioned far forward of the hangrips.
[0061] Conventional walkers usually require a cross-bar between the front leg members to strengthen the frame against collapse when the walker is bearing substantial weight, for example, when the user is seated. A front cross-bar is particularly required where the front leg members are pivotally attached to the frame to permit folding, which pivotal attachment provides little resistance to outward splaying of the legs under load.
[0062] For conventional walkers, the presence of a cross-bar between the front legs of the walker typically does not interfere with the user's movements, as the user is positioned behind the walker in both the walking and sitting positions. However, the front cross-bar on a conventional walker interferes with its use as a transport chair. In particular, in order to assume the forward facing sitting position in the transport chair mode, a user must be able to position his heels very close to a point on the ground directly under the front edge of the seating surface. If the user is positioned too far forwards, he tends to lose balance when attempting to assume the seated position, falling backward in an uncontrolled manner onto the seating surface. This can cause the walker to upset resulting in serious injury to the user. Conventional cross-bars are usually positioned well forward of the front edge of the seating surface and accordingly tend to prevent a user from positioning his heels close to a point on the ground directly under the front edge of seating surface.
[0063] The walker/transport chair design of the present invention is configured to overcome the limitations of conventional walker frame design. First, as seen in FIG. 1 front leg members 12 are positioned at an angle closer to vertical than are most conventional walkers. This minimizes the extent to which the lower ends of front leg members 12 , and consequently cross-bar 72 , project forward of the forward edge 90 of seating surface 34 . However, this has the undesirable effect of shortening the wheelbase and lessening stability. In order to provide for a lengthened wheelbase, the front fork assemblies 48 are not secured axially inside the lower end of front legs 12 as is conventional practice in walker design. Instead, front fork assemblies 48 are secured in end fittings 40 which project forwardly from the lower end of leg members 12 , effectively lengthening the wheelbase.
[0064] Another feature of the present invention that enhances its use as a transport chair is the design of cross-bar 68 . As best shown in FIGS. 4 and 5, cross-bar 68 attaches to front leg members 12 at their lower ends, which point is forward of the forward edge 90 of seating surface 34 . In order to permit the user to more safely assume the forward-facing seated transport chair position, cross-bar 68 is rearwardly curved such that its central portion is located substantially under the forward edge 90 of seating surface 34 . This curved cross-bar arrangement permits the user to place his heels close to a point on the ground directly under the front edge of seating surface, and thereby. While a curved geometry is shown in the drawings, other configurations could be used so long as the cross-bar is configured such that its central portion is located substantially under or behind the forward edge 90 of seating surface 34 .
[0065] Construction details of cross-bar 68 and end fittings 40 can be seen in FIGS. 9 to 11 . Cross-bar 68 and end fittings 40 are unitarily moulded or cast from a material of suitable strength. For example cross-bar 68 can advantageously be formed of cast aluminum. Cylindrical bores 120 are provided in cross-bar 68 to receive connector piece 122 which is bolted into the lower ends of forward leg member 12 . Front fork shaft 124 is vertically received in bore 126 and is rotatable retained by upper and lower bearings 128 fitted in bore 126 .
[0066] As noted above, the front fork assemblies of conventional walkers are typically inserted directly into the hollow ends of the leg members. The fork mounting shaft is usually carried in a single bearing which is press-fitted into the bottom end of the leg member. This arrangement is prone to failure. In particular, repetitive striking of the wheels into curbs and other obstacles and impact over rough road surfaces has a tendency to deform and widen the lower end of the leg members into which the bearing is pressed. This can cause the bearing, and the entire fork/wheel assembly to fall out of the bottom of the leg member. By mounting the front fork assemblies 48 to end fittings 40 fitted with two bearings, rather than directly into a single bearing in the bottom end of the leg, the ability of the fork assemblies and the lower leg mounting hardware to absorb shock, without failure is greatly improved.
[0067] The design of the walker/transport chair 10 permits the use of a novel and effective braking system. Conventional walkers use Bowden cables which extend from the hand grip mounted brake levers to the braking wheels. Bowden cables are relatively inexpensive and because they are flexible, can be installed with excess length in a free standing loop or bight to accommodate changes in length occasioned by the adjustment of handgrip height. However, the use of a Bowden cable arrangement has a number of disadvantages. The same free standing loop or bight that permits handgrip height adjustability is prone to being caught or hooked on various obstructions, particularly when the walker is loaded into, or unloaded from the trunk of a car. In addition, Bowden cables must be accurately adjusted and even a slight lack of adjustment can cause unsatisfactory braking action.
[0068] The design of the present invention permits the use of an internal brake actuating mechanism. Referring to FIGS. 12 and 13, handle housing 62 comprises right side housing shell 200 and left side housing shell 202 which are bolted at their lower ends to telescopic tube 52 . Hand grip 60 is bolted between right side housing shell 200 and left side housing shell 202 at their upper ends. Brake lever 64 is retained between right side housing shell 200 and left side housing shell 202 in the manner described below.
[0069] Referring to FIG. 12, the inside face of right side housing shell 200 is shown. Raised wall 204 forms an elongated groove 206 on the inside face with a longitudinal axis that is parallel to telescopic lube 52 . Semicircular bearing surfaces 208 are formed in the lower portion of the inside face.
[0070] Referring to FIGS. 14 to 16 , brake actuator 210 has raised tongue portion 212 which is sized to be slidably retained in elongated groove 206 of right side housing shell 200 and cylindrical portion 214 which is sized to be slidably retained in semicircular bearing surfaces 208 of right side housing shell 200 .
[0071] [0071]FIG. 17 shows the position of brake actuator 210 when it is slidably received in right side housing shell 200 . Bias spring 218 is carried between retaining lug 216 formed at the upper end of brake actuator 210 and stop wall 220 formed at the upper end of groove 206 and biases brake actuator 210 in the downward direction. Brake actuator 210 has elongated aperture 215 formed through cylindrical portion 214 . This elongated aperture 215 permits cylindrical portion 214 to extend down into telescopic tube 52 and allow bolts to pass through bolt holes 217 in right side housing shell 200 , telescopic tube 52 , elongated aperture 215 , telescopic tube 52 and bolt holes 217 in left side housing shell without interfering with the vertical sliding motion of brake actuator 210 . Such a through-bolting arrangement greatly improves the mechanical strength of the attachment of push handle assemblies 50 to telescopic tubes 52 .
[0072] Referring to FIGS. 18 and 19, brake lever 64 comprises upper arm 220 and lower arm 222 joined at their rear extremities by ball shaped gripping projection 224 . Brake lever 64 is shaped such that braking action, as more completely described below, can be effected by placing the hands on handle grips 50 , inserting fingers through opening 226 and pulling up on upper arm 220 with inward gripping action. Downward pressure on lower arm 222 will move brake lever 64 downward into a locked or “parked” position, also as more completely described below. Ball shaped gripping projection 224 assists in moving brake lever in a downward direction by enabling the user to hook a thumb over the projection to apply downward force. This is particularly useful for a user with strength or mobility limitations in the hands.
[0073] Pivot pin 228 projects from the left side of brake lever 64 at its forward end and is sized to be received in slot 230 formed in the inside surface of left side housing shell 202 . Brake actuating lug 232 projects from the right side of brake lever 64 and its upper surface engages downward facing abutment surface 234 formed in brake actuator 210 . Camming lug 236 projects from the left side of brake lever 64 . Brake lock actuating lug 238 projects from the right side of brake lever 64 at its forward end opposite pivot pin 228 .
[0074] Referring to FIGS. 20 and 22, brake lever 64 is shown in the neutral position when no manual braking action is applied. In this position, the brake lever 64 projects rearwardly in a direction slightly below horizontal. Pivot pin 228 rests at the bottom of slot 230 in left side housing shell 202 and camming lug 236 (shown in phantom lines) rests on upward facing abutment surface 240 formed on the inside surface of left side housing shell 202 . Brake lever 64 is retained in this position by the downward pressure of bias spring 218 acting on brake actuator 210 , as can be seen with reference to FIG. 17.
[0075] Downward facing abutment surface 242 (shown in phantom lines) formed in brake actuator 210 abuts the upper surface of brake lock actuating lug 238 (shown in phantom lines) formed in brake lever 64 and the downward action of bias spring 218 on brake actuator 210 urges pivot pin 228 to the bottom of slot 230 . Similarly, downward facing abutment surface 234 (shown in phantom lines) formed in brake actuator 210 abuts the upper surface of brake actuating lug 232 (shown in phantom lines) formed in brake lever 64 and the downward action of bias spring 218 on brake actuator 210 urges camming lug 236 into engagement with upward facing abutment surface 240 .
[0076] Thus in the neutral position as shown in FIGS. 20 and 22, brake lever 64 rests with pivot pin 228 at the bottom of slot 230 and camming lug 236 resting on upward facing abutment surface 240 . Brake actuator 210 is urged downwardly by bias spring 218 and rests with downward facing abutment surface 242 resting on brake lock actuating lug 238 and downward facing abutment surface 234 resting on brake actuating lug 232 .
[0077] Referring to FIG. 23, brake lever 64 is shown in the braking position when manual braking action is applied. In this position, the brake lever 64 has been pivoted about pivot pin 228 in the bottom of slot 230 until the upper arm 220 of brake lever 64 is substantially horizontal. This pivoting action causes brake actuating lug 232 (shown in phantom lines) to raise brake actuator 210 by engagement with downward facing abutment surface 234 (shown in phantom lines). By manually releasing brake lever 64 , bias spring 218 will urge brake actuator 210 back to the neutral position shown in FIG. 13. The upward motion of brake actuator 210 between the neutral and braking positions is transmitted to rear wheel brake shoes 66 in a manner described below.
[0078] Referring to FIGS. 21 and 24, brake lever 64 is shown in the locked or “park” position. In this position, brake lever 64 has been pivoted down about camming lug 236 (shown in FIG. 21 in phantom lines). This pivoting motion causes pivot pin 228 to move upward in slot 230 and draws camming lug 236 forward over upward facing abutment surface 240 onto lower abutment surface 246 .
[0079] As can be seen with reference to FIG. 24, this pivoting motion causes brake lock actuating lug 238 (shown in phantom lines) to raise brake actuator 210 by engagement with downward facing abutment surface 242 (shown in phantom lines). Brake lever 64 is retained in this locked or “park” position by the downward pressure of bias spring 218 acting on brake actuator 210 which urges camming lug 236 backwards into engagement with forward facing abutment surface 248 . Downward bias is also provided by spring 290 (see FIG. 27). By applying manual pressure to raise brake lever 64 , camming lug 236 is raised over forward facing abutment surface 248 and returns to the neutral position shown in FIG. 22. Thus, the sliding movement of camming lug 236 over forward facing abutment surface 248 provides an overcentre action to lock and unlock brake lever 64 . The upward motion of brake actuator 210 between the neutral and lock or “park” positions is transmitted to rear wheel brake shoes 66 , as described below.
[0080] As is evident from the foregoing description, the user can apply and release a braking force to the walker by pulling up and releasing brake lever 64 , and can apply a constant braking force by pushing brake lever 64 down into the locked or “park” position.
[0081] Referring now to FIG. 25, the manner in which the upward motion of brake actuator 210 is transmitted to rear wheel brake shoe 66 is shown. Brake actuator 210 is bolted in the upper end of telescopic tube 52 as described above. Telescopic tube 52 is slidably received inside rear leg member 16 . Rear leg member 16 is fixedly attached to fixed rear leg bracket 26 in a manner that leaves the inside volume of rear leg member 16 open to permit telescopic tube 52 to slide therein. For example, bosses having threaded sockets can be provided on the outer surface of rear leg member 16 and corresponding keyway can be formed in fixed rear leg bracket 26 to receive such bosses. Leg 16 and bracket 26 can then be secured by bolting through an aperture in the keyway into the threaded sockets.
[0082] Telescopic tube 52 is provided with a series of evenly spaced holes 254 along a portion of its length. Fixed rear leg bracket 26 has a transverse bore 256 formed in each side, with the inner bore being internally threaded to receive the threaded end of thumb screw 54 (see FIG. 1). Handgrip assembly 50 may be fixed at the desired height by aligning a selected hole 254 in telescopic tube 52 with bore 256 in bracket 26 . Thumb screw 54 is inserted into the outer bore 256 of bracket 26 , through the selected hole 254 in telescopic tube 52 , and is screwed into the threaded inner bore 256 on the opposite side of bracket 26 .
[0083] This arrangement provides for a secure manner of adjustably attaching handgrip assembly 50 to the fixed rear leg bracket 26 of the walker. The use of thumb screw 54 which passes entirely through telescopic tube 52 and is threaded into the opposite side of bracket 26 distributes the load applied by the user on handgrip assemblies 50 evenly across bracket 26 . This is a far more durable means of attachment than that one which merely secures the telescopic tube by a thumbscrew which passes through one wall of the bracket and squeezes against the outer surface of the telescopic tube. A solid attachment between the telescopic tube 52 and bracket 26 is extremely important not only for reasons of durability and safety, but also because of the sense of security imparted to the user. Users are far less willing to accept a walker if the handgrip assemblies feel loose or flimsily mounted. While the through-bolt arrangement of thumbscrew 54 does offer enhanced durability, it does requires a special arrangement to permit brake actuation internally within telescopic tube 52 .
[0084] Referring to FIG. 25, brake wire 250 is formed in an inverted “U” shape with its bight at its upper end being retained in groove 252 formed in the cylindrical portion 214 of actuator 210 . Downwardly extending legs 258 and 260 of brake wire 250 are attached to brake rod 262 by means of clamp 264 . Brake rod 262 is an elongated “U” shaped channel member.
[0085] Referring to FIG. 26, clamp 264 has back surface 268 and side surfaces 270 which are sized to be closely received in the “U” channel of brake rod 262 . Recesses 272 are provided to accommodate downwardly extending legs 258 and 260 of brake wire 250 and teeth 274 are formed in recesses 272 to grip brake wire 250 . Clamp 264 is drawn tight against the upper end of brake rod 262 by means of Allen screw 266 and teeth 274 trap and secure brake wire 250 to brake rod 262 . Allen screw 266 is axially aligned with the first hole 254 in telescopic tube 52 above bracket 26 permitting a wrench or key to be inserted therethrough for the purpose of loosening or tightening clamp 264 . Brake wire 250 can advantageously be formed of wound steel piano wire (e.g. 0.09 inch diameter) as the ridged surface thereof can be securely gripped by teeth 274 .
[0086] Elongated slot 276 is formed in the centre web of brake rod 262 . Thumbscrew 54 which is threaded into transverse bore 256 passes through slot 276 . Slot 276 is sized as to permit brake rod 262 to be displaced longitudinally by the upward and downward movement of brake actuator 210 without contacting thumbscrew 54 .
[0087] In order to adjust the height of handgrip assemblies 50 , a key or wrench is inserted through hole 254 above bracket 26 and Allen screw 266 is loosened to permit relative longitudinal movement between brake wire 250 and brake rod 262 . Thumb screw 54 is then unscrewed and withdrawn from transverse bore 256 . Telescopic tube is then raised or lowered until the desired hole 254 is axially aligned with transverse bore 256 and thumbscrew 54 is reinserted and tightened to secure telescopic tube 52 in bracket 26 . Finally, Allen screw 266 is tightened to secure brake wire 250 to brake rod 262 .
[0088] Referring to FIG. 27, rear fork assembly 44 comprises inner and outer fork housings 280 (only one of which is shown in FIG. 20) between which rear wheel 42 is mounted for rotation about axle 282 . Rear fork assembly 44 is attached to rear leg member 16 by means of through-bolts (not shown) which pass through holes 283 in the fork housings and rear leg member 16 . Brake shoe 66 is pivotally mounted on shaft 284 which is transversely secured between fork housings 280 . Brake rod 262 is connected at its bottom end to brake shoe 66 at pivot point 286 . Elongated slot 288 is provided in the centre web of brake rod 262 to permit the through-bolts to pass therethrough and is sized to permit brake rod 262 to be displaced longitudinally by the upward and downward movement of brake actuator 210 without contacting the through-bolts. Spring 290 is retained between lug 292 and housing 280 and biases brake shoe out of engagement with rear wheel 42 .
[0089] Referring to FIGS. 28 to 30 , the details of brake shoe 66 can be more readily seen. Brake shoe 66 has a horizontally disposed upper surface 294 an vertical sidewalls 296 which together bound a downwardly open cavity. Friction member 294 is carried within said cavity and is attached thereto at point 300 . Friction member 294 has downwardly protruding tang 302 at its rearward end. Adjusting screw 304 is threaded through the upper surface 294 of brake shoe 66 and contacts the upper surface of friction member 294 . The extent to which tang 302 protrudes below brake shoe 66 can be varied by turning adjusting screw 304 in or out. This adjustability permits fine tuning of the braking action and compensates for tire wear.
[0090] When brake rod 262 is moved upwardly by the operation of brake lever 64 , brake shoe 66 is caused to pivot about shaft 284 forcing tang 302 downward into frictional engagement with rear wheel 42 . When brake lever 64 is released and returns to its neutral position, brake rod 262 moves downwardly and brake shoe 66 pivots out of frictional engagement with rear wheel 42 . In this manner, braking action is transmitted from brake lever 64 to brake shoe 66 internally of telescopic tube 52 and rear leg member 16 .
[0091] While the present invention has been described with reference to the embodiments disclosed in the Figures, it will be understood that variations and modifications may be made without necessarily departing from the scope of the invention. Accordingly, the scope of the invention is to be determined in accordance with the claims appended hereto.
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A wheeled walker convertible to a transport chair. The walker has a strap-type backrest that is pivotally attached to the upper end of the handlebars. The backrest can be placed in a forward position when the apparatus is used as a walker and the user wishes to rest in a rearward facing sitting position and in a rearward position when the apparatus is used as a transport chair and the user sits in a forward facing position and is propelled by a care-giver. A novel braking system locates the brake actuating linkage inside the leg and handlebar members and provides accommodates extension height adjustment of the handlebars. A brake lever system providing a linear pull non-cable brake actuation is also disclosed.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U. S. Provisional Application No. 60/735,925 , filed Nov. 10, 2005 , which is incorporated herein by reference.
INCORPORATION BY REFERENCE OF SEQUENCE LISTING
A sequence listing submitted as a text file via EFS-Web is incorporated Herein by reference. The text file containing the sequence listing is named “PB 050538F_Sequence _List_Final. txt”; its date of creation is Nov. 8, 2006; and its size is 10,855 bytes.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention provides comprehensive compositions for treating The problems associated with hair graying and balding via the incorporation of: (i) Cell growth factor of HSCF to induce the migration of melanocyte stem cells and keratinocyte stem cells and then to increase the growth of melanocytes and keratinocytes in hair follicles, (ii) a formula of amino acids and vitamins to provide the nutritional factors for hair growth and pigmentation, and (iii) minoxidil to enhance the function of HSCF on hair re-growth. The compositions comprising at least one of (i), (ii) or (iii) are administered on skin and/or scalp through the liposome in the follicular delivery systems, including penetration enhancers and suitable carrier bases. The composition packaged in liposome in the follicular delivery systems of this invention has been proven to reach the dermis from the skin surface within 15-30 min. The essential function of the liposome is to maintain the activity of the growth factor of HSCF for at least one to three years.
2. Description of the Prior Art
Dual therapies of hair graying and balding in topical delivery systems have never been claimed in the market. When a graying hair derives in large part from a mixture of pigmented and white hair, it can clearly be noted that individual hair follicles indeed exhibit pigment dilution or true graying. This dilution could be due to a reduction in tyrosinase activity of hair bulbar melanocytes, sub-optimal melanocyte-cortical keratinocyte interaction, or defective migration of melanocytes from a reservoir in the upper outer root sheath to the pigment-permitting microenvironment close to dermal papilla of the hair bulb (12) . Some studies have reported that stem cell factor (SCF) has the functions to proliferate and migrate to the melanoblasts and keratinoblasts restored in the upper outer root sheath, called hair bulge (1, 2) . These melanoblasts and keratinoblasts, called melanocyte and keratinocyte stem cells, respectively, in hair bulge, could proliferate and migrate to dermal papilla in hair bulb and then differentiate to become melanocytes and keratinocytes (12, 13, 14) . Hair pigmentation is mostly produced by melanin accumulation, which is secreted from melanocytes (12, 16) . And hair shaft is mostly produced by keratin accumulation, which is secreted from keratinocytes. This growth factor of SCF has been proven to stimulate stem cells in hair bulge (3, 6, 9) . However, mice with homozygous SCF gene mutation (SL − /SL − ) show the symptoms of white hair, infertility, and anemia (1, 5) . It suggests the importance of SCF in hair pigmentation (7, 13) , but effects on hair growth are limited because the mutated mice still have hair. In addition, many growth factors and signals through different pathways control the hair growth. Especially, insulin-like growth factor-I (IGF-I) has been reported to induce growth of hair in many papers (4, 15) . Based on our previous data, the same results have also been obtained. Although the amino acid sequence and protein structure of recombinant human SCF has been clearly studied (17) and also been applied as a patent (U.S. Patent Publication No.: 20050080250, application Ser. No. 10/620,642, filed: Jul. 16, 2003. Methods of stimulating growth of stromal cells in a human.), SCF and other ingredients are incorporated to claim the dual therapies for hair aging in our experimental data.
The combination of the two growth factors, SCF and IGF-I, has been studied to have the more advanced functions on the hair follicles in our study, because it significantly stimulates the hair growth and melanin synthesis at the same time. We gave the definition of the two growth factors of SCF and IGF-I as HSCF (hair stem cell factor), meaning either the combination, named HSCF-I, or the recombinant protein, named HSCF-II. The recombinant protein of HSCF-II is first established by our group, which is produced by a cloning vector inserted with a combination of human SCF and IGF-I sequence together. The medium containing HSCF results in a higher increase of shaft length of mouse hair follicles cultured in vitro, when compared with SCF or IGF-I alone. After the above compositions are administered along with a hair follicular delivery vehicle and/or device on the skin of mice, longer hair length and darker pigmentation of hair shaft are obtained.
Minoxidil, being a potassium channel opener, has been proven to induce human hair growth from many papers and is popular in the market to treat patients with androgenic alopecia. But the effects of minoxidil on treating hair balding are still limited (10) . The functions of minoxidil could reduce continuous hair loss, but couldn't increase hair amount and density or recover the pigment of graying hair. We tried to amplify the function of minoxidil by adding the above compositions, because it has been proven by the inventors of this invention that HSCF could stimulate the stem cells in hair bulge to migrate into hair bulb, and then differentiate to melanocyte and keratinocyte to regenerate a newly pigmented hair in a hair follicle.
The results showed that compositions of (i) HSCF, (ii) a formula of some amino acids and vitamins, and (iii) minoxidil could achieve the best efficiency on hair growth and melanin synthesis. It also has been proven to treat the graying and balding problems by the in vitro culture of hair follicle organ and also by the in vivo animal models of graying and balding mice. The invention could be further applied to treat the hair aging of human beings.
REFERENCE
1. Broudy, V. C. (1997) Stem cell factor and hematopoiesis. Blood 90:1345-1364.
2. Botchkareva, N. V., M. Khlgatian, B. J. Longley, V. A. Botchkarev, B. A. Gilchrest, 2001. SCF/c-KIT signaling is required for cyclic regeneration of the hair pigmentation unit. FASEB J. 15(3):645-658.
3. Botchkareva, N. V., V. A. Botchkarev, B. A. Gilchrest. 2003. Fate of melanocytes during development of the hair follicle pigmentary unit. J. Investig. Dermatol. Symp. Proc. 8(1):76-79.
4. Frankel, S. K., B. M. Moats-Staats, C. D. Cool, M. W. Wynes, A. D. Stiles, D. W. Riches. 2005. Human insulin-like growth factor-IA expression on transgenic mice promotes adenomatous hyperplasia but not pulmonary fibrosis. Am. J. Physiol. Lung Cll Mol. Physiol. 288(5):L805-812.
5. Guyonneau, L., F. Murisier, A. Rossier, A. Moulin, F. Beermann. 2004. Melanocytes and pigmentation are affected in dopachrome tautomerase knockout mice. Mol. Cell Biol. 24:3396-3403.
6. Hemesath, T. J., E. R. Price, C. Takemoto, T. Badalian, D. E. Fisher. 1998. MAP kinase links the transcription factor microphthalmia to c-kit signaling in melanocytes. Nature 391:298-301.
7. Ito, M., Y. Kawa, H. Ono, M. Okura, T. Baba, Y. Kubao, S. I. Nishikawa, M. Mizoguchi, 1999. Removal of stem cell factor or addition of monoclonal anti-c-kit antibody induces apoptosis in murine melanocyte precursors. J. Invest. Dermatol. 112(5):796-801.
8. Jiang, X., O. Gurel, E. A. Mendiaz, G W. Stearns, C. L. Clogston, H. S. Lu, T. D. Osslund, R. S. Syed, K. E. Langley, W. A. Hendrickson. 2000. Structure of the active core of human stem cell factor and analysis of binding to its receptor kit. EMBO J. 19:3192-3203.
9. Nishimura, E. K., S. A. Jordan, H. Oshima, H. Yoshida, M. Noriyama, I. J. Jackson, Y. Barrandon, Y. Miyachi, S. I. Nishikawa. 2002. Dominant role of the niche in melanocyte stem-cell fate determination. Nature 416:854-860.
10. Mager, M., R. Pause, N. Farjo, S. Muller-Rover, E. M. J. Peters, K. Foitzik, D. J. Tobin. 2004. Limitations of human occipital scalp hair follicle organ culture for studying the effects of minoxidil as a hair growth enhancer. Exp. Dermatol. 13:635-642.
11. Mol, C. D., K. B. Lim, V. Sridhar, H. Zou, E. Y. T. Chien, B. C. Sang, J. Nowakowski, D. B. Kassel, C. N. Cronin, D .E. McRee. 2003. Structure of a c-kit product complex reveals the basis for kinase transactivation. J. Biol. Chem. 278:31461-31464.
12. Panteleyev, A. A., C. A. B. Jahoda, A. M. Christiano. 2001. Hair follicle predetermination. J. Cell Sci. 114:3419-3431.
13. Peters. E. M. J., D. J. Tobin, N. Botchkareva, M. Maurer, R. Paus. 2002. Migration of melanoblasts into the developing murine hair follicle is accompanied by transient c-Kit expression. Histochem. Cytochem. 50:751-766.
14. Peters, E. M. J., M. Maurer, V. A. Botchkarev, K. deM. Jensen, P. Welker, G. A. Scott, R. Paus. 2003. Kit is expressed by epithelial cells in vivo. J. Invest. Dermatol. 121:976-984.
15. Philpott, M. P., D. A. Sander, T. Kealey. 1994. Effects of insulin and insulin-like growth factors on cultured human hair follicles: IGF-I at physiologic concentrations is an important regulator of hair follicle growth in vitro. J. Invest. Dermatol. 102(6):857-861.
16. Sulaimon, S. S.,B. E. Kitchell. 2003. The biology of melanocytes. Vet. Dermatol. 14(2):57-65.
17. Zhang, Z., R. Zhang, A. Joachimiak, J. Schlessinger, X. P. Kong. 2000. Crystal structure of human stem cell factor: Implication for stem cell factor receptor dimerization and activation. Proc. Natl. Acad. Sci. USA 97:7732-7737.
18. Park, W. S., C. H. Lee, B. G Lee, I. S. Chang. 2003. The extract of Thujae occidentalis semen inhibited 5α-reductase and androchronogenetic alopecia of B6CBAF1/j hybrid mouse. J. Dermatol. Sci. 31:91-98.
SUMMARY OF THE INVENTION
In a first aspect, the present invention provides the compositions for dual hair therapies for balding and graying. The best composition of (i) the recombinant growth factor of HSCF, (ii) a formula of some amino acids and vitamins, and (iii) minoxidil significantly increases the degree of hair pigmentation and the length of hair shaft, not only in in vivo but also in in vitro models. In the base formula (ii), the effects of the mixture of HSCF and minoxidil are much stronger than those of HSCF (i) or minoxidil (iii) alone. It provides strong evidence for the effects of these compositions and methods for dual therapies of hair graying and balding in the follicular delivery systems.
In the invention, each of the recombinant human growth factors, including SCF, IGF-I and HSCF-II, has been cloned, expressed, and purified ( FIG. 1-6 ). The activities of these proteins have been tested in different cell lines, respectively ( FIGS. 3 , 5 ). The artificial recombinant protein of HSCF-II is first established in this invention by integrating the human SCF and IGF-I sequence together into the expressing vector. When the pET24a vector was inserted with the sequence of HSCF-II, the expressed protein also has the combined functions of both SCF and IGF-I. Moreover, it appears that the combined functions on hair follicles are even better than each of SCF and IGF-I ( FIG. 7 ). The HSCF-II possesses the benefits of being efficient, economical, and convenient. The major functions of HSCF-II on hair follicles are to induce the proliferation of melanocyte stem cells and keratinocyte stem cells, their migration from the bulge to the hair bulb, and also their differentiation into melanocytes and keratinocytes. It could revitalize the hairless follicles to regenerate pigmented hair shaft ( FIG. 8 ).
The graying animal model to mimic human hair graying is first established by our invention. It is derived from the hybrid of the C3H and BALB/C mice. The hybrid possessing the heterologous tyrosinase gene (Tyr+/Tyr−) appears in light brown color, which is the mimic to the genotype of aging human in hair follicles because of tyrosinase depletion. In fact, tyrosinase is the most important enzyme to produce melanin. If any reason causes the inactivation of tyrosinase during aging, the hair would lose its color and becomes gray. We used the whiting gel (containing 1-20% hydroquinone and 1-20% glycolic acid) on the dorsal skin of the hybrid to cause the inhibition of the tyrosinase activity. After 7 days of treatment, the hair color of the re-grown hair in the hybrid becomes white. Actually, it is very easy to observe the hair color from the graying animal model to check if these treatments indeed work. In fact, it has been proven in this invention. The compositions significantly change the hair color ( FIG. 8 ) and increase the melanin level ( FIG. 9 ) of the hair shaft in the graying animal model.
Minoxidil has been popular in the market to treat patients with androgenic alopecia for many years. It has been theoretically explained that minoxidil could be a potassium-ion channel opener on cell membrane to help with the entrance of amino acids and other nutrients. But the effects of minoxidil on treating hair balding are still limited because it can reduce continuous hair loss but not increase the hair amount, density, or the pigment of the graying hair. The compositions in this invention can indeed amplify the function of minoxidil, by the extra additions of the growth factor of HSCF and a formula of some amino acids and vitamins ( FIG. 7 and FIG. 10 d ). The function of HSCF on hair follicles is to stimulate the proliferation and migration of stem cells. And the formula supports rich nutrients to hair follicles. Since the best combination consists of three parts, it enhances not only the pigmentation of graying hair but also the regeneration of hairless follicles.
To prove the therapeutic function of these compositions on hair balding, we established the androchronogenetic alopecia (AGA) animal model, which was modified from a paper by Park et al. (18) . It is derived from the hybrid of C57BL/6J female×CBA/J male, and is called B6CBAF1/j hybrid. It has been proved that hair loss of the female of the hybrid can be induced by the subcutaneous injection of testosterone (1-100 mg/mice/day) for 3 weeks. Thus, the AGA animal model is the human AGA mimic. From the in vivo data ( FIG. 10 ), it strongly suggests that even HSCF alone has the function to improve hair re-growth in the AGA mice. Moreover, the combination of HSCF and minoxidil has more efficacy in treating hair loss in the AGA mice, which re-grows hair more quickly. The result also shows that the mixture has the best efficacy in the hair growth of the hair follicle cultured in vitro ( FIG. 7 ). In summary, the effect of the mixture on hair re-growth in the follicles is significantly better than minoxidil alone.
These compositions which are topically applied to the graying and AGA animal models through the follicular delivery systems should be packaged in liposome to preserve their activities, especially for the HSCF protein. The follicular delivery systems include penetration enhancers and suitable carrier bases. The term “penetration enhancers” as used herein means a compound that facilitates the movement of substances into and/or through the epidermis of skin. Examples of penetration enhancers include, but are not limited to, lipids, lipoproteins, fatty acids and fatty alcohol, detergents, alcohols, glycols, mineral oils, liposome, and transdermal delivery vehicles or devices. And the term “suitable carrier” as used herein means a carrier suitable for the topical application to mammalian skin without causing undue toxicity, irritation, allergic response, and the like. The addition of penetration enhancers and suitable carrier bases in the follicular delivery systems contribute to the most effectiveness on the dermis through the topical applications. We have proven that the penetration rate is limited to 15-30 min to reach the dermis from the skin application by the liposome of the follicular delivery system. It showed on the immunofluorescence of the liposome ( FIG. 11 a ), the sizes of which are limited to 50 nm-2 μm, and the frozen specimen of mice skin after 15-30 min of the topical application of the liposome packaged with these compositions ( FIG. 11 b ).
In summary, the present invention provides the compositions and methods for dual therapies of hair graying and balding. The compositions comprise (i) the growth factor of HSCF, (ii) a formula of amino acids and vitamins, and (iii) minoxidil in the topical delivery systems. The invention also provides two experimental animal models for testing the functions of the compositions on hair graying and balding in vivo. The invention further relates to dual therapeutic methods useful for treating disorders of human hair graying and balding due to aging.
These features and advantages of the present invention will be fully understood and appreciated from the following detailed description in view of the accompanying Drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 . The PCR products of human SCF, IGF-I, and HSCF-II.
FIG. 2 . The protein expression of soluble form of human SCF with results of SDS-PAGE shown in (a) and Western blot shown in (b).
FIG. 3 . The protein activity of SCF in the TF-I cell line.
FIG. 4 . The protein expression of human IGF-I. The result of SDS-PAGE is shown.
FIG. 5 . The protein activity of IGF-I in the 3T3 cell line.
FIG. 6 . The protein expression of the human HSCF-II is shown in SDS-PAGE.
FIG. 7 . The effect of IGF-I, SCF, HSCF and/or minoxidil on hair growth in vitro. (a) The whole follicle organ was dissected to culture and the length of the re-grown hair was measured from the top of the hair follicle as the beginning site (pointed by an arrow). (b) The data of hair length in the different treatments were shown. *Data of each treatment, compared with the positive control, is significantly different (P<0.05). † Data of each treatment, compared with the group of minoxidil, is significantly different (P<0.05).
FIG. 8 . The effect of HSCF on the hair color of the graying animal model. The dorsal hair color after the treatment was much darker than the control and similar to the wild type.
FIG. 9 . The effect of HSCF on the melanin synthesis of the re-grown hair on the graying animal model. The symbol * means a statistically significant difference, when compared with the control to be significant (P<0.05).
FIG. 10 . The mutant C57BL/6J with jb/jb is shown before weaning (a) and after weaning (b). The AGA animal model is shown before treatment (c) and after 14 days of the treatment (d). The numbers indicate different treatments: No. 1 is the balding mice of the control, No. 2 is the balding mice treated with HSCF and minoxidil, and No. 3 is the balding mice treated with HSCF alone.
FIG. 11 . It shows the particle size of liposome packaged with HSCF (a) and the penetration rate into the dermis (b) after 15-30 min of the topical application with immunofluorescence staining.
FIG. 12 shows the gene construction of three different stem cell factors (SCF).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Example 1
Materials and Methods
(1). Expression and Purification of Human Stem Cell Factor (SCF)
A. Gene Construction
SCF (kit ligand, mast cell growth factor, or steel factor) is encoded by the S1 locus on human chromosome 12q22-12q24. The soluble and Tran membrane forms of SCF are generated from the alternative splicing that includes or excludes a proteolytic cleavage site. Both the soluble and the transmembrane form of SCF are biologically active. SCF248 includes exon 6, which encodes a proteolytic cleavage site, resulting in the production of soluble SCF, which has 165 amino acids. The cleavage occurs after Ala. The lack of exon 6 in human SCF220 results in production of the transmembrane form of human SCF. In SCF220, amino acids 149-177 are replaced by a Gly residue. The three different SCF forms are illustrated in FIG. 12 .
The soluble form of human SCF cDNA was obtained from the total RNA of human placenta by RT-PCR. The primers were designed as SEQ. ID NO:7 and SEQ ID NO:8 as Follows:
SCF primer: F (BamHI): 5′cgggatccatgaagaagacacaaacttggattc 3′ (SEQ ID NO: 7) R (XhoI): 5′ccgctcgagaaccacacaatcactagtttcag 3′ (SEQ ID NO: 8)
The PCR cycles and products of SCF were described in FIG. 1 . The nucleotide sequence of soluble SCF cDNA (495 bp) is set forth in SEQ ID NO:1. The 165 amino acids of soluble SCF are set forth in SEQ ID NO:2.
B. Protein Expression
The protein expression of the soluble form of human SCF is shown as the results of SDS-PAGE and Western blot in FIG. 2 .
C. Protein Purification
The pET24a-SCF was transformed into expression competent BL21-codon plus E. coli cells. The cells were grown in 5 ml LB containing 35 μg/ml kanamycin in a shaking incubator at 37□ overnight. Then, 5 ml of the culture was added to 500 ml LB containing 35 μg/ml kanamycin and the culture was continued to grow in a 37° C. shaker for approximately 3 h until the OD550 reached 0.5-1. After the OD550 was around 0.5-1, protein expression was induced with isopropylthiogalactoside (IPTG) at concentration of 0.5 mM. After an incubation time of 6 h at 37° C., the cells were harvested by centrifugation and resuspended in 50 ml PBS containing 100 μg/ml lysozyme, pH 7.5. Store the suspension at 4° C. for 30 min. And then, the suspension were sonicated on ice (15×1.5 s pulses with 1 s intervals) and centrifuged for 10 min at 10000 g. The precipitate was resuspended in 50 ml IB wash buffer (20 mM Tris-HCl, pH 7.5, 10 mM EDTA, 1% Triton X-100) and centrifuged again at 10000 g for 10 min. Repeat this step three times. The supernatant was decanted and the inclusion body-containing precipitate of pET24a-SCF /BL21 codon plus was suspended in 25 ml 8 M urea buffer containing 20 mM Tris-HCl, 0.5 M NaCl, pH 7.8. Store the suspension at 4° C. for overnight to dissolve the inclusion bodies. Residual insoluble matter was removed by centrifuging at 15000 g for 30 min. The protein suspension was loaded onto a His-Bind resin column. After loading the sample, the purified protein was eluted by elute buffer (8 M urea, 20 mM Tris-HCl, 0.5 M NaCl, 0.25 M imidazole, pH 7.8). The purified protein solution was diluted with 9 volumes of rapid refolding buffer (2.5 M urea, 20 mM Tris-HCl, 0.01 mM EDTA, 2 mM GSH, 0.2 mM GSSG, 0.02% sodium azide, 0.2 M arginine, pH 8.5). After 48 h at room temperature, the mixture was concentrated ten-fold by ultrafiltration, and dialyzed against 1000 ml of refolding buffer (20 mM Tris-HCl, 0.01 mM EDTA) containing a descending gradient of urea (2-0 M) at 4° C.
D. Activity Analysis
The purified protein was prepared with PBS, 1 μl/well was transferred to microtiter plates mixed with 100 μl of TF-I cells (1×10 4 cells/ml), which had been washed three times with PBS and then re-suspended with RPMI 1640 medium containing 10% FCS and 0.08 ng/ml IL-3. The plates were incubated for 48 h, and then 10 μl of Alamarblue was added to each well, and incubated for another 4 h. After incubation, the fluorescence was monitored at 530-560 nm excitation wavelength and 590 nm emission wavelength. The assay of SCF activity in the TF-I cell line is shown in FIG. 3 .
(2) Expression and Purification of Human Insulin-like Growth Factor-I (IGF-I)
A. Gene Construction
The 210 bp DNA sequence of human IGF-I cDNA was obtained from the total RNA of human placenta by RT-PCR. The primers were designed as SEQ ID NO:9 and SEQ ID NO:10 as follows:
IGF-I primer: F (BamHI): 5′ cgggatccggaccggagacgctctgcg 3′(SEQ ID NO: 9) R (XhoI): 5′ ccgctcgagagctgacttggcaggcttga 3′(SEQ ID NO: 10)
The PCR cycles and products of IGF-I were described in FIG. 1 . The nucleotide sequence of human IGF-I cDNA (210 bp) is set forth in SEQ ID NO:3. The 70 amino acids of human IGF-I are set forth in SEQ ID NO:4.
B. Protein Expression
The protein expression of human IGF-I is shown as the result of SDS-PAGE in FIG. 4 .
C. Protein Purification
The pET24a-IGF-I was transformed into expression competent BL21-codon plus E. coli cells. The cells were grown in 5 ml LB containing 35 μg/ml kanamycin in a shaking incubator at 37° C. overnight. Then, 5 ml of the culture was added to 500 ml LB containing 35 μg/ml kanamycin and the culture was continued to grow in a 37° C. shaker for approximately 3 h until the OD550 reached 0.5-1. After the OD550 was around 0.5-1, protein expression was induced with isopropylthiogalactoside (IPTG) at concentration of 0.5 mM. After an incubation time of 6 h at 37° C., the cells were harvested by centrifugation and resuspended in 50 ml PBS containing 100 μg/ml lysozyme, pH 7.5. Store the suspension at 4° C. for 30 min. And then, the suspension were sonicated on ice (15×1.5 s pulses with 1 s intervals) and centrifuged for 10 min at 10000 g. The precipitate was resuspended in 50 ml IB wash buffer (20 mM Tris-HCl, pH 7.5, 10 mM EDTA, 1% Triton X-100) and centrifuged again at 10000 g for 10 min. Repeat this step three times. The supernatant was decanted and the inclusion body-containing precipitate of pET24a-IGF-I/BL21 codon plus was suspended in 25 ml 8 M urea buffer containing 20 mM Tris-HCl, 0.5 M NaCl, pH 7.8. Store the suspension at 4° C. for overnight to dissolve the inclusion bodies. Residual insoluble matter was removed by centrifuging at 15000 g for 30 min. The protein suspension was loaded onto a His-Bind resin column. After loading the sample, the purified protein was eluted by elute buffer (8 M urea, 20 mM Tris-HCl, 0.5 M NaCl, 0.25 M imidazole, pH 7.8). The purified protein solution was diluted with 9 volumes of rapid refolding buffer (2.5 M urea, 20 mM Tris-HCl, 0.01 mM EDTA, 2 mM GSH, 0.2 mM GSSG, 0.02% sodium azide, 0.2 M arginine, pH 8.5). After 48 h at room temperature, the mixture was concentrated ten-fold by ultrafiltration, and dialyzed against 1000 ml of refolding buffer (20 mM Tris-HCl, 0.01 mM EDTA) containing a descending gradient of urea (2-0 M) at 4° C.
D. Activity Analysis
The sample was prepared with PBS, 1 μl/well was transferred to microtiter plates mixed with 100 μl of 3T3 cells (1×10 4 cells/ml), which had been washed three times with PBS then suspended with DMEM medium containing 1% FCS. The plates were incubated for 48 h, then 10 μl of Alamarblue was added to each well, and incubated for another 4 h. After incubating, the fluorescence was monitored at 530-560 nm excitation wavelength and 590 nm emission wavelength. The assay of IGF-I activity is shown in FIG. 5 .
(3) Expression and Purification of Human Hair Stem Cell Factor-II (HSCF-II)
A. Gene Construction
The human hair stem cell factor-II (HSCF-II), which has never been reported before, is developed for the first time in our study. The 759-bp DNA sequence of HSCF-II, which is combined with human SCF of 510 bp, the linking peptide of 39 bp and IGF-I of 210 bp, is inserted into pET24a vector to express protein. The PCR cycles and products of HSCF-II were described in FIG. 1 . The cDNA sequence of human HSCF-II is set forth in SEQ ID NO:5. The 253 amino acids of HSCF-II are set forth in SEQ ID NO:6.
B. Protein Expression
The protein expression of the human HSCF-II is shown as the results of SDS-PAGE in FIG. 6 .
C. Protein Purification
The pET24a-HSCF-II was transformed into expression competent BL21-codon plus E. coli cells. The cells were grown in 5 ml LB containing 35 μg/ml kanamycin in a shaking incubator at 37° C. overnight. Then, 5 ml of the culture was added to 500 ml LB containing 35 μg/ml kanamycin and the culture was continued to grow in a 37° C. shaker for approximately 3 h until the OD550 reached 0.5-1. After the OD550 was around 0.5-1, protein expression was induced with isopropylthiogalactoside (IPTG) at concentration of 0.5 mM. After an incubation time of 6 h at 37° C., the cells were harvested by centrifugation and resuspended in 50 ml PBS containing 100 μg/ml lysozyme, pH 7.5. Store the suspension at 4° C. for 30 min. And then, the suspension were sonicated on ice (15×1.5 s pulses with 1 s intervals) and centrifuged for 10 min at 10000 g. The precipitate was resuspended in 50 ml IB wash buffer (20 mM Tris-HCl, pH 7.5, 10 mM EDTA, 1% Triton X-100) and centrifuged again at 10000 g for 10 min. Repeat this step three times. And the inclusion body-containing precipitate of pET24a-HSCF-II/BL21 codon plus was suspended in 25 ml 6 M Gn-HCl buffer containing 20 mM Tris-HCl, 0.5 M NaCl, pH 7.8. Store the suspension at 4° C. for overnight to dissolve the inclusion bodies. Residual insoluble matter was removed by centrifuging at 15000 g for 30 min. The resulted protein solution was loaded onto a His-Bind resin column. After loading the sample, the purified protein was eluted by elute buffer (8 M urea, 20 mM Tris-Hcl, 0.5 M NaCl, 0.25 M imidazole, pH 7.8). The purified protein solution was diluted with 9 volumes of rapid refolding buffer (2.5 M urea, 20 mM Tris-HCl, 0.01 mM EDTA, 2 mM GSH, 0.2 mM GSSG, 0.02% sodium azide, 0.2 M arginine, pH 8.5). After 48 h at room temperature, the mixture was concentrated ten-folds by ultrafiltration, and dialyzed against 1000 ml of refolding buffer (20 mM Tris-HCl, 0.01 mM EDTA) containing a descending gradient of urea (2-0 M) at 4° C.
(4) The Preparation for Hair Follicle Organ Cultured in Vitro
At the age of 8 weeks, the F1 generation of C3H mated with BALB/C supplies the hair follicle material. By plucking the whiskers by depilating forceps, an anagen phase of the hair follicle can be induced. After three days of whisker plucking, the mice were killed and the hair follicle samples were harvested. Each selected hair follicle was then carefully isolated from the subcutaneous fat and the connective tissue surrounding the capsule was removed under a stereo-dissection microscope with fine forceps. We picked up the intact hair follicles with average size for the next step of culture, and which is in the early anagen stage, which is determined by the hair follicle conformation. Before culture, the hair fibre was first cut out at the surrounding line of the hair follicle to make the length measurement of hair growth much more easily in the future ( FIG. 7 ).
Hair follicle were incubated at 37° C. in a water-saturated atmosphere of 5% CO 2 plus 95% air and cultured for 12 days in a 96 well-cell culture cluster (Falcon) containing 200 μl of cultural medium, supplemented with antibiotic penicillin 100 unit/ml-streptomycin 0.1 mg/ml (Sigma). The hair follicles were cultured in phosphate buffered saline (PBS, pH 7.4) as the negative control, containing NaCl 8 g/L, KCl 0.2 g/L, Na 2 HPO 4 1.44 g/L, and KH 2 PO 4 0.24 g/L. And the positive control was cultured in the formula of the control medium, containing some amino acids and vitamins, including 5-100 mg/L amino acids of alanine, arginine, asparagine, aspartic acid, cysteine, cystine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine; and 0.1-10 mg/L vitamins of ascorbic acid, biotin, pantothenate, choline chloride, ergocalciferol, folic acid, inositol, menadione sodium bisulfate, niacinamide, pyridoxal HCl, riboflavin, tocopherol, thiamine, vitamin A, and vitamin B12. The formula in the claim herein is briefly extended to the complex of any amino acid and vitamin.
There were several treatments, including SCF, IGF-I, HSCF, minoxidil alone, and the mixture of HSCF and minoxidil The ranges of these additional compositions in a formula were minoxidil 10-1000 μM, SCF 10-1000 ng/ml, IGF-I 1-1000 ng/ml, and HSCF 1-1000 ng/ml.
Ten hair follicles were cultured in each treatment. The cultured medium in each well was carefully removed every other day and replaced by the same compositions of the fresh medium. The length of the hair growth beginning from the cutting site was measured at Day 12. The whole procedure to compare the different treatments was repeated for 3 times.
Hair follicle was observed by the Inverted microscope (Lieca DM, IL) and captured with the image by CCD connecting with a computer. The hair length was analyzed with the computer software: Northern Eclipse image system. The data of hair length were analyzed with the Duncan's new multiple range test by one way analysis of variance (ANOVA) using the SigmaStat program (2002).
(5) The Graying Animal Model in Vivo
The graying animal model used to simulate human hair graying and to test the effects of the compositions on hair pigmentation in vivo, is established by the F1 generation. It is derived from the hybrid of the C3H and BALB/C mice, which grow white hair after the treatment with the whiting gel, containing 1-20% hydroquinone and 1-20% glycolic acid. In fact, tyrosinase has been proven to dominantly control the synthesis pathway of melanin. When human ages, the tyrosinase genes in melonocytes gradually become depleted, so white hair grows as a result. We establish a kind of mice with the heterologous tyrosinase gene (Tyr+/Tyr−), the activity of which is easy to inhibit by the treatment of whiting agent like hydroquinone. The BALB/C mice is in white color because of homologous depletion of tyrosinase gene (Tyr−/Tyr−) and the C3H strain with (Tyr+/Tyr+) appear in brown color. Heterologous tyrosinase gene (Tyr+/Tyr−) of the F1 generation is to simulate the genotype of human aging in hair follicles, which is much easier to induce tyrosinase depletion or inactivation to appear in white color. After the treatment with the whiting gel for 7 days, the F1 generation starts to grow white hair. If the treatment with HSCF makes the hair darker on the graying animal model, it could have the similar effect on the graying hair of human beings. There were three groups in this experiment, including the untreated group of the wild type as the negative control (without the whiting gel and without liposome), the positive control treated with the whiting gel and the liposome packaged with phosphate buffered saline (PBS), and the treated group of HSCF, which was treated with the whiting gel followed by the functional liposome of HSCF (1-200 μg/ml). There were six mice in each group at total three numbers of repeating times. Before the topical application, the dorsal hair (about 2×2 cm 2 area on skin) has been depilated carefully with fine forceps at Day 0. At Day 2, each mouse was treated with the whiting gel (containing 1-20% hydroquinone and 1-20% glycolic acid) once a day at p.m. for only one week. At the same time, it was also treated with 50 μl of the liposome onto the depilating area once a day at a.m. for two weeks, which duration is one week longer than the application of whiting gel.
In order to analysis the melanin level in the hair fibre, two mg of dorsal hair of each treatment was shaved and cut into small fragments. Then, each hair sample was dissociated by 1 M NaOH 1 ml and heated at 85° C. about 4 h, in order to dissociate the membrane of melanosome to release melanin. It should be protected from light. The colorful aqua from hair dissolution could be used for the melanin detection by spectrophotometer at OD 475 nm. The standard curve of melanin is measured at first by the commercial product of melanin.
(6) The AGA Animal Model in Vivo
The spontaneous mutation of C57BL/6J mouse in our lab has an appearance of hair balding with homologous jb/jb genes ( FIG. 10 ). We chose the mutant mice as the female parent. The androchronogenetic alopecia (AGA) animal model was then established by the hybrid of C57BL/6J female×CBA/J male. This hybrid is called the B6CBAF1/j hybrid mouse. It has been proved that hair loss can be induced for the female of the hybrid by the subcutaneous injection of testosterone (1 mg/mice/day) for 3 weeks. The female of the hybrid is more sensitive to testosterone than male mice, and therefore is appropriate for use as the human AGA balding mimic 18) .
(7) The Penetration Rate of the Liposome in the Folliclular Delivery System
In order to confirm the penetration and distribution of the follicular delivery system into dermis, we took the dorsal skin of mice after the topical application of the liposome containing HSCF. After 15-30 min of application, skin samples were embedded with the compound of Optimal Cutting Temperature (OCT, Tissue-Tek, 4583), frozen and sectioned at 8 μm thickness. Then, the sample was fixed with 4% paraformaldehyde, and blocked with 0.5% slim milk overnight at 4° C. for immunohistochemistry ( FIG. 11 ). In order to label the liposome containing HSCF-II, the primary antibody rabbit anti-SCF (stem cell factor) (1:500) was used (PeproTech). The secondary antibody was florescence (FITC)-conjugated goat anti-rabbit IgG (1:1000) (Jackson ImmunoReasearch).
(8) The Stability of Growth Factor Activity in Liposome
In order to prove the maintenance of the activity of the growth factor HSCF in liposome, we used the reporter protein, enhanced green fluorescence protein (EGFP), to mix with HSCF together in liposome which were stored at the 37° C. incubator for three years. And then, the liposome was checked for the green fluorescence of EGFP to prove the activity of HSCF under the fluorescence microscopy every month. It showed that the protein activity of EGFP could last more than one to three years at 37° C.
Example 2
Effect of HSCF, the Formula and Minoxidil on Hair Growth in Vitro Culture
The hair follicle organs were completely dissected and cultured in vitro to test the effects of the different compositions on the hair re-growth. The results shown in FIG. 7 suggest that the best significant effect of the treatment on the hair re-growth is obtained from the mixture of HSCF, the formula and minoxidil. When hair follicles were cultured in the phosphate buffer solution (PBS), they didn't grow at all. In fact, the hair re-growth effect of HSCF is better than that of SCF and IGF-I each. It indeed proves the effect of HSCF on the hair growth. Moreover, it strongly suggests that the mixture of HSCF and minoxidil is better than minoxidil or HSCF alone (P<0.05).
The ranges of these compositions in a formula were minoxidil 10-1000 μM, SCF 10-1000 ng/ml, IGF-I 1-1000 ng/ml, and HSCF 1-1000 ng/ml. The formula of the cultural medium contains some amino acids and vitamins, including 5-100 mg/L each of amino acids of alanine, arginine, asparagine, aspartic acid, cysteine, cystine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine; and 0.1-10 mg/L each of vitamins of ascorbic acid, biotin, pantothenate, choline chloride, ergocalciferol, folic acid, inositol, menadione sodium bisulfate, niacinamide, pyridoxal HCl, riboflavin, tocopherol, thiamine, vitamin A, and vitamin B12.
Example 3
Topical Application of HSCF for Hair Melanin Synthesis on the Graying Animal Model
Based on the function of HSCF on melanocyte stem cells, we chose the graying animal model to test the therapeutic effect of HSCF on hair graying through topical application. The HSCF protein was packaged in liposome and applied on the dorsal skin through the topical application of the follicular delivery system. The results showed that the hair color of the treated group appeared much darker than the graying mice of the control ( FIG. 8 ). The pigment in the hair shaft was then tested for the content of melanin. It also showed that the content of melanin is higher in this treated group (P<0.05), as well as in the wild type ( FIG. 9 ). It proves the therapeutic effect of HSCF in the claims on the recovery of the pigment in the graying hair.
Example 4
Topical Application of HSCF and Minoxidil for Hair Regeneration on the AGA Animal Model
Based on the function of HSCF on keratinocyte stem cells, we chose the AGA animal model to test the therapeutic effect of HSCF on hair loss through topical application. The HSCF protein was packaged in liposome and applied on the dorsal skin through the topical application of the follicular delivery system. The results showed that the hairless follicles re-grew new hair more quickly in the mice treated with HSCF and/or minoxidil than in the balding mice of the control ( FIG. 10 ). Although the effect of HSCF alone is enough to stimulate the hair growth, it is recommended that minoxidil be combined with HSCF to heal the hair balding. The invention proves the therapeutic effect of HSCF in the claims on the hair re-growth of baldness and the even more effective effect of HSCF combined with minoxidil in the claims on the balding therapy.
Example 5
Liposome in the Follicular Delivery systems
In the study, we test the extent of deposition of the compositions containing the HSCF, the formula of amino acids and vitamins, and minoxidil into the hair follicles of the graying mice model and AGA mice model following a topical liposome-application in the follicular delivery systems. The follicular delivery systems include penetration enhancers and suitable carrier bases and/or devices. The term “penetration enhancer” as used herein means a compound that facilitates the movement of substances into and/or through the epidermis of skin. Examples of penetration enhancers include, but are not limited to, lipids, lipoproteins, fatty acids and fatty alcohol, detergents, alcohols, glycols, mineral oils, liposome, a trans-dermal delivery vehicle or device. And the term “suitable carrier” as used herein means a carrier suitable for topical application to mammalian skin without causing undue toxicity, irritation, allergic response, and the like. The addition of penetration enhancers and suitable carrier bases in the mixture contributes to the effectiveness of topical delivery system on hair follicles.
The HSCF packaged in liposome in the follicular delivery systems in this invention has been proven to reach the dermis from the skin surface within 15-30 min ( FIG. 11 b ). The essential function of the liposome could maintain the activity of the growth factors for at least 1-3 years, because the green fluorescence of EGFP in the liposome could be detected under the fluorescence microscope for 1-3 years ( FIG. 11 a ).
Many changes and modifications in the embodiments of the invention described above can, of course, be carried out without departing from the scope thereof. Accordingly, to promote the progress in science and the useful arts, the invention is disclosed and is intended to be limited only by the scope of the appended claims.
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The present invention provides comprehensive compositions for treating problems associated with hair graying and balding via the incorporation of: (i) the cell growth factor of HSCF to induce the migration of melanocyte stem cells and keratinocyte stem cells and then to increase the growth of melanocytes and keratinocytes in hair follicles, (ii) a formula of amino acids and vitamins to provide the nutritional factors for hair growth and pigmentation, and (iii) minoxidil to enhance the function of HSCF on hair re-growth. The compositions comprising at least one of (i), (ii) or (iii) are administered on skin and/or scalp through liposome in the follicular delivery systems, including penetration enhancers and suitable carrier bases. The compositions packaged in liposome in the follicular delivery systems in this invention has been proven to reach the dermis from the skin surface within 15-30 min.
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FIELD OF THE INVENTION
[0001] The present invention relates generally to an adapter for receiving at least two separate sizes of tools and, more particularly, to an adapter having at least two sized cavities and/or extensions for mounting on a variety of different sized ratchets and other like tools.
BACKGROUND OF THE INVENTION
[0002] Socket wrenches, including a drive tool and socket, are commonly used to turn fasteners, such as nuts and bolts. A first end of the socket is placed over the bolt and the drive tool is inserted into a second socket end. A user then applies force directly to the drive tool for rotating the bolt.
[0003] A standard socket set includes a number of sockets each having different first end sizes for accommodating a variety of sizes of bolt heads and other like fasteners. Commonly, the sockets are dimensioned according to the common sizes of fasteners, such as the metric or English systems. The second socket end attaches to the drive tool and may have a variety of sizes, depending upon the manufacturer, year of manufacture, first socket end dimensions, and the like. Each of the second ends is substantially rectangular in shape, but there are no standardized sizes or dimensions.
[0004] A problem occurs for persons that use a variety of different sockets and drive tools. When working on fasteners of unknown or varying size, the user is required to have a variety of sockets to accommodate the fasteners, and a variety of drive tools to accommodate the socket second ends. This gets extremely burdensome for the user requiring them to carry numerous extra tools that may or may not be necessary. Additionally, different sized sockets may get mixed together within a tool box thereby requiring the user to always bring different sized drive tools to ensure they can accommodate the sockets.
[0005] Prior art designs have focused more on the first socket ends that accommodate the fasteners, and have largely ignored adapting to the socket second end. U.S. Pat. No. 4,840,094 to Macor discloses a multiple socket wrench having inner and outer members that are slidably engaged to accommodate a variety of fasteners. However, Macor does not provide for accommodating different sizes of drive tools. U.S. Pat. No. 5,048,379 to Gramera et. al. discloses a double-ended hollow core socket with a first end having a diameter sized to accommodate a first fastener size, and a second end having a different diameter. Again, the socket cannot accommodate various sizes of drive tools.
[0006] There are many types of sockets for accommodating various fastener sizes. However, these sockets often overlook the necessity of attachment to the drive tool. Thus, there remains a need for an adapter to accommodate at least two separate sizes of drive tools and/or socket second ends.
SUMMARY OF THE INVENTION
[0007] The present invention allows for a single tool to accommodate a number of different sizes of tools and different sizes of adapters. Existing tools currently on the market may be used and are interchangeable with the tools described in the present invention. In one embodiment, the invention is an adapter for receiving at least two separate sizes of tools. The adapter has a first adapter end having an inwardly extending cavity with at least two substantially rectangular cross-sectional areas including a distal cavity having a smaller diameter than a proximal cavity. A second adapter end is positioned opposite the first adapter end.
[0008] In another embodiment, the invention includes a tool adapter having a first receiving end having substantially rectangular outer and inner cavities. A second extension end is positioned opposite the first receiving end and includes outer and inner extensions being substantially rectangularly shaped.
[0009] In another embodiment, the adapter includes a first end having at least two axially aligned receiving cavities. A first receiving cavity is positioned proximate the first end and has a larger diameter than a second distal receiving cavity. A second end has at least two receiving cavities axially aligned. A third receiving cavity is positioned proximate the second end and has a larger diameter than a fourth distal receiving cavity.
[0010] A drive tool embodiment is also disclosed having a handle, and a head positioned at one end of the handle. At least two extensions extend outward from the head including a first inner extension having a substantially rectangular shape, and an outer extension centered on the inner extension and having a substantially rectangular shape having smaller dimensions than said inner extension.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] [0011]FIG. 1 is a side view with hidden lines of one embodiment of an adapter constructed in accordance with the present invention;
[0012] [0012]FIG. 2 is a cross-sectional side view illustrating a socket constructed according to one embodiment of the present invention;
[0013] [0013]FIG. 3 is a partial perspective view of a drive tool;
[0014] [0014]FIG. 4 is a side view with hidden lines of the drive tool with attached adapter and socket mounted together in accordance with one embodiment of the present invention;
[0015] [0015]FIG. 5 is a perspective view with hidden lines illustrating an alternative tool adapter embodiment having a receiving end and a tool end;
[0016] [0016]FIG. 6 is a cross-sectional side view of yet another alternate embodiment of an adapter and
[0017] [0017]FIG. 7 is a cross-sectional side view of another embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0018] Referring now to the drawings and general in FIG. 1 in particular, it will be understood that the illustrations are for the purpose of describing a preferred embodiment of the invention and are not intended to limit the invention thereto. As seen in FIG. 1, an adapter, generally designated 10 , is shown constructed according to one embodiment of the present invention. The adapter 10 includes a receiving end 20 having an outer cavity 22 and an inner cavity 24 . Positioned on the opposite end, extension end 30 includes an outer extension 32 and an inner extension 34 . The adapter 10 provides for mounting a variety of different sized sockets and other like tools onto a single drive tool 100 (FIG. 3).
[0019] Receiving end 20 includes at least two cavities for mounting to at least two different sized drive tools or adapters. Preferably, both the outer cavity 22 and inner cavity 24 are aligned along the center line CL as illustrated in FIG. 1. The outer cavity 22 has a larger diameter than inner cavity 24 such that a smaller drive tool that does not mount within the outer cavity 22 can extend into the inner cavity 24 . For example, the outer cavity 22 could have an effective diameter of ⅜″ and the inner cavity 24 have an effective diameter of ¼″. Larger or smaller variations on this are possible, with the limiting criterion being that the inner cavity 24 have a smaller effective diameter than the outer cavity 22 . In one embodiment, both inner and outer cavities 22 , 24 have substantially rectangular shapes to conform to the drive tool or adapter extensions. The depth of the cavities 22 , 24 may vary depending upon the specific embodiments. Ball detent receivers (not illustrated) may also be positioned within the cavities 22 , 24 for receiving a ball detent from the drive tool. Additionally, square shapes are specifically contemplated as being included in the rectangular shapes described.
[0020] Body section 40 extends between the receiving end 20 and extension end 30 . Again, the body may have a variety of dimensions and sizes depending upon the desired usage of the adapter 10 . As illustrated in FIG. 1, body 40 has an elongated shape which has substantially the same diameter throughout the length. Body 40 may be substantially solid or may be hollow to reduce the amount of material necessary during manufacturing.
[0021] Extension end 30 includes extensions 32 , 34 for mounting into sockets or other like tools. Inner extension 34 has a larger cross-sectional span than outer extension 32 . This configuration allows for the outer extension 32 to mount into smaller sized receptacles such as a complementary inner cavity 24 on a second adapter 10 without being blocked by the larger outer cavity 22 . In an exemplary embodiment, both inner and outer extensions 34 , 32 are substantially rectangular-shaped for mounting into the different sizes of sockets. The length of the inner and outer extensions 34 , 32 may vary depending upon the specific embodiment. For example, the outer extension 32 may have an effective span of ¼″ and the inner extension 34 have an effective span of ⅜″, each with a depth of ¼″. As with the receiving end, the inner and outer extensions 34 , 32 are preferably coaxially aligned on the centerline CL. A ball detent (not illustrated) may be positioned along the extensions 32 , 34 for maintaining the socket or tool adapter. The length of the extensions 32 , 34 may vary depending upon the specific environment in which the tool is used. This variance may be from the exemplary ¼″ described for both depths, or the depths may vary independently of one another.
[0022] It is possible that the adapter 10 of FIG. 1 may include only one cavity 22 and two extensions 32 , 34 or two cavities 22 , 24 , and only one extension 32 . The variety of combinations possible is one of the things that makes the present invention versatile and desirable to those who use these sorts of tools as they may mix and match as they need to to accommodate their needs.
[0023] [0023]FIG. 2 illustrates another adapter 80 of the present invention having two receiving ends each of different sizes. By way of example, a first side 84 a , 86 a may be sized for a drive tool size produced by a first manufacturer, and the second side 84 b , 86 b sized in accordance with another manufacturer. Alternatively, the two sides may be equipped for the same manufacturer and each be of a different size to increase the likelihood of mounting to the drive tool. In another embodiment illustrated in FIG. 2, the inner receiving cavities 86 a , 86 b may extend through the length of the adapter 80 and connect forming a substantially hollow interior. The inner receiving cavities 86 a , 86 b may be of the same size, or may be of differing sizes. The adapter 80 illustrated in FIG. 2 allows for a single adapter 80 to be used on a variety of drive tools 100 (FIG. 3) to reduce the amount of tools necessary for the user to handle and purchase.
[0024] Adapter 80 may further include one or more socket adapters 82 a , 82 b positioned along an exterior edge of end. Each socket adapter 82 a , 82 b is sized to mount over a fastener 55 (FIG. 4). In one embodiment, socket adapters 82 a , 82 b are centered about the adapter center and are hexagonal to mate with a standard multi-sided bolt head. Additionally, more than one different sized adapter may be mounted on each end. Thus, a first end socket adapter 82 a may be sized to accommodate ½″ fasteners and the second end socket adapter 82 b may be sized to accommodate a 12 mm fastener.
[0025] The drive tool 100 is illustrated in FIG. 3. Drive tool 100 includes a handle 102 and a head 104 having a plurality of extensions 132 , 134 extending outwardly therefrom. The extensions 132 , 134 are of different sizes to accommodate a variety of sockets or adapters, and are substantially identical to the extensions 32 , 34 on the adapter 10 . However, the extensions 132 , 134 are mounted on a ratchet mechanism that mounts within the head 104 for rotation in a clockwise and counter-clockwise directions as is well known to one skilled in the art. Extensions 132 , 134 are preferably substantially rectangular shaped to conform to the sockets and adapters.
[0026] [0026]FIG. 4 illustrates the drive tool 100 with a first adapter 10 and second adapter 80 . The drive tool inner extension 134 is sized, within this embodiment, to be received by the outer cavity 22 of the first adapter 10 . The first adapter outer extension 132 is sized to fit within the inner receiving end 86 b of the second adapter 80 and not interfere with the mounting. As the drive tool 100 and attached first adapter 10 are moved in the direction of arrow 9 , the outer extension 32 is sized to mount into the inner cavity 86 b of the second adapter 80 . The second adapter outer receiving end 84 b and socket adapter 82 b are of a large enough size so as not to interfere. The second adapter socket 82 a is sized to accommodate the fastener 55 . Rotation of the drive tool 100 is transferred through the first and second adapters 10 , 80 for rotating the fastener 55 . It should be appreciated that while one mating arrangement between the elements are shown, other permutations are contemplated wherein the drive tool 100 fully mates with the first adapter 10 and the first adapter 10 only partially mates with the second adapter 80 .
[0027] It should be noted that the second adapter socket 82 a may not be sized to accommodate the fastener 55 , thereby requiring the second adapter 80 to be reversed such that the second socket 82 b may accommodate the fastener 55 , or another second adapter may be placed on the first adapter 10 as necessary. Additionally, the second adapter 80 may be sized to be mounted directly to the drive tool 100 .
[0028] [0028]FIG. 5 illustrates an alternative embodiment of a tool adapter 200 . Tool adapter 200 includes a first receiving end 201 having at least two cavities 222 , 224 for receiving extensions 32 , 34 , 132 , or 134 similar to the adapter 10 or drive tool 100 . A second tool end 202 features a tool fixedly mounted to the body 240 . This design allows for the drive tool 100 to be used as a rotational tool. Tools that may be positioned on the second tool end 202 include a screwdriver, universal joint, hex driver, spark plug socket, open-ended wrench, posi-drive wrench, ALLEN wrench, TORX wrench, and the like. One skilled in the art will understand that there are other numerous other tools that may be mounted to the tool adapter 200 . The body 240 may have a variety of orientations depending upon the desired positioning of the tool.
[0029] In addition to using a tool adapter 200 so that the drive tool may be converted into a different rotational tool, it is possible to modify the cavities and extensions of any of the adapters 10 , 80 or tools 100 , 200 . In particular, any outer extension 32 may be modified such that it is in fact a tool end comparable to tool end 202 , and any interior cavity 24 , 84 a , 84 b , 86 a , 86 b , or 224 may be modified to receive such a tool end type extension. Thus, for example as shown in FIG. 6, an adapter 300 includes an outer rectangularly shaped cavity 302 and an inner ALLEN wrench shaped cavity 304 . Further, the adapter 300 includes a rectangularly shaped inner extension 306 and an ALLEN wrench shaped outer extension 308 . Variations of the tool shaped extension cavity 304 and extension 308 are possible both in size and in type of tool end. Thus, as listed above a screwdriver, universal joint, hex driver, spark plug socket, open-ended wrench, posi-drive wrench, ALLEN wrench, TORX wrench, and the like may all be used. Further, it is possible that the outer cavity 302 and inner extension 306 could also be shaped to correspond to a tool end. However, care must be taken that a small tool end is still able to pass through the outer cavity 302 to reach inner cavity 304 and that there are no obstructions. Further, a large cavity must still fit over outer extension 308 to fit properly on inner extension 306 . As long as these criteria are met, the tool end type cavities and extensions may be mixed and matched with rectangularly shaped and other tool type cavities and extensions as needed or desired.
[0030] [0030]FIG. 7 illustrates another embodiment of the present invention having a first end with a pair of receiving cavities 702 , 704 , and a second end 706 sized to mount about a fastener 55 . This embodiment may be mounted directly to the extensions of a drive tool, and does not require any intermediate device for making a connection.
[0031] The elements of present invention are both preferably constructed of a unitary construction. Preferably, they are constructed of a durable material that resists bending or deformation. In one embodiment, the pieces are constructed of a forged steel.
[0032] In the foregoing description, like reference characters designate like or corresponding parts throughout the several views. Also in the following description, it is to be understood that such terms as “forward”, “rearward”, “left”, “right”, “upwardly”, “downwardly”, and the like are words of convenience and are not to be construed as limiting terms. The present invention may be carried out in other specific ways than those herein set forth without departing from the spirit and essential characteristics of the invention. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, and all changes coming within the meaning and equivalency range of the appended claims are intended to be embraced therein.
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A tool for receiving adapters and sockets of various sizes. One embodiment includes a first receiving end having outer and inner cavities being substantially rectangular with the inner cavity having a smaller diameter than the outer cavity. A second extension end is positioned opposite the first receiving end and includes outer and inner extensions being substantially rectangular shaped with the outer extension having a smaller width than the inner extension. Another embodiment includes a first end having at least two receiving cavities axially aligned. A first receiving cavity is positioned proximate the first end and has a larger diameter than a second distal receiving cavity. A second end includes at least two receiving cavities axially aligned including a third receiving cavity positioned proximate the second end having a larger diameter than a fourth distal receiving cavity.
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FIELD OF THE INVENTION
The present invention relates to an improvement in artificial wave generating pools, and, more specifically, to a novel means for producing a circular standing wave for recreational use by surf riders, both prone (known as body boarders) and stand-up ("traditional") surfers.
BACKGROUND OF THE INVENTION
Many pools have been constructed for the purpose of creating artificial surfing breakers. These pools are, however, limited in that they require sizable areas in which to operate and a large investment in motors, pumps and caissons. Also, once a site is chosen and the wave pool constructed, there is no viable or expedient means for dismantling and transporting the pool if desired.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a more economical device for producing surfing waves in a compact area, and to make the device portable by design. The invention realizes this object by taking advantage of the laws of centrifugal force.
According to one aspect of the present invention, a rotatable circular platform is mounted to a truck bed and a circular pool is mounted in turn to the platform. With additional hardware and the use of a motor and drive system, the pool is rotated at sufficient speed so as to cause a specified volume of water within the pool to move in the direction of rotation. The centrifugal force acting on the rotating flow causes it to bend and rise, giving it the slope, crest, trough and velocity of a surfable wave. The addition of a board attachment means and safety nets allows surf riding to be performed within the simulator. The investment and space required for such a system is considerably less than other wave pools in existence.
Another object of the invention is to simulate ideal surfing waves for both novice and expert riders, with the waves possessing a shape and surface quality previously unattainable outside the natural confines of the ocean.
Still another object of the present invention is to provide a standing rotary wave that does not diminish in size or quality with the passage of time, thus providing riders with a prolonged surfing duration.
Yet another object of the invention is to produce waves of a size, power and magnitude heretofore unknown to devices of this nature, and naturally found only in remote areas. Such waves are created only when very specific conditions are manifest, such as swell size and direction, reef slope and depth. Surf riders previously had to travel great distances to such locations as Indonesia and more notably the North shore of the Hawaiian Island Oahu to find and ride such breakers. Such waves usually encompass a height of ten feet or more from trough to crest, and are prized by master surfriders for the challenge and thrill that accompany riding surf of this nature.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects and features of the invention will be better understood from the following detailed description with reference to the accompanying drawings, wherein:
FIG. 1 is a top view of the support and drive system of the invention;
FIG. 2 is a top view of the rotatable platform shown as a partial-cutaway;
FIG. 3 is a side view of the platform and the support structure therefor in its folded position mounted on a truck bed;
FIG. 4a is a side, partial-cutaway view of the pool and platform according to the invention;
FIGS. 4b and 4c are enlarged detailed portions of the structure shown in FIG. 4a;
FIG. 5 is a perspective view of the simulator in operation;
FIGS. 6 and 7 are top views of surf craft used in conjunction with the device of the present invention;
FIG. 8 is an enlarged detail of the retaining pin taken in frontal cross-section from the surf craft shown in FIGS. 6 and 7;
FIG. 9 shows the effect on the wave form of the various crest baffle positions; and
FIGS. 10-12 show various embodiments of the crest baffle and its mounting means according to the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to the drawings, a standard truck bed 1 is provided having normal dimensions and structure. The bed is positioned in an area suitable to the simulator's unfolded dimensions. A hub 2 of suitable materials, load bearing capacity and rotational integrity is mounted at the central area of the bed for rotation with respect thereto. A circular platform 15 is supported on the upper surface of the hub. Retractable beams 3 may be hinged on the truck bed on opposite sides of the hub 2 and are movable between a vertical stored position and a horizontal deployed position. Wheel mounts 4 are bolted or welded to the outer ends of the beams 3, and circumferential support tires 5 are rotatably mounted on the wheel mounts. Industrial-grade support jacks 6 are placed at spaced points underneath both the truck bed 1 and retractable beams 3 when the simulator is disposed in operative position. These jacks bear load and, in conjunction with support posts 7, serve to stabilize the under carriage of the simulator. Wood blocks or other like objects may be placed under the jacks as needed to level the simulator. A braking system 8 is provided on one or more tires as needed. Standardized automotive braking systems are suitable in this capacity.
A drive motor 9 of adequate horsepower, a reduction gear 10, and a split-phase gear motor 11 to provide varying speeds and reverse drive are welded or bolted as shown to the bed and, in conjunction with drive shaft 12, serve to rotate friction drive wheel 13. The friction drive wheel necessarily has a sturdier mounting to truck bed 1 than the support tires 5 but is of the same nature and size as tires 5. The drive system can be configured to allow for clockwise or counter-clockwise rotation by control of the split-phase gear motor.
A circular platform 15 is formed of a strong metallic substance such as steel and includes a central portion 15a, which is generally rectangular in configuration, and a pair of generally semi-circular side portions 15b and 15c each of which has a linear edge thereof pivotally attached to one of the linear sides of the central portion by hinges 17. The side portion may be moved into a vertical storage position as shown in FIG. 3 or moved into a horizontal operative position as shown in FIGS. 2 and 4a. Support members 16 are formed of material similar to that of portions 15a, 15b and 15c and are secured as by welding to the undersurfaces thereof to strengthen the platform. A drive ring 14 also formed of steel or the like is formed of circular segments secured as by welding to the peripheral portions of the undersurfaces of members 15a, b and c to define a complete circular drive ring when the device is in operative position.
As seen more clearly in FIGS. 2, 3 and 4a, the system serves to support and rotate a circumferential drive ring 14 made of a suitable rigid material. The ring is bolted, welded or otherwise secured to the underside of the circular platform 15, which is further supported along the underside by members 16 which are made of similar material and affixed in like manner. The platform and drive ring are preferably made compact atop truck bed 1 for transportational purposes by the segmentation of the platform along lines a'. The segments 15b, 15c are secured to the centrally disposed section 15a by industrial hinges 17, so that the resulting crescent-shaped sections 15b, 15c can be pulled up and secured by locking means, perpendicular to truck bed 1, as shown in FIG. 3. This embodiment, along with other facets of the invention's design, serve to make the device transportational as desired. Of course, other infrastructure designs may be implemented, such as a waterpark design wherein the unit would be permanently mounted in one location. Additionally, circumferential partition 18 may be implemented to cosmetically hide the underworkings of the simulator.
As seen in FIGS. 4a-4c a multiplicity of "Doughboy"-style pool wall sections 19 can be secured to the mainframe in the following manner. Inner L-brackets 20 are welded to each section 19 and the horizontally disposed portion of the bracket is in turn securely bolted to the surface of circular platform 15. The lower portion of each vertical portion of the bracket is in turn secured in like manner to the outer periphery of circumferential drive ring 14 as is the lower portion of the pool wall 19. When completed, a container for holding the body of water, herein referred to as the pool, is formed. Additionally, outer retention bands 21 may be secured to the pool's upper and lower circumferences to preserve the necessarily round shape of the assembled pool wall when the simulator is rotating.
Horizontal padding 22a is installed on the surface of the platform 15 and is assembled in pie- or crescent-shaped pieces so that the whole of padding 22a fits flush along the inner periphery of the assembled pool wall. Vertical wall padding 22b is also installed for rider safety. The padding may be of any suitable type such as inflatable sections, expanded foam or alternate materials, and may be secured to the platform and pool wall by well-known means such as hook and loop (Velcro™) fastening strips, clips or other viable means.
Paddings 22a and 22b may be molded or otherwise shaped so as to affect flow shape in a specific manner, i.e. a pond or multiple flume shape could easily be fabricated by implementing the appropriate shaped padding. Such alterations of pool shape may be employed to positively modify resultant simulator flow shape.
A fitted pool liner 23, made of polypropylene, vinyl or other suitable material is then fitted within the simulator and secured to the upper rim of pool the wall 19 by suitable means, such as clips, retention copings or grommet and pin devices (not shown). A water line, which would normally mark one-quarter to one-third of the simulator's total potential volume, may be embossed upon the liner's inner surface for precision filling of the simulator.
A raised pool deck 24 is provided around the circumference of the simulator. The deck is made of suitable materials preferably having a non-skid surface texturing. Pool deck 24 is elevated by normal means, such as legs or scaffolding with stairs (not shown) provided for user access. As shown in FIGS. 4a and 4c, the upper circumference of the pool wall closely underlaps the vertically disposed circumferential area of pool deck 24 so as to eliminate the possibility of individual injury that would occur should the upper edge of the wall be exposed, allowing surf riders to grab, fall upon or otherwise come in contact with the rotating pool edge. A safety stripping 25, made of thin plastic, rubber or other material further inhibits the likelihood of injury. The stripping lines the gap between the pool wall 19 and the vertically disposed lip area of deck 24. As shown in the drawings, the pool shape just underneath the pool/deck juncture is noticeably curved. The curvature is provided to prevent the centrifugally created wave shaped flow from swirling out of the simulator upon rotation. Additionally, a drain plug (not shown) may be secured within the simulator to expedite the removal of pool volume when necessary.
The pool structure may alternatively comprise a reinforced fiberglass pool and the driving means may comprise a chain or belt drive system.
The present invention does not, technically, create a wave (i.e. the propagation from point to point of a disturbance or oscillation), but is employed to simulate the general shape and physical attributes necessary for the surf riding sport to be practiced thereon. These attributes include, but are not limited to, flow velocity, trough, crest and the resulting inclined surface between the trough and the crest on a body of water known as a "wave", per se. Additionally, the invention introduces a new type of surfing wave by applying the laws of centrifugal force and the action the force has on a body of water in a circular pool structure. Normally, surfing waves and/or artificially-generated flows for similar purposes possess a shape and dimensions usually having the following characteristics: 1) the wave/flow embodies an inclined surface wherein movement of flow is primarily from trough-to-crest, in that order; and 2) individuals riding on such a wave/flow are normally in a state of motion across the inclined surface of the wave/flow, so that the surf rider's original point of catching the wave/flow versus the point he ceases from riding the wave/flow is at a distance proportional to the length of time the surfer rode the wave/flow and the forward momentum of the wave, etc. In other words, the surf rider, in the act of riding the wave/flow, travels a distance from his original point of departure, and the surfing action is dependent on both the forward movement of the wave/flow and the trough-to-crest flow action, allowing the rider to slide up and down the inclined wave/flow surface as it moves shoreward. The present invention proposes that, if an inclined surface is provided and flow is in a non-traditional direction, a surf rider may mount a surfing craft, as will become apparent later, and ride the aforementioned inclined surface with no forward momentum, but in a side-to-side (trough-to-crest) fashion. The invention realizes this object by rotating the simulator to cause the horizontally disposed water volume within the simulator to move in the direction of rotation. Due to the centrifugal force imposed upon the volume, the volume rises and bends, thus creating a wave shaped inclined body of water. The wave-shaped flow is mostly free of the turbulence associated with surfing waves as the system does not create any "whitewater". Additionally, the deck and recessed nature of the pool keep wind from disturbing the flow, thus giving the flow an outstanding shape and surface quality.
A preferred ratio of simulator radius to wall height is approximately 2:1. Taking into account the wave shaped flow created within the confines of the simulator, this ratio facilitates the creation of ridable flows of a size and magnitude previously unattainable outside the ocean, i.e. Radius=20 feet and height=10 feet. Other ratios are of course possible and can create other desired wave simulations. It has been found, however, that substantial deviations from the 2:1 ratio may cause a centrally disposed circular balded area devoid of any substantial depth of water in the pool at optimum rotations. This condition is generally undesirable for safety reasons.
The speed is dependent on diameters of the pool which are normally between twenty and forty feet. Sufficient speeds are attained at 15-25 r.p.m.s. The flow of the body of water moves not from trough to crest but radially, across and perpendicular to the angle of the incline and in the direction of simulator rotation. As the surf rider alternates starboard and port surfcraft angularization against the centrifugally created radial flow he is able to bank up and down the centrifugally created inclined surface, thus successfully simulating the surfing sport within the simulator.
To restrain movement of a surf craft and a rider which are both supported on the generated wave, a restraining wire 26, being of a length equal to or greater than the width of the pool and possessing the necessary tensile strength for rider support, is horizontally positioned across the length of the pool and affixed to the uppermost area of vertically disposed support posts 27. The posts are made of a material and length to enable support of restraining wire 26. Posts 27 are then bolted or otherwise secured, as shown, to raised pool deck 24. A roller mechanism 28, comprised of one or more bearing assemblies, or a similar device suitable to the purpose of 28, is secured to the restraining wire 26 in such a way so that it is allowed to move along the length of the wire without undue friction or resistance. A tether line such as retention leash 29 is provided and is made of nautical type rope or the like. Leash 29 has two ends and is of a length of between eight and fifteen feet. One end of the retention leash shall be clipped, knotted or otherwise affixed to roller mechanism 28 through a cleat or similar means while the other end of 29 is provided with a spring clip 30 or other quick attachment/release device. A leash plug 31 is affixed to a predetermined position on the individual surf craft 32, 32', normally near the bow (nose) and centered flush upon the craft as shown in FIGS. 6-8. The exact measurements of surf crafts 32 and 32' are not critical as long as standard hydrodynamic principles are observed. Spring clip 30 then clamps onto the retention pin within 31. As the simulator becomes activated this system allows a surf rider to bank across the wave shaped flow created therein, with the juncture of 26, 27 and 28 acting as a kinetic pivot point for the surf rider, allowing a more dynamic range of motion than would be realized with a fixed and/or stationary anchoring of retention leash 29. Additionally, this system, in conjunction with the prolonged formation of a ridable wave-shaped flow as provided by the simulator, allows for surfing activity of a duration previously unattainable in or out of the ocean.
A net system is used for the entrance and exit of riders, and for the safe apprehension and subsequent exit of riders who "take a spill" while in the act of surfing the flow. Additional posts 27 are implemented to attach the net in a fixed position to the pool deck 24, with the addition of horizontal extension posts 33 which are affixed securely to the uppermost ends of their respective posts 27. Extending down from the ends of posts 33 are vertical net support posts 34 fashioned so as to be near flush with the rotating walls of the simulator. Safety stripping 25, similar to that used between the pool and the deck, is affixed between the post and simulator for similar safety reasons. Additionally, horizontal net support posts 35 extend across the pool and connect in similar fashion to the respective top and bottom ends of their diametrically opposite posts 34. All posts 27, 33, 34, and 35 utilize a tubular waterproof padding for safety, with individual posts 34 and 35 having apertures for the connecting of safety net 36, which is then positioned and affixed by well-known means across the length of the pool. Safety net 36 shall be made of a suitable material such as nylon webbing, water-proof fabric or the like. The net has eyes large enough to allow pool flow to continue unhindered yet small enough to hinder riders from becoming entangled or otherwise injured. Normally, the eyes of safety net 36 will therefore be between three and six inches.
A possible configuration would allow for many individuals to ride the simulator at once, i.e., multiple net systems may be deployed, thus creating individual web shaped safety zones within the pool. These zones, in conjunction with the implementation of additional transverse surf craft restraining means would allow several riders to surf the simulator at once.
With the net in place, a simulator rider may enter and exit the simulator in a safe manner, and if the rider has a fall or mishap while riding the wave flow he is carried by the flow into safety net 36. The rider may then exit the simulator by climbing up and out to the pool deck 24. Additionally, the rider can ensure additional safety to his person while utilizing the simulator by the donning of such protective gear as a helmet and a personal flotation device.
A crest baffle 37 may be employed to give the simulated wave flow specific shape and contour at the crest area. The purpose of the crest baffle is to aid the rider as he banks off of the crest shaped contour as is natural for indigenous surface riding in coastal areas. As seen in FIGS. 9-12 a baffle piece 38 is provided for this purpose. The piece is normally between one-half and two feet long and is constructed of a flat, rigid and preferably transparent material such as plastic or plexiglass. The baffle may be patterned in a rudder-like shape, as shown, or in other shaped pieces. Rectangular, oval, triangular or round shaped pieces may be employed with satisfactory results. In fact, a multiplicity of baffle pieces 38 in various shapes may be made available for rider use, the pieces attaching to an armature 39 by wing-nuts, spring pins or other means convenient for stable and speedy attachment of the baffle. It will be recognized by those skilled in the art that alternate multidimensional baffle structures may be implemented, encompassing complex hydrodynamically precise curvatures and/or linear conformations. A handle 40 is in turn fitted within the circumference of armature 39 and holes are provided near the mated rims of both the handle and armature for the introduction of at least one retaining pin 41. An additional pin 41' is positioned through a hole provided at the end of handle 40 for the purpose of anchoring the crest baffle 37 at a predetermined angle with respect to the pool deck 24 as shown. A multiplicity of slots are provided upon the pool deck for this purpose. Brackets 42 are bolted, welded or otherwise affixed to the vertically disposed circumferential area of pool deck 24 as shown and give the crest baffle 37 a solid pivot when the baffle is immersed in the rotary flow of the simulator.
The aforementioned system gives the advanced surf rider a choice of crest curvature and character upon which to perform maneuvers. Normally, crest baffle angularization between zero and thirty degrees creates a vertically disposed crest b', and between thirty and ninety degrees creates a tubing crest c', a phenomena wherein the crest throws out and forward from its point of origin thus creating a tubular partition of water within which the rider may test his skill. Additionally, from ninety to approximately one hundred and thirty degrees crest baffle 37 will form a jump wake, which is not unlike that formed by a boat's wake. This allows surf riders to perform aerial maneuvers thereon. A reversal of the baffle piece on its armature is used to form the jump wake at ninety to one hundred thirty degrees.
Optimally, the invention will be capable of clockwise and counter-clockwise rotation for the successful simulation of both right- and left-breaking waves. Therefore, in the event that such a reversed rotation is desired, baffle piece 38 would be removed from armature 39, reversed in position and reaffixed to 39. It is the flat and symmetrical nature of 38 that shall make this adaptation for reverse rotation position possible.
The crest baffle is optimally for use in crest enhancement primarily for the riding thereon by seasoned surf riders, with novices having the system removed for safety purposes. The simulator's centrifugally created wave flow may of course be ridden successfully without the deployment of crest baffle 37. Thus, the non-breaking and turbulence-free wave shaped flow is created which is well-suited for riding by beginners.
Splash guards 43, being preferably constructed of similar material as baffle piece 38, may be predisposed as shown for retaining water spray within the simulator which normally results from a banking by advanced riders off of the aforementioned crest portion of the wave shaped flow.
A control panel (not shown) is provided for simulator operation, with individual controls primarily for the acceleration and braking of the simulator. Other monitoring instruments, such as those normal as to the gauging of R.P.M's, flow rate and for the altering of rotational direction, etc., may be provided as deemed necessary.
Additionally, appropriate water filtration and purification means may be employed for hygienic safety, with the hardware for such devices adapted to the rotational nature of the simulator.
Although the present invention has been described in connection with preferred embodiments, it will be appreciated by those skilled in the art that additions, modifications, substitutions and deletions not specifically described may be made without departing from the spirit and scope of the invention defined in the appended claims.
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A wave simulator comprises a circular pool containing a volume of water which rotates about a central axis. The pool is rotatably mounted on a truck bed so that transportation of the wave simulator is facilitated. A surf craft is movably attached to a stationary structure so that a surf craft rider may practice the sport of surfing within the simulator.
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BACKGROUND OF THE INVENTION
The following invention relates to a rotating platen member for a printer.
More particularly, though not exclusively, the invention relates to a rotating platen member incorporating a platen surface, a capping device and a test print blotter for an A 4 pagewidth drop on demand printhead in a printer.
The overall design of a printer in which the rotating platen member can be utilized revolves around the use of replaceable printhead modules in an array approximately 8 inches (20 cm) long. An advantage of such a system is the ability to easily remove and replace any defective modules in a printhead array. This would eliminate having to scrap an entire printhead if only one chip is defective.
A printhead module in such a printer can be comprised of a “Memjet” chip, being a chip having mounted thereon a vast number of thermo-actuators in micro-mechanics and micro-electromechanical systems (MEMS). Such actuators might be those as disclosed in U.S. Pat. No. 6,044,646 to the present applicant, however, there might be other MEMS print chips.
The printhead, being the environment within which the rotating platen member of the present invention is to be situated, might typically have six ink chambers and be capable of printing four color process (CMYK) as well as infra-red ink and fixative. An air pump would supply filtered air to the printhead, which could be used to keep foreign particles away from its ink nozzles. The printhead module is typically to be connected to a replaceable cassette which contains the ink supply and an air filter.
Each printhead module receives ink via a distribution molding that transfers the ink. Typically, ten modules butt together to form a complete eight inch printhead assembly suitable for printing A 4 paper without the need for scanning movement of the printhead across the paper width.
The printheads themselves are modular, so complete eight inch printhead arrays can be configured to form printheads of arbitrary width.
Additionally, a second printhead assembly can be mounted on the opposite side of a paper feed path to enable double-sided high speed printing.
CO-PENDING APPLICATIONS
Various methods, systems and apparatus relating to the present invention are disclosed in the following co-pending applications filed by the applicant or assignee of the present invention simultaneously with the present application:
PCT/AU00/00518, PCT/AU00/00519, PCT/AU00/00520, PCT/AU00/00521, PCT/AU00/60522, PCT/AU00/00523, PCT/AU00/00524, PCT/AU00/00525, PCT/AU00/00526, PCT/AU00/00527, PCT/AU00/00528, PCT/AU00/00529, PCT/AU00/00530, PCT/AU00/00531, PCT/AU00/00532, PCT/AU00/00533, PCT/AU00/00534, PCT/AU00/00535, PCT/AU00/00536, PCT/AU00/00537, PCT/AU00/00538, PCT/AU00/00539, PCT/AU00/00540, PCT/AU00/00541, PCT/AU00/00542, PCT/AU00/00543, PCT/AU00/00544, PCT/AU00/00545, PCT/AU00/00547, PCT/AU00/00546, PCT/AU00/00554, PCT/AU00/00556, PCT/AU00/00557, PCT/AU00/00558, PCT/AU00/00559, PCT/AU00/00560, PCT/AU00/00561, PCT/AU00/00562, PCT/AU00/00563, PCT/AU00/00564, PCT/AU00/00565, PCT/AU00/00566, PCT/AU00/00567, PCT/AU00/00568, PCT/AU00/00569, PCT/AU00/00570, PCT/AU00/00571, PCT/AU00/00572, PCT/AU00/00573, PCT/AU00/00574, PCT/AU00/00575, PCT/AU00/00576, PCT/AU00/00577, PCT/AU00/00578, PCT/AU00/00579, PCT/AU00/00581, PCT/AU00/00580, PCT/AU00/00582, PCT/AU00/00587, PCT/AU00/00588, PCT/AU00/00589, PCT/AU00/00583, PCT/AU00/00593, PCT/AU00/00590, PCT/AU00/00591, PCT/AU00/00592, PCT/AU00/00584, PCT/AU00/00585, PCT/AU00/00586, PCT/AU00/00594, PCT/AU00/00595, PCT/AU00/00596, PCT/AU00/00597, PCT/AU00/00598, PCT/AU00/00516, PCT/AU00/00517, PCT/AU00/00511, PCT/AU00/00501, PCT/AU00/00502, PCT/AU00/00503, PCT/AU00/00504, PCT/AU00/00505, PCT/AU00/00506, PCT/AU00/00507, PCT/AU00/00508, PCT/AU00/00509, PCT/AU00/00510, PCT/AU00/00512, PCT/AU00/00513, PCT/AU00/00514, PCT/AU00/00515
The disclosures of these co-pending applications are incorporated herein by cross-reference.
OBJECTS OF THE INVENTION
It is an object of the present invention to provide a rotating platen member incorporating a platen surface, a capping device and a test print blotter for a printer.
It is another object of the present invention to provide a rotating platen member incorporating a platen surface, a capping device and a test print blotter suitable for the pagewidth printhead assembly as broadly described herein.
It is another object of the present invention to provide a rotating platen member incorporating a platen surface, a capping device and a test print blotter for a printhead assembly on which there is mounted a plurality of print chips, each comprising a plurality of MEMS printing devices.
It is yet another object of the present invention to provide a method of rotating a platen member incorporating a platen surface, a capping device and a test print blotter in a printer without damaging the printing devices in the printer.
SUMMARY OF THE INVENTION
The present invention provides a platen assembly for a printer, comprising:
a chassis to which there is mounted a printhead,
a pair of bearing members supported by the chassis and movable toward and away from the printhead,
a body rotatably mounted between said bearing members, the body having a platen surface extending therealong and a capping device extending therealong, the platen surface and capping device being selectively aligned with the printhead upon rotation of the body from one angular orientation to another, and
means to move said bearing members toward and away from said printhead during said rotation of the body so that the body does not damage the printhead
Preferably the means to move said bearing members toward and away from said printhead comprise a pair of end caps upon the body, each end cap having a cam surface or surfaces that engage with a protrusion affixed to or formed integrally with the chassis.
Preferably the body also includes a blotting device exiling therealong.
Preferably the capping device and the blotting device are offset from one another by 120 degrees about the body.
Preferably the bearing members are bearing moldings, each riding upon one or more tracks affixed to the chassis.
Preferably the tracks are straight and parallel so as to allow linear movement of the bearing members and body toward and away from the printhead.
Preferably the bearing members are resiliently biased in a direction toward the printhead
Preferably the said resilient bias is by means of a spring ending between the respective bearing member and the chassis.
Preferably the body includes a flat portion forming a base for attachment of a capping member, the capping member having a capper house and capper seal member for sealing a nozzle guard of said printhead.
Preferably the blotting device includes a shaped body of blotting material housed with the body and including a part projecting through a longitudinal slot in the body to form an exposed blotting surface.
The present invention also provides a method of capping a printhead in a printer in which there is provided a chassis to which the printhead is mounted, the method comprising:
providing a selectively rotatable platen body alongside the printhead, which platen body includes a platen surface extending therealong and a capping device also extending therealong,
rotating the platen body from an orientation wherein the platen surface is aligned with the printhead to an orientation wherein the capping device is aligned with the printhead, and
causing movement of the platen body away firm the printhead during rotation thereof, such that the body does not damage the printhead during rotation
Preferably the method also serves to absorb ink during a test print phase, wherein said platen body also incorporates a blotting device extending therealong and the method includes rotating the platen body into a position wherein the blotting device is aligned with the printhead.
Preferably the method also includes the step of moving the platen body toward and/or away from the printhead during rotation thereof so at to bring said blotting device into alignment with said printhead.
As used herein, the term “ink” is intended to mean any fluid which flows through the printhead to be delivered to a sheet. The fluid may be one of many different coloured inks, infra-red ink, a fixative or the like.
BRIEF DESCRIPTION OF THE DRAWINGS
A preferred foam of the present invention will now be described by way of example with reference to the accompanying drawings wherein:
FIG. 1 is a front perspective view of a print engine assembly
FIG. 2 is a rear perspective view of the print engine assembly of FIG. 1
FIG. 3 is an exploded perspective view of the print engine assembly of FIG. 1 .
FIG. 4 is a schematic front perspective view of a printhead assembly.
FIG. 5 is a rear schematic perspective view of the printhead assembly of FIG. 4 .
FIG. 6 is an exploded perspective illustration of the printhead assembly.
FIG. 7 is a cross-sectional end elevational view of the printhead assembly of FIGS. 4 to 6 with the section taken through the centre of the printhead.
FIG. 8 is a schematic cross-sectional end elevational view of the printhead assembly of FIGS. 4 to 6 taken near the left end of FIG. 4 .
FIG. 9A is a schematic end elevational view of mounting of the print chip and nozzle guard in the laminated stack structure of the printhead
FIG. 9B is an enlarged end elevational cross section of FIG. 9A
FIG. 10 is an exploded perspective illustration of a printhead cover assembly.
FIG. 11 is a schematic perspective illustration of an ink distribution molding.
FIG. 12 is an exploded perspective illustration showing the layers forming part of a laminated ink distribution structure according to the present invention.
FIG. 13 is a stepped sectional view from above of the structure depicted in FIGS. 9A and 9B,
FIG. 14 is a stepped sectional view from below of the structure depicted in FIG. 13 .
FIG. 15 is a schematic perspective illustration of a first laminate layer.
FIG. 16 is a schematic perspective illustration of a second laminate layer.
FIG. 17 is a schematic perspective illustration of a third laminate layer.
FIG. 18 is a schematic perspective illustration of a fourth laminate layer.
FIG. 19 is a schematic perspective illustration of a fifth laminate layer.
FIG. 20 is a perspective view of the air valve molding
FIG. 21 is a rear perspective view of the right hand end of the platen
FIG. 22 is a rear perspective view of the left hand end of the platen
FIG. 23 is an exploded view of the platen
FIG. 24 is transverse cross-sectional view of the platen
FIG. 25 is a front perspective view of the optical paper sensor arrangement
FIG. 26 is a schematic perspective illustration of a printhead assembly and ink limes attached to an ink reservoir cassette.
FIG. 27 is a partly exploded view of FIG. 26 .
DETAILED DESCRIPTION OF THE INVENTION
In FIGS. 1 to 3 of the accompanying drawings there is schematically depicted the core components of a print engine assembly, showing the general environment in which the laminated ink distribution structure of the present invention can be located. The print engine assembly includes a chassis 10 fabricated from pressed steel, aluminium, plastics or other rigid mater. Chassis 10 is intended to be mounted within the body of a printer and serves to mount a printhead assembly 11 , a paper feed mechanism and other rated components within the external plastics casing of a printer.
In general terms the chassis 10 supports the printhead assembly 11 such that ink is ejected therefrom and onto a sheet of paper or other pint medium being transported below the printhead then through exit slot 19 by the feed mechanism. The paper feed mechanism includes a feed roller 12 , feed idler rollers 13 , a platen generally designated as 14 , exit rollers 15 and a pin wheel assembly 16 , all driven by a stepper motor 17 . These paper feed components are mounted between a pair of bearing moldings 18 , which are in turn mounted to the chassis 10 at each respective end thereof.
A printhead assembly 11 is mounted to the chassis 10 by means of respective primed spacers 20 mounted to the chassis 10 . The spacer moldings 20 increase the printhead assembly length to 220 mm allowing clearance on either side of 210 mm wide paper.
The printhead construction is shown generally in FIGS. 4 to 8 .
The printhead assembly 11 includes a printed circuit board (PCB) 21 having mounted thereon various electronic components including a 64 MB DRAM 22 , a PEC chip 23 , a QA chip connector 24 , a microcontroller 25 , and a dual motor driver chip 26 . The printhead is typically 203 mm long and has ten print chips 27 (FIG. 13 ), each typically 21 mm long. These print chips 27 are each disposed at a slight angle to the longitudinal axis of the printhead (see FIG. 12 ), with a slight overlap between each print chip which enables continuous transmission of ink over the entire length of the array. Each print chip 27 is electronically connected to an end of one of the tape automated bond (TAB) films 28 , the other end of which is maintained in electrical contact with the undersurface of the printed circuit board 21 by means of a TAB film backing pad 29 .
The preferred print chip construction is as described in U.S. Pat. No. 6,044,646 by the present applicant. Each such print chip 27 is approximately 21 mm long, less man 1 mm wide and about 0.3 mm high, and has on its lower surface thousands of MEMS inkjet nozzles 30 , shown schematically in FIGS. 9A and 9B, arranged generally in six lines-one for each ink type to be applied. Each line of nozzles may follow a staggered pattern to allow closer dot spacing. Six corresponding lines of ink passages 31 extend through from the rear of the print chip to transport ink to the rear of each nozzle. To protect the delicate nozzles on the surface of the print chip each print chip has a nozzle guard 43 , best seen in FIG. 9A, with microapertures 44 aligned with the nozzles 30 , so that the ink drops ejected at high speed from the nozzles pass through these microapertures to be deposited on the paper passing over the platen 14 .
Ink is delivered to the print chips via a distribution molding 35 and laminated stack 36 arrangement forming part of the printhead 11 . Ink from an ink cassette 37 (FIGS. 26 and 27) is relayed via individual ink hoses 38 to individual ink inlet ports 34 integrally molded with a plastics duct cover 39 which forms a lid over the plastics distribution molding 35 . The distribution molding 35 includes six individual longitudinal ink ducts 40 and an air duct 41 which extend throughout the length of the array. Ink is transferred from the inlet ports 34 to respective ink ducts 40 via individual cross-flow ink channels 42 , as best seen with reference to FIG. 7 . It should be noted in this regard that although there are six ducts depicted, a different number of ducts might be provided. Six ducts are suitable for a printer capable of printing four color process (CMYK) as well as infra-red ink and fixative.
Air is delivered to the air duct 41 via an air inlet port 61 , to supply air to each print chip 27 , as described later with reference to FIGS. 6 to 8 , 20 and 21 .
Situated within a longitudinally extending stack recess 45 formed in the underside of distribution molding 35 are a number of laminated layers forming a laminated ink distribution stack 36 . The layers of the laminate are typically formed of micro-molded plastics material. The TAB film 2 extends from the undersurface of the printhead PCB 21 , around the rear of the distribution molding 35 to be received within a respective TAB film recess 46 (FIG. 21 ), a number of which are situated along a chip housing layer 47 of the laminated stack 36 . The TAB film relays electrical signals from the printed circuit board 21 to individual print chips 27 supported by the laminated structure.
The distribution molding, laminated stack 36 and associated components are best described with reference to FIGS. 7 to 19 .
FIG. 10 depicts the distribution molding cover 39 formed as a plastics molding and including a number of positioning spigots 48 which serve to locate the upper printhead cover 49 thereon.
As shown in FIG. 7, an ink transfer port 50 connects one of the ink ducts 39 (the fourth duct from the left) down to one of six lower ink ducts or transitional ducts 51 in the underside of the distribution molding. All of the ink ducts 4 D have corresponding transfer ports 50 communicating with respective ones of the transitional ducts 51 . The transitional ducts 51 are parallel with each other but angled acutely with respect to the ink ducts 40 so as to line up with the rows of ink holes of the first layer 52 of the laminated stack 36 to be described below.
The first layer 52 incorporates twenty four individual ink holes 53 for each of ten print chips 27 . That is, where ten such print chips are provided, the first layer 52 includes two hundred and forty ink holes 53 . The first layer 52 also includes a row of air holes 54 alongside one longitudinal edge thereof.
The individual groups of twenty four ink holes 53 are formed generally in a rectangular array with aligned rows of ink holes. Each row of four ink holes is aligned with a transitional duct 51 and is parallel to a respective pint chip.
The undersurface of the first layer 52 includes underside recesses 55 . Each recess 55 communicates with one of the ink holes of the two centre-most rows of four holes 53 (considered in the direction transversely across the layer 52 ). That is, holes 53 a (FIG. 13) deliver ink to the right hand 55 a shown in FIG. 14, whereas the holes 53 b deliver ink to the left most underside recesses 55 b shown in FIG. 14 .
The second layer 56 includes a pair of slots 57 , each receiving ink from one of the underside recesses 55 of the first layer.
The second layer 56 also includes ink holes 53 which are aligned with the outer two sets of ink holes 53 of the first layer 52 . That is, ink passing through the outer sixteen ink holes 53 of the first layer 52 for each print chip pass directly through corresponding holes 53 passing through the second layer 56 .
The underside of the second layer 56 has formed therein a number of transversely extending channels 58 to relay ink passing through ink holes 53 c and 53 d toward the centre. These channels extend to align with pair of slots 59 formed though a third layer 60 of the laminate. It should be noted in this regard that the third layer 60 of the laminate includes four slots 59 corresponding with each print chip, with two inner slots being aligned with the pair of slots formed in the second layer 56 and outer slots between which the inner slots reside.
The third layer 60 also includes an array of air holes 54 aligned with the corresponding air hole arrays 54 provided in the first and second layers 52 and 56 .
The third layer 60 has only eight remaining ink holes 53 corresponding with each print chip. These outermost holes 53 are aligned with the outermost holes 53 provided in the first and second laminate layers. As shown in FIGS. 9A and 9B, the third layer 60 includes in its underside surface a transversely extending channel 61 corresponding to each hole 53 . These channels 61 deliver ink from the corresponding hole 53 to a position just outside the alignment of slots 59 therethrough.
As best seen in FIGS. 9A and 9B, the top three layers of the laminated stack 36 thus serve to direct the ink (shown by broken hatched lines in FIG. 9B) from the more widely spaced ink ducts 40 of the distribution molding to slots aligned with the ink passages 31 through the upper surface of each print chip 27 .
As shown in FIG. 13, which is a view from above the laminated stack, the slots 57 and 59 can in fact be comprised of discrete co-linear spaced slot segments.
The fourth layer 62 of the laminated stack 36 includes an array of ten chip-slots 65 each receiving the upper portion of a respective print chip 27 .
The fifth and final layer 64 also includes an array of chip-slots 65 which receive the chip and nozzle guard assembly 43 .
The TAB film 28 is sandwiched between fourth and fifth layers 62 and 64 , one or both of which can be provided with recesses to accommodate the thickness of the TAB film.
The laminated stack is formed as a precision micro-molding, injection molded in an Acetal type material. It accommodates the array of print chips 27 with the TAB film ala attached and mates with the cover molding 39 described earlier.
Rib details in the underside of the micro-molding provides sit for the TAB film when they are bonded together. The TAB film forms the underside wall of the printhead module, as there is sufficient structural integrity between the pitch of the ribs to support a flexible film. The edges of the TAB film seal on the underside wall of the cover molding 39 . The chip is bonded onto one hundred micron wide ribs that run the length of the micro-molding, providing a final ink feed to the print nozzles.
The design of the micro-molding allow for a physical overlap of the print chips when they are butted in a line. Because the printhead chips now form a continuous strip with a generous tolerance, they can be adjusted digitally to produce a near perfect print pattern rather than relying on very close toleranced moldings and exotic materials to perform the same function. The pitch of the modules is typically 20.33 mm.
The individual layers of the lied stack as well as the cover molding 39 and distribution molding can be glued or others bonded together to provide a sealed unit. The ink paths can be sealed by a bonded transparent plastic film serving to indicate when inks are in the ink paths so they can be fully capped off when the upper part of the adhesive film is folded over. Ink charging is then complete
The four upper layers 52 , 56 , 60 , 62 of the laminated stack 36 have aligned air holes 54 which communicate with air passages 63 formed as channels formed in the bottom surface of the fourth layer 62 , as shown in FIGS. 9 b and 13 . These sages provide pressurised air to the space between the print chip surface and the nozzle guard 43 whilst the printer is in operation. Air from this pressurised zone passes through the micro-apertures 44 in the nozzle guard, thus preventing the build-up of any dust or unwanted contaminants at those apertures. This supply of pressurised air can be turned off to prevent ink drying an the nozzle surfaces during periods of non-use of the printer, control of this air supply being by means of the air valve assembly shown in FIGS. 6 to 8 , 20 and 21 .
With reference to FIG. 6 to 8 , within the air duct 41 of the printhead there is located an air valve molding 66 formed as a channel with a series of apertures 67 in its base. The spacing of these apertures corresponds to air passages 68 formed in the base of the air duct 41 (see FIG. 6 ), the air valve molding being movable longitudinally within the air duct so that the apertures 67 can be brought into alignment with passages 68 to allow supply the pressurized air through the laminated stack to the cavity between the print chip and the nozzle guard or moved act of alignment to close off the air supply. Compression springs 69 maintain a sealing inter ngagement of the bottom of the air valve molding 66 with the base of the air duct 41 to prevent leakage when the valve is closed.
The air valve molding 66 has a cam follower 70 tending from one end thereof which engages an air valve cam surface 71 on an end cap 74 of the platen 14 so as to selectively move the air valve molding longitudinally within the air duct 41 according to the rotational positional of the multi-function platen 14 , which may be rotated between printing, capping and blotting positions depending on the operational status of the printer, as will be described below in more detail with reference to FIGS. 21 to 24 . When the platen 14 is in its rotational position for printing, the cam holds the air valve in its open position to supply air to the print chip surface, whereas the platen is rotated to the non-printing position in which it caps off the micro-apertures of the nozzle guard, the cam moves the air valve molding to the valve closed position.
With reference to FIGS. 21 to 24 , the platen member 14 extends parallel to printhead, supported by a rotary shaft 73 mounted in bearing molding 18 and rotatable by means of gear 79 (see FIG. 3 ). The shaft is provided with a right hand end cap 74 and left hand end cap 75 at respective ends, having cams 76 , 77 .
The platen member 14 has a platen surface 78 , a capping portion 80 and an exposed blotting portion 81 extending along its length, each seperated by 120°. During printing, the platen member is rotated so that the platen surface 78 is positioned opposite the printhead so that the platen surface acts as a support for that portion of the paper being printed at the time. When the printer is not in use, the plan member is rotated so that the capping potion 80 contacts the bottom of the printhead, sealing in a locus surrounding the microapertures 44 . Thus, in combination with the closure of the air valve by means of the air valve arrangement when the platen 14 is in its capping position, maintains a closed atmosphere at the print nozzle surface. This serves to reduce evaporation of the ink solvent (usually water) and thus reduce drying of ink on the pint nozzles while the printer is not in use.
The third function of the rotary plate member is as an ink blotter to receive ink from priming of the print nozzles at printer start up or maintenance operations of the printer. During this printer mode, the platen member 14 is rotated so that the exposed blotting portion 81 is located in the ink ejection path opposite the nozzle guard 43 . The exposed blotting portion 81 is an ear part of a body of blotting material 82 inside the platen member 14 , so that the ink received on the exposed portion 81 is drawn into the body of the platen member.
Further details of the platen member construction may be seen from FIGS. 23 and 24. The platen member consists generally of an extruded or molded hollow platen body 83 which forms the platen surface 78 and receives the shaped body of blotting mater 82 of which a put projects through a longitudinal slot in the platen body to form the exposed blotting surface 81 . A flat portion 84 of the platen body 83 serves as a base for attachment of the capping member 80 , which consists of a capper housing 85 , a capper seal member 86 and a foam member 87 for contacting the nozzle guard 43 .
With reference again to FIG. 1, each bearing molding 18 rides on a pair of vertical rails 101 . That is, the capping assembly is mounted to four vertical rails 101 enabling the assembly to move vertically. A spring 102 under either end of the capping assembly biases the assembly into a raised position, maintaining cams 76 , 77 in contact with the spacer projections 100 .
The printhead 11 is capped when not is use by the full-width capping member 80 using the elastomeric (or similar) seal 86 . In order to rotate the platen assembly 14 , the main roller drive motor is reversed. This brings a reversing gear into contact with the gear 79 on the end of the platen assembly and rotates it into one of its three fictional positions, each separated by 120°.
The cams 76 , 77 on the platen end caps 74 , 75 co-operate with projections 100 on the respective printhead spacers 20 to control the spacing between the platen member and the printhead depending on the rotary position of the platen member. In this manner, the platen is moved away from the printhead during the transition between platen positions to provide sufficient clearance from the printhead and moved beck to the appropriate distances for its respective paper support, capping and blotting functions.
In addition, the cam arrangement for the rotary platen provides a mechanism for fine adjustment of the distance between the platen surface and the printer nozzles by slight rotation of the platen 14 . This allows compensation of the nozzle-platen distance in response to the thickness of the paper or other material being printed, as detected by the optical paper thickness sensor arrangement illustrated in FIG. 25 .
The optical paper sensor includes an optical sensor 88 mounted on the lower surface of the PCB 21 and a sensor flag arrangement mounted on the arms 89 protruding from the distribution molding. The flag arrangement comprises a sensor flag member 90 mounted on a shaft 91 which is biased by torsion sprig 92 . As paper enters the feed rollers, the lowermost portion of the flag member contacts the paper and rotates against the bias of the spring 92 by an amount dependent on the paper thickness. The optical sensor detects this movement of the flag member and the PCB responds to the detected paper thickness by causing compensatory rotation of the platen 14 to optimize the distance between the paper surface and the nozzles.
FIGS. 26 and 27 show attachment of the illustrated printhead assembly to a replaceable ink cassette 93 . Six different ink are supplied to the printhead through hoses 94 leading from an array of female ink valves 95 located inside the printer body. The replaceable cassette 93 containing a six compartment ink bladder and corresponding male valve array is inserted into the printer and mated to the valves 95 . The cassette also contains an air inlet 96 and air filter (not shown), and mates to the air intake connector 97 situated beside the ink valves leading to the air pump 98 supplying filtered air to the printhead. A QA chip is included in the cassette. The QA chip meets with a contact 99 located between the ink valves 95 and air intake connector 96 in the printer as the cassette is inserted to provide communication the QA chip connector 24 on the PCB.
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A platen assembly for a printer includes a chassis to which there is mounted a printhead and a pair of bearing moldings supported by the chassis and movable toward and away from the printhead. A platen body ( 83 ) is rotatably mounted between the bearing moldings and includes a platen surface ( 78 ) extending therealong, a capping device ( 80 ) extending therealong and a blotting device ( 81 ) also extending therealong. Each device is selectively aligned with the printhead upon a rotation of the body between respective angular orientation. The body includes end caps having cam surfaces engageable with a projection affixed to the chassis to cause movement of the bearing members toward and away from the printhead during rotation of the body so that the body does not damage the printhead.
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RELATED APPLICATIONS
This application is a continuation of Ser. No. 09/742,126 file date Dec. 22, 2000, now U.S. Pat. No. 6,408,469, issued Jun. 25, 2002, which is a continuation-in-part of Ser. No. 09/482,591 file date Jan. 13, 2000, now U.S. Pat. No. 6,243,900, issued Jun. 12, 2001, all of which are incorporated herein by referenced in their entirety.
BACKGROUND OF THE INVENTION
The present invention relates generally to a bed construction, and more particularly to a bed construction having a one-sided mattress assembly supported on a rigid foundation that offers significant reduction in the amount of permanent deflection or sagging of sleeping surface of the mattress.
A conventional inner spring mattress as known in the bedding industry generally comprises a resilient construction consisting of two sleep surfaces (a top layer and a bottom layer) enclosing an assembly of wire springs. The wire springs are typically covered with padding layers on the top and bottom surfaces, and the whole assembly is encased within a ticking, often quilted, that is sewn closed around its periphery to a border or boxing. For many years, one form of spring assembly construction has been known as Marshall construction. In Marshall construction, individual wire coils are each encapsulated in fabric pockets and attached together in strings which are arranged to form a closely packed array of coils in the general size of the mattress. Examples of such construction are disclosed in U.S. Pat. Nos. 685,160, 4,234,983, 4,234,984, 4,439,977, 4,451,946, 4,523,344, 4,578,834, 5,016,305 and 5,621,935, the disclosures of which are incorporated herein by reference in their entireties.
Conventionally, inner spring mattresses, with either pocketed coils or open coils, have had identical top and bottom layers. During normal life of such conventional mattresses some degree of permanent deflection, or sag, can develop in the mattress surfaces due to compaction of the component padding materials in the top and bottom layers. This permanent deflection can interfere with the mattresses' intended function of providing a supportive and resilient sleep surface. Inner spring mattress manufacturers recommend periodically rotating and turning over the mattress thereby utilizing the top and bottom sleep surfaces in order to counteract, minimize, and/or delay the aforementioned permanent deflection or sag. Under continued use, this compaction or sag becomes more permanent. The degree of permanent deflection is directly related to the type and amount of padding installed both over and under the wire spring core assembly. To remedy this shortcoming, manufacturers utilize materials that produce less permanent compaction. These materials are generally more dense but can be less comfortable and more expensive.
Conventional foundations, such as box springs, often contributed to the problem of sagging by providing a compressible top layer. Any additional compaction of the top layer of the foundation contributes to the overall sagging of the sleeping surface of the mattress.
Accordingly, it is desirable to provide a bed construction having an inner spring mattress assembly which exhibits a reduced amount of permanent deflection due to compaction of padding materials while at the same time exhibiting substantial comfort in use. It is further desirable to provide a mattress assembly that can be constructed by conventional known manufacturing techniques. Still further, it is desirable to provide a mattress assembly that is cost-effective to produce.
SUMMARY OF THE INVENTION
The present invention improves over the prior art by providing a bed construction with a one-sided mattress assembly supported on a rigid foundation. The one-sided mattress assembly includes a core of wire springs including, but not limited to, pocketed or open coil springs. The spring core of the mattress is covered by a layer of resiliently compressible material covering the upper sleeping surface thereof. The spring core of the mattress is supported on a bottom layer constructed of a substantially rigid material that is not generally compressible. The core of coil springs is attached to the bottom layer around its periphery. The rigid bottom layer of the mattress assures firm support for the coil springs and thereby reduces sagging that may result from the springs being poorly supported by the compressible padding under the springs of a conventional two-sided mattress.
In connection with the present invention, the padding for the top layer is selected to resist permanent compaction or deflection. Moreover, padding is only needed on the top layer of the mattress thereby reducing by one-half the amount of padding required. Consequently, the mattress construction of the present invention with a padded top layer and a rigid bottom layer necessarily reduces the amount of material that is subject to permanent compaction and therefore reduces the amount of permanent deflection of the mattress overall. Maintenance of the mattress of the present invention by rotating or turning the mattress over is also avoided.
In order to further reduce sagging of the sleeping surface of the mattress, a rigid foundation is provided to give further support to the rigid bottom layer of the one-sided mattress and therefore the spring core.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other novel features and advantages of the invention will be better understood upon a reading of the following detailed description taken in conjunction with the accompanying drawings wherein.
FIG. 1 is an exploded cross-section view of a conventional two-sided inner spring mattress;
FIG. 2 is an exploded cross-sectional view of a one-sided inner spring mattress constructed according to the principles of the invention;
FIG. 3 is a schematic plan view of a complete assembly of Marshall coils for use in the mattress construction according to the present invention illustrated in FIG. 2;
FIG. 4 is a partial perspective view, partly broken away, of the Marshall coil assembly illustrated in FIG. 3; and
FIG. 5 is a partially exploded elevation view of a foundation used in connection with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawings, and initially to FIG. 1, a conventional two-sided mattress is illustrated in exploded cross-section and designated generally by the reference numeral 10 . The conventional mattress 10 includes as a principal component a wire spring assembly 12 of Marshall spring coils, as will be described in detail hereinafter and which comprises the central core of the mattress 10 . The mattress 10 could also incorporate an assembly of open coil springs or other wire inner springs. The mattress 10 has an upper sleep surface 14 and a lower sleep surface 16 , and therefore, is of a conventional type intended to be turned over periodically to help minimize compaction of its padding material and the resulting sagging of the mattress 10 . Padding material 18 , which is identical on both sides 14 and 16 includes a layer of closed-cell foam such as polyurethane. Covering the material 18 , on both sides of the mattress, is a ticking layer 20 which may be quilted and which may include additional foam in a manner well-known in the art. The ticking layers 20 are fastened such as by sewing to a border 22 which extends around the entire periphery of the core 12 of coil springs.
Turning now to FIG. 2, a mattress 30 constructed according to the invention is shown in exploded cross-section. The mattress 30 , like the conventional mattress 10 illustrated in FIG. 1, has a central core 12 of the Marshall coils. The mattress 30 , however, may have a central core 12 comprising open coil springs or other wire springs. An upper sleep surface 34 is formed over the central core 12 by a layer of foam padding 18 and a layer of ticking 20 . In accordance with the invention, however, the mattress 30 has an underside 36 , positioned under the central core 12 and which comprises a substantially rigid layer 38 of material covered by a thin layer 40 of a non-woven sheeting. A border 42 connects the ticking 20 and sheeting layer 40 and extends around the periphery of the coil spring assembly 12 . A lower border wire 44 is secured to the coil spring assembly 12 around its periphery as well as to the layer 38 such as by hog rings 46 .
FIGS. 3 and 4 illustrate one form of mattress core 12 of the aforementioned Marshall coil construction. In this construction, closely positioned coil springs are aligned in a string assembly 50 (FIG. 4) wherein individual springs 52 are each encapsulated within a pocket of 54 of fabric material 56 which may be sewn or ultrasonically welded to create the pockets 54 and to create a unitary Marshall coil type assembly 12 . An example of such construction is more fully disclosed in U.S. Pat. No. 5,621,935 which is commonly assigned herewith and the disclosure of which is incorporated herein by reference in its entirety. A person of ordinary skill in the art will appreciate that opened coil springs or other wire springs may be used for the mattress core 12 as well as Marshall coil springs.
As previously described, the sleeping surface 34 comprises a layer of foam padding 18 and a layer of ticking 20 . The ticking 20 is of conventional construction. In accordance with the present invention, however, the foam padding 18 is specifically selected to provide comfort yet minimize compaction. Particularly, the foam padding 18 is a high density polyurethane foam having a density from about 1.0 lbs./cu. ft. to 2.5 lbs./cu. ft. The foam layer 18 also has a firmness in a range of between 10 and 55 ILD, where “ILD” refers to the standard Indented Load Deflection test. Within the ranges specified, the foam padding 18 for the sleeping surface 34 is selected to provide varying degrees of firmness or softness to accommodate individual preferences.
The relatively rigid bottom layer 38 is a high density polyurethane foam having a density of approximately 1.85 lbs./cu. ft. The foam layer 38 also has a firmness above 30 ILD. In practice, an ILD above 55 has proven to be most effective based on considerations of cost and durability. Other rigid materials may be used in place of the foam layer 38 . Such materials may include solid plastic, wood, or other nonyielding rigid materials. To the extent such materials for the layer 38 yield to pressure, such materials must have at least a high degree of recoverability once the pressure has been removed so that the materials are not compacted.
Turning to FIG. 5, there is shown a foundation 60 for use in connection with the construction of a bed in accordance with the present invention. The most important aspect of the foundation 60 for the present invention is providing a rigid top surface 62 to support the mattress 30 (FIG. 2 ). Rigid support of the mattress 30 by the foundation 60 further reduces the amount of sagging of the sleeping surface 34 . In order to achieve rigid support of the mattress 30 , the foundation 60 is constructed in accordance with the disclosure of commonly assigned U.S. Pat. No. 5,940,908, and particularly FIG. 6 of that patent.
The foundation 60 has a structural frame 64 . The structural frame 64 has a rectangular border including a pair of side rails (only rail 66 is shown in FIG. 5 ). The side rails may be formed from standard lumber of construction grade in nominal 1×3 size, connected at a head end of the frame 64 by a head end rail 68 and at the foot end of the frame 64 by a foot end rail 70 . The end rails 68 and 70 may be formed, for example, from a lower 1×2 end filler slat which butts the side rails in the plane thereof. Cross slats 72 , 74 , 76 , 78 , 80 , 82 , and 84 are positioned on the upper surfaces of the side rails and extend laterally to span the transverse distance between the side rails. Optionally, a longitudinally extending center support rail may be attached to an undersurface of the head and foot rails 68 and 70 and secured to an underside of each of the cross slats 72 - 84 to provide additional structural integrity and strength for the frame 64 .
As further illustrated in FIG. 5, it will be seen that cross slats 80 , 82 , and 84 are centrally positioned along the length of the frame 10 and have an L-shaped cross-section configuration. However, it should be noted that the L-shaped cross slats may be positioned elsewhere along the length of the frame 64 or be employed in a lesser or a greater number. The L-shaped cross slats 80 , 82 , and 84 act as reinforcing braces or beams to reduce deflection of the frame 64 .
As illustrated in FIG. 5, the non-resilient bedding foundation 60 has a mattress support assembly 86 . The mattress support assembly 86 comprises a plurality of wire support members 88 supported on and attached to the cross slats 68 , 70 , 72 , 74 , 76 , 78 , 80 , 82 , and 84 . In this embodiment, a top layer 63 is applied over the assembly 86 and a cover or ticking 90 is provided to form the exterior surface for the entire foundation 60 . The top layer 63 is similar in construction and performance to the bottom layer 68 of the mattress 30 . Particularly, the top layer 63 is designed to provide a rigid support surface for the mattress 30 with a firmness above 30 ILD and specifically above 55 ILD.
The one-sided inner spring mattress 30 constructed according to the invention offers considerable advantages over prior art conventional two-sided mattresses in terms of reducing the amount of permanent deflection of the sleeping surface due to undesirable compaction of padding materials. Because the mattress 30 essentially has a 50 percent reduction in padding due to the rigid bottom layer 38 , the coil assembly 12 does not settle into and compact a lower padding layer as would happen with a two-sided mattress of conventional construction having identical padding layers on both sides. The addition of a rigid foundation beneath the one-sided mattress 30 also provides additional support for the coil springs of the mattress 30 and thus helps further reduce sagging.
The one-sided mattress 30 of the invention also offers the advantage of eliminating maintenance of the mattress by periodically turning it over as is recommended for conventional two-sided mattresses. Accordingly, the one-sided mattress 30 is more convenient for the consumer to use. Further, the Marshall coil construction or open spring construction use conventional materials so that the one-sided mattress 30 may be readily manufactured by techniques that are well known in the industry. The foundation 60 likewise can be constructed using conventional manufacturing techniques.
While the present invention has been described in connection with certain embodiments thereof, it will be apparent to those skilled in the art that many changes and modifications can be made without departing from the true spirit and scope of the present invention. Accordingly, it is intended by the appended claims to cover all such changes and modifications as come within the scope of the invention.
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A bed construction having a one-sided mattress assembly supported on a rigid foundation. The one-sided mattress assembly includes a core of pocketed coil springs having a layer of resiliently compressible material covering the upper surface thereof and having a bottom surface constructed of a substantially rigid material without a compressible layer. The core of coil springs is attached to the bottom surface around its periphery. The foundation has a rigid inner construction and a noncompressible top layer. The bed construction reduces the amount of compressible padding in the mattress by one-half and consequently the mattress is capable of exhibiting a substantial reduction in the amount of permanent deflection in use.
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BACKGROUND OF THE INVENTION
The present invention relates to a torque transmitting unit in the power train of a motor vehicle for transferring torque between a drive unit, in particular a combustion engine, having an output shaft, in particular a crankshaft, and a transmission having at least one input shaft, in particular two input shafts, with at least one clutch device and at least one vibration damping unit having an input part and an output part, which is connected between the output shaft of the drive unit and the clutch device, the clutch unit having a clutch housing section, in particular a clutch cover, which limits the volume accommodating the clutch device and is supported by a transmission housing section, the vibration damping unit being positioned in the volume limited by the clutch housing section, which accommodates the clutch device.
The object of the invention is to create a torque transmission device described above, optimized with regard to the construction space, which is simply constructed and is capable of being manufactured economically.
SUMMARY OF THE INVENTION
The problem is solved in a torque transmitting unit in the power train of a motor vehicle for transferring torque between a drive unit, in particular a combustion engine, having an output shaft, in particular a crankshaft, and a transmission having at least one input shaft, in particular two input shafts, with at least one clutch device and at least one vibration damping unit having an input part and an output part, which is connected between the output shaft of the drive unit and the clutch device, the clutch unit having a clutch housing section, in particular a clutch cover, which limits the volume accommodating the clutch device and is supported by a transmission housing section, the vibration damping unit being positioned in the volume limited by the clutch housing section, which accommodates the clutch device, in that both the input part and the output part of the vibration damping unit or the input part of the clutch device are borne or supported in the radial direction directly or indirectly on the clutch housing section. The vibration damping unit is preferably a damped flywheel. Due to the support of the device according to the invention, bearing devices between the input part and/or the output part of the vibration damping unit and the transmission input shaft or the output shaft of the combustion engine may be dispensed with. In addition, the tolerance chain from the output shaft of the combustion engine to the transmission input shaft is reduced.
The problem stated above is also solved in a torque transmitting unit described above by having the vibration damping unit positioned radially outside of the clutch device and overlapping it in the axial direction. That makes it possible to save construction space in the axial direction.
The problem stated above is also solved in a torque transmitting unit described above by having the input part of the vibration damping unit comprise a vibration damping unit cage in which spring devices are at least partially contained, which are engaged by the output part of the vibration damping unit. An essentially circular-ring-shaped connecting piece, which extends out of the vibration damping unit cage, is preferably positioned between the clutch housing section and the clutch device, viewed in the axial direction.
A preferred exemplary embodiment of the torque transmitting unit is characterized in that the input part of the vibration damping unit is welded to a hub part which is supported in the radial direction on the clutch housing section. The hub part can also be formed in a single piece with the input part of the vibration damping unit.
Another preferred exemplary embodiment of the torque transmitting unit is characterized in that the hub part includes a hub bearing part which is of conical design on the inside and is provided with internal toothing that engages the external toothing which is formed on a coupling part that has a section which is formed complementarily to the cone of the hub bearing part. A separable attachment of the coupling part to the hub part is made possible through the conical, toothed sections which are engaged with each other.
Another preferred exemplary embodiment of the torque transmitting unit is characterized in that the coupling part is attached to the hub bearing part so that it can repeatedly be separated non-destructively, in particular with the help of a screw connection. However, the coupling part can also be formed in a single piece with the hub part or welded to it.
Another preferred exemplary embodiment of the torque transmitting unit is characterized in that the output part of the vibration damping unit is supported on the hub part, in particular in both the axial and the radial directions. For this purpose an essentially circular-ring-shaped indentation may be provided on the hub part, having a rectangular cross section which engages an essentially complementarily shaped elevation which is formed on the output part.
Another preferred exemplary embodiment of the torque transmitting unit is characterized in that the clutch device includes a wet-operating clutch arrangement, in particular a multiple-disk clutch arrangement. Preferably, the clutch device includes two wet-operating multiple-disk clutch arrangements.
Another preferred exemplary embodiment of the torque transmitting unit is characterized in that two wet-operating clutch arrangements are positioned coaxially and overlapping each other in the axial direction. That makes it possible to save construction space in the axial direction.
In a power train of a motor vehicle, the problem indicated above is solved by installing a torque transmitting unit described above.
BRIEF DESCRIPTION OF THE DRAWINGS
Additional advantages, characteristics, and details of the present invention are evident from the following description, in which various embodiments are described in detail with reference to the drawing. The characteristics mentioned in the claims and in the description may be essential to the invention individually by themselves or in any combination. The figures show the following:
FIG. 1 shows a half-sectional view of a torque transmitting unit according to the present invention, in accordance with a first exemplary embodiment;
FIG. 2 shows an enlarged cutout of a longitudinal section of a torque transmitting unit according to the present invention in accordance with another exemplary embodiment; and
FIG. 3 shows a half-sectional view of a torque transmitting unit according to the present invention, in accordance with another exemplary embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Part of a power train 1 of a motor vehicle is illustrated in FIG. 1 . Positioned between a drive unit 3 , in particular a combustion engine, and a transmission 5 , is a wet-operating double clutch 6 of multiple-disk design. Connected between drive unit 3 and double clutch 6 is a vibration damping unit 8 . The vibration damping unit is preferably a two-mass flywheel.
An output shaft (not shown) of drive unit 3 is coupled with a drive output part 10 . Drive output part 10 has essentially the form of a circular ring extending in the radial direction, to which a starter gear rim 11 is welded radially on the outside. Drive output part 10 is connected through a screw connection 12 (of a plurality of screw connections which are evenly distributed around the circumference of drive output part 10 ) in a rotationally fixed connection to a connecting piece 14 . Welded radially on the inside of connecting part 14 is a hub part 15 , to which in turn an input part 17 of vibration damping unit 8 is welded. Positioned radially outside of hub part 15 and in the axial direction between connecting part 14 and input part 17 of vibration damping unit 8 is a clutch cover 20 , which extends essentially in the radial direction. Clutch cover 20 , with a seal 21 interposed, is supported on a transmission housing section 24 , which is shown with broken lines in FIG. 1 . Transmission section 24 and clutch cover 20 , supported on it, are rigidly attached to the support structure of a motor vehicle.
Clutch cover 20 has radially on its inside an essentially round cylindrical jacket-like bearing body 25 . Positioned on the side facing drive unit 3 , between bearing body 25 of clutch cover 20 and hub part 15 , is a sealing device 26 , in particular a radial shaft seal ring. Positioned on the side facing transmission 5 , between bearing body 25 of clutch cover 20 and hub part 15 , is a radial bearing device 28 , in particular a deep-groove ball bearing. Radial bearing device 28 is supported in the axial direction, toward drive unit 3 , on a shoulder 27 , which runs radially around the inside approximately in the middle of bearing body 25 of clutch cover 20 . Hub part 15 is supported on clutch cover 20 by means of radial bearing device 28 . Because of the support on shoulder 27 of bearing body 25 of clutch cover 20 , support in the axial direction toward drive unit 3 is also made possible.
An additional mass 29 is attached radially on the outside of input part 17 of vibration damping unit 8 . The attachment of additional mass 29 to input part 17 of vibration damping unit 8 is preferably accomplished by a welded joint, as indicated in FIG. 1 . In addition, attached to input part 17 of vibration damping unit 8 is a vibration damping cage 30 , which incorporates a plurality of spring devices 32 which extend in the circumferential direction. An output part 34 of vibration damping unit 8 , which is shown in FIG. 1 with broken lines, engages spring devices 32 . Output part 34 is attached to a connecting part 36 , which forms the input part of the clutch. Output part 34 of vibration damping unit 8 may also be made in a single piece with clutch input part 36 . Clutch input part 36 transitions internally into a bearing cup 38 , which is supported in both the radial and axial directions and toward drive unit 3 in a complementarily formed bearing recess 40 , which is provided on the side of hub part 15 that faces transmission 5 .
Clutch input part 36 is joined in one piece to an outer disk carrier 41 of a first multiple-disk clutch arrangement 42 . Positioned radially inside outer disk carrier is an inner disk carrier 44 , which is attached to a hub part 46 . Hub part 46 of first multiple-disk clutch arrangement 42 is connected in a rotationally-fixed connection to a first transmission input shaft 47 .
Clutch input part 36 is connected in a rotationally fixed connection through a connecting part 50 , to which an additional mass 51 is attached radially on the outside, to an outer disk carrier 52 of a second multiple-disk clutch arrangement 54 , which is positioned radially inside of first multiple-disk clutch arrangement 42 . The two multiple-disk clutch arrangements 42 and 54 completely overlap each other in the axial direction. The second multiple-disk clutch arrangement 54 has an inner disk carrier 56 which is attached to a hub part 58 . Hub part 58 is connected in a rotationally fixed connection to a second transmission input shaft 59 , which is designed as a hollow shaft. The first transmission input shaft 47 is positioned in hollow shaft 59 so that it can rotate.
The two multiple-shaft clutch arrangements 54 and 42 are operated by means of operating levers 61 and 62 , whose radially inner ends are supported on operating bearings 65 , 66 . Operating bearings 65 and 66 are operated in the axial direction with the help of operating pistons 67 , 68 . Operating pistons 67 and 68 are arranged in fixed positions with respect to operating levers 61 and 62 , which pivot with clutch input part 36 .
FIG. 2 shows a longitudinal sectional view of a cutout of a clutch cover 80 , which is connected radially on the inside in a single piece to a bearing body 81 . Clutch cover 80 is positioned between two connecting pieces 82 and 85 which are attached to each other by a welded seam radially on the inside, in reference to clutch cover 80 . Welded seam 86 is located radially on the inside, partially under a bearing device 88 , which, viewed in the radial direction, is positioned between bearing body 81 of clutch cover 80 and the axially extending attaching sections of connecting parts 82 and 85 . Bearing device 88 is a deep-groove ball bearing, which is supported in the axial direction both on clutch cover 80 and on connecting parts 82 and 85 . Deep-groove ball bearing 88 is supported radially outwardly in the axial direction on a shoulder 89 , which is provided radially inwardly on bearing body 81 . On the opposite side, deep-groove ball bearing is supported radially outwardly on a supporting ring 91 , which is fixed in the axial direction on bearing body 81 , being partially accommodated in a groove which runs radially inside in bearing body 81 . Radially inwardly, deep-groove ball bearing 88 is supported in an axial direction on a fixing element 92 of hardened material. Fixing element 92 in turn is supported in the axial direction on connecting part 82 . In the opposite radial direction, deep-groove ball bearing 88 is supported radially inwardly on connecting part 85 . In addition, between bearing body 81 of clutch cover 80 and the attaching section of connecting part 82 , which extends in the radial direction, is a radial shaft seal ring 90 .
Radially inside connecting parts 82 and 85 , a transmission shaft 94 is rotatably mounted with the help of a radial bearing device 96 . Between connecting part 82 and radial bearing device 96 is a sleeve 98 of hardened material. Sleeve 98 is connected in a single piece to a closing wall 99 , which is positioned at the end of transmission input shaft 94 , which is internally hollow, at a small distance from it. The open end of transmission input shaft 94 is closed by a cover 101 , through which the lubricants can pass from the interior of transmission input shaft 94 to reach bearing device 96 .
Transmission input shaft 94 is connected through toothing 103 in a rotationally fixed connection to an output part 105 of a clutch device or vibration damping unit. An axial bearing device 108 is positioned in the axial direction between output part 105 and connecting part 85 . A retaining ring 110 , which is positioned partially in a groove in transmission input shaft 94 , fixes transmission input shaft 94 in an axial position relative to output part 105 . Connecting part 82 is connected in a rotationally fixed connection to an output shaft (not shown) of a drive unit, in particular a combustion engine. Connecting part 85 is the input part of a vibration damping unit.
FIG. 3 shows an exemplary embodiment of a torque transmitting unit according to the present invention, similar to that in FIG. 1 . The same reference labels are used to designate the same or similar parts. To avoid repetitions, we refer to the preceding description of FIG. 1 . In the following description we will only go into the differences between the two embodiments.
In the exemplary embodiment shown in FIG. 3 , hub part 15 is not formed in one piece but in two parts. Hub part 15 includes a hub bearing part 121 which is releasably attachable, i.e., repeatedly non-destructively separable, in a rotationally fixed attachment to a hub bearing part 124 . Hub bearing part 121 has a cone-shaped section 126 , which tapers down in the direction of the transmission. Furthermore, cone-shaped section 126 has inner teeth. Coupling part 124 has a cone-shaped section 125 which is complementary in design to cone-shaped section 126 of hub bearing part 121 . Cone-shaped section 125 of coupling part 124 is provided with external teeth which engage the internal teeth of hub bearing part 121 . The cone-shaped form guarantees attachment of coupling part 124 to hub bearing part 121 without any play.
Coupling part 124 is fixed on hub bearing part 121 in the axial direction with the help of a threaded bolt 128 . At the end of threaded bolt 128 facing the transmission there is a shoulder 130 , with which the threaded bolt 128 is supported on the end of hub bearing part 121 facing the transmission. A threaded sleeve 132 having outside threading is threaded into complementary inside threading of coupling part 124 in the radial direction between threaded bolt 128 and coupling part 124 . The end of threaded sleeve 132 which faces the transmission is supported on a hub bearing part 121 . On its end facing away from the transmission, threaded sleeve 132 has a collar 134 , with a nut 136 contacting its side which faces away from the transmission, which nut is screwed onto the end of threaded bolt 128 which points away from the transmission. At the end of threaded bolt 128 that points toward the transmission there is a radial bearing 140 , through which an inner transmission input shaft 142 is supported indirectly on hub bearing part 121 . Inner transmission input shaft 142 is positioned rotatably in a hollow outer transmission input shaft 144 .
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A torque transmitting unit in the power train of a motor vehicle for transmitting torque between a drive unit having an output shaft and a transmission having at least one input shaft. At least one clutch unit is positioned between the drive unit and the transmission, and at least one vibration damping unit having an input part and an output part is provided and is connected between the drive unit output shaft and the clutch unit. The clutch unit includes a clutch cover that defines a clutch-containing volume and that is supported by a transmission housing section. The vibration damping unit is positioned with in the clutch-containing volume defined by the clutch cover. For optimization of structural space, both the input part and the output part of the vibration damping unit are supported in the radial direction by the clutch cover.
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This is a divisional application of U.S. Ser. No. 606,053 filed May 2, 1984, (now U.S. Pat. No. 4,649,012 issued Mar. 10, 1987) which is a divisional application of U.S. Ser. No. 269,924 filed June 2, 1981 (now U.S. Pat. No. 4,468,190 issued Aug. 28, 1984).
BACKGROUND OF THE INVENTION
The invention relates to a mold for shaping elongated, softened plastic products and more particularly to shaping such products into an arcuate configuration.
Plastic hollow sections for window frames have found wide spread use where the usually plane window borders and frames make it easy to use basically plane special plastic sections for such purposes. The advantages of such sectional construction, highly developed since their inception, have resulted in a need for curved sections of special shapes, particularly when repairing older buildings. Basically, it has been possible to prepare such arches for a long time, particularly according to a more recent process where preshaped sections are dipped into a special liquid and are heated to a predetermined temperature, 120° C., for instance. Thereafter the sections are easily shaped.
The customary shaping process, however, is afflicted with difficulties. When the sections are bent over a template or are bent within a mold, bulge waves and bulge folds occur along the internally located areas of the arches which depend on the properties of the sections. Furthermore, such specialized arches result in large costs and are time consuming to manufacture due to the relatively large amount of labor because changed arch shapes regularly require new molds or at least molds which are varied sectionally by joining parts thereof. Such dismountable molds frequently result in unacceptable products. These problems which occur frequently in the production of windows are basically applicable not only for these products but generally when forming complicated plastic sections.
An object of the present invention is to provide for the shaping of straight plastic sections into arcuate shapes simpler and more securely as well as more flexibly in respect to various arcuate shapes in order to obtain better and cheaper parts.
According to the invention this objective is achieved with a mold or template according to the disclosure which follows.
In applicant's invention, a mold formed by flexible guide rails allows the curvature of the template to be varied in an easily understood manner by more or less intensive bending in an elastic or a plastic mode and to produce thereby a fast accommodation to varied radii or shapes. Experimental sample or trial arches or arcuate shapes may be prepared and it is also possible to change a shape that is distorted due to cold-flow by correcting such effects. Such corrections may be achieved costing little labor or time. A mold constructed according to such a principle allows also an uninterrupted support for the formed shape which is at least at the beginning relatively soft and does so in the particularly critical inner and outer areas. It creates thereby good conditions for a product free of damages and irregularities or almost free of such defects.
The construction of the mold by aid of guide rails has shown particularly that the work piece may be pulled longitudinally through the mold thereby not only resulting in a steady and well controlled shaping process but also is particularly apt to prevent bulge waves and bulge folds. This procedure of shaping has shown that the customary frequently occurring danger of bulge waves and bulge folds is prevented and that now, after each hardening process, a plastic section may be removed from the mold which is uniform as to its cross section and has a smooth surface. An advantageous embodiment allows entry laterally into the mold with a drawing tool and to pull in this mold a section, held by its head, while the drawing tool follows the mold longitudinally.
A particularly advantageous mold allows the use of an extremely strong and rigid or tough material for the parts of the mold like polyethylene, particularly ultrahigh molecular low pressure polyethylene without restrictions when light variations of curvatures occur. Continuous rear edges allow the use of the bending strength of such a material and to retain its property of a sliding or slippery material and still retain the required bendability. While the mold parts change their shape exclusively in their rear area, their cross sectional shape is not impaired. The recesses intruding from the edge particularly prevent dislocations of the material caused by the curvature which could impair the cross sectional shape of the mold.
Other features which are considered characteristic of the invention are set forth in the appended claims.
Although the invention is illustrated and described in relationship to specific embodiments, it is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
The construction and operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partial perspective view of a mold according to one embodiment of the invention,
FIG. 2 is a cross sectional view of two mold parts according to FIG. 1 with an inserted section,
FIG. 3 is a partial perspective view of a mold according to another embodiment of the invention,
FIG. 4 is a cross sectional view of the mold according to FIG. 3 with an inserted section, and
FIG. 5 is a cross sectional view of a further alternative embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawings, FIG. 1 shows a mold, partially broken away, and generally denoted by the numeral 1. The mold 1 consists of two mold parts, namely an inner part 2 and an outer part 3. Each of the parts 2 and 3 are fastened to a mounting plate 4 and 5, respectively, and both mounting plates 4, 5 are disposed upon a common guide plate 6.
Each of the mold parts 2 and 3 consists of a section of high molecular low pressure polyethylene, a material known for its notched bar impact strength, flex-strength, and its property as a slippery raw material and which is recommendable for the present use. Other materials having sufficient flex-strength and sufficient slipperiness may be used, in which case also resistance against temperatures up to 120° C., humidity and noxious chemical substances must be taken into account.
The cross section of the mold parts, which is unimportant on its outer side, is determined on its inner side by the shape of the plastic part to be molded. The parts of the section must abut the inner sides of the mold with little play. Therefore, the frontal planes 7 and 8 of the mold parts 2 and 3 have on their edges facing towards each other, a complex shape adapted to the shape of the plastic part to be shaped. These adapted sectional areas are disposed upon the inner or outer side, respectively, of the arch to be manufactured. The mold parts 2 and 3 keep a distance between these so that no completely closed mold results. In order to save on mold material upon the sides where the mold parts 2 and 3 abut the mounting plates 4 and 5, the mounting plates form the bottom closure of the mold. Furthermore, the accessability of the inside of the mold is here advantageously taken care of.
At the side of the mold parts 2 and 3 facing away from the mounting plates, a permanently shaped free slot 9 is provided which makes it possible to reach into the mold with a tool, for instance a plier-shaped tool. This tool may serve to pull in longitudinally and "head first" a previously softened plastic section between the frontal sides 7 and 8 of the mold parts 2 and 3. Also a drawing tool following the arch shape from its end may be used, and a closed mold cross section may be provided thereby. It has been found that the aforedescribed shape of a mold and this method of feeding-in are particularly simple and easily understood.
The particular manner of shaping, where the softened plastic section is pulled longitudinally into the mold is easily understood because no adjustments of the mold must be performed during the molding operation like a bending operation from both sides against a piece to be molded, as in a conventional mold. This molding operation has been found surprisingly capable of preventing fold and wave phenomena due to dislocations of material caused by the molding process. Waves and folds which had to be fearfully expected in conventional molds and working processes therewith were not found here, a fact which might be apportioned to the uniform sliding intromission into the mold and also to the slight stretching of the whole molded part.
The sectional piece, shaped while softened, remains in the mold 1 between the mold parts 2 and 3 for a period of time sufficient for the prevention of back-forming, for instance 5 minutes, and is then taken out. Due to the fact that the mold parts 2 and 3 are disposed upon individual mounting plates 4 and 5, they may be moved apart. That is shown in the drawing by the butt joint 10 and the common rest upon the guide plate 6. It is evident that there are many constructive solutions of this function. The guide plate 6, could, of course, be replaced by rails or struts. The mounting plates 4 and 5 also may be replaced by other planar mounts, where the planarity only serves to define a curving plane for the mold parts and to allow simple changes.
Opposite to the mounting plates 4 and 5, the mold parts 2 and 3 are connected by, only schematically shown, struts 13, which, in the simplest case may have the shape of thrust blocks but may also provide various fastening and regulating means of a known kind for a simple and exact mounting. In order to fix the mold parts 2 and 3 relative to the mounting plates 4 and 5, at least two struts are needed each time arranged at the end. Preferably, though, a plurality of struts will be provided in order to stabilize the mold.
Furthermore, mold 1 allows the provision of variations in the longitudinal shape to be prepared, particularly in the curvature. In this respect it is particularly important that the mold parts 2 and 3 are formed flexible in the sense of changes of longitudinal curvatures, so that the mold parts may be bent more or less and also be bent non-uniformly along their length, and that they may be fastened to the mounting plates 4 and 5 in the shapes thusly obtained. For that purpose an elastic material is most advantageous. The longitudinal formability, though, is created particularly by recesses or cross cuts 14 or 15 following each other at uniform distances. These recesses or cross cuts 14, 15 begin at the rim of the mold parts 2 and 3, respectively, and leave out only an easily shaped back part. These rim recesses open up more or less in the inner mold part 2 as a function of the curvature and are pressed together in the outer mold part, so that deformations may be accepted without loss of fidelity to the shape of the mold by, for instance, deflecting inwardly or outwardly. In other words, a mold built for a certain hollow section may be used for such a section independently of the needed curvature. According to individual requirements, as they occur for instance for window enclosures and frames for older buildings, such changes are taken care of by moving the struts 12, 13 and if so needed, additional struts of identical or similar kind, in order to make the mold ready for a new shaping process.
With regard to the embodiment shown in FIG. 1, the horizontal position of the partly shown mold arch may not be a particularly preferred position, and a vertical position with a uniform accessability of the mold and particularly of slot 9 may be preferred in many occasions. The schematic illustration must be understood only as a means to make understandable the principle of the invention. For that purpose two points 16 of attachment for connecting elements are shown which have the purpose of fixing the mounting plate 4 relative to the guide plate 6, while the mounting plate 5 must be fixed immovably relative to guide plate 6.
FIG. 2 shows an enlarged position of the mold parts 2 and 3 relative to each other and their position to a section 17 to be shaped while soft. This sectional piece 17 basically has thin walls and fine sections and is a typical product for shaping into an arch or arcuate form. The particular demands resulting from such a construction are satisfied by guiding the cross section of the sectional piece narrowly between the mold parts 2 and 3 and by preventing irregular shifting because there is no room available for such an effect.
The drawing of the cross section shows furthermore that the cross hatched rear areas 18, 19 amount to a small part of the cross section of the mold parts 2 or 3, respectively, while the rest of the cross section areas are covered by the cross recesses 14 or 15. That makes it clear that the cross section of the mold parts 2, 3 is exposed only in the rear areas 18, 19 to deformation by bending and by changes of bending while those areas which effectively carry the hollow sector do not have to bear any deformation and thus retain their nominal cross section.
FIGS. 3 and 4 show another embodiment of the invention where corresponding mold parts 2 and 3 are used and where also identical numerals are used. The mold parts 2 and 3 in FIG. 3, however, do here not sit upon two planar mounting plates but upon two superimposed mounting plates 20 and 21, respectively. The upper plate 21 is limited by a curvilinear edge, concentrical to the shape of the mold. The plates, preferably woodchip plates, are planarly movable against each other and are capable of being arrested in the position of molding by rods, screws or the like, reaching through holes 22. These holes 22 are provided early when building the mold in order to ascertain exact centering and plate correlation.
The mold parts 2 and 3 may be used particularly simple, uniformly and also reliably mounted by the aid of two mounting or supporting molds 23 and 24 which, like the mold parts 2 and 3, are made of plastic and which are also formed comb-like by means of equidistant recesses. These comb-like recesses face towards the plane of curvature and thereby allow easy bending of the mounting or supporting molds along predetermined curves. The supporting molds 23 and 24 have a substantially L-shaped profile which assures on one hand abutting the back of mold parts 2 or 3, and on the other hand, abutting the individual mounting plate 20 or 21. The supporting molds 23 and 24 are easily connected to their respective mounting plates by screws which is facilitated by mounting holes 25 and 26, respectively, disposed within the comb tines.
FIG. 4 shows also screws 27, 28, 29, 30 and 31 which connect the supporting molds 23, 24 to the mounting plates 20, 21 and also to the mold parts 2, 3.
These supporting molds 23, 24 act in a simple manner as uniform supports requiring less expense than the supports 12, 13, drawn as in the embodiment of FIG. 1 or the otherwise needed arch shaped supports made out of woodchip material that is a few centimeters thick. Due to the rigidity of the supports, plate 21 may be made out of intermediate strength chip plate (19 mm) which allows fast and easy work and still assures safety of the mold part against dislocation, longitudinal deformation, and swivelling through the supporting mold 24.
FIG. 5 shows another alternate embodiment wherein, here again, respective parts are provided with the same reference numerals as in FIGS. 1 to 4 because the basic construction has not been changed. The main change in respect to the embodiment of FIG. 5 consists in a spacer strip 32 disposed between the mold part 2 and the supporting mold 24. This spacer strip 32 is for instance 42 mm broad and causes a corresponding distance between mold part 2 and supporting mold 24. Such spacer strips may basically aid in changes of the radius in order to use an occasionally available mounting plate 21 for a slightly different radius. In this respect staggered spacer strips may also make it possible to find multiple uses for off-the-shelf stored mounting plates.
Much more important is the case that for wings of a window. At first the window frame must be bent and then the casement and a difference of the radii exists between these two, differing according to the hollow section out of which it is to be made. This difference of radii may be corrected by the use of such a spacer strip by frontally disposing the strip once, for the wings of the window, to the inner supporting mold and then, for the casement, to the outer supporting mold. Thus a simple and exact work process results by the use of common mold elements and mold adjustments.
The solid but soluble connection of spacer strip, mold part, and supporting mold, is also engineered by screws which create a simple, solid but soluble connection and are easily built, particularly from a plastic material.
The spacer strip 32 is again preferably made out of a plastic material and again is also provided, like mold parts 2, 3 and supporting molds 23, 24, with a comb-like shape by cross recesses worked in its side. This comb-like construction allows simple and uniform bending along its longitudinal extension.
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A mold for synthetic resin products which are to be shaped while soft, includes a pair of elongated mold parts each having opposed complementary faces with contours at least partially conforming to at least parts of the product to be shaped. A support means on which the mold parts are mounted provide for moving at least one of the mold parts relative to the other mold part to effect removal therefrom of a finished product. The mold parts are constructed and arranged so as to be bendable along their longitudinal axes to effect a change in arcuate configuration, the mold parts being made of a material which facilitates sliding of the synthetic resin product through the mold, the support means supporting the mold parts in fixed spaced apart disposition as the product is moved longitudinally between the mold parts to thereby impart to the product an arcuate configuration corresponding to the arcuate configuration of the mold parts.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method and system for epitaxial growth of high purity materials on an atomic or molecular layer by layer basis.
2. Brief Description of the Prior Art
Atomic layer epitaxy (ALE) has been in existence for in excess of ten years as noted by M. A. Harman in Vacuum, volume 42, page 61 (1991) and Atomic Layer Epitaxy by T. Suntola and M. Simpson, Editors, Chapman and Hall (1990) and U.S. Pat. No. 4,048,430 of T. Suntola and M. Antson. ALE has been shown to produce high quality crystalline films of a variety of materials. The ALE approach is, in actuality, a special mode of other physical and chemical deposition growth techniques, such as chemical vapor deposition (CVD) or molecular beam epitaxy (MBE). ALE is based upon chemical reactions at carefully prepared, typically heated, substrate surfaces. The constituent elements of the film are delivered to the sample sequentially as pulses of neutral molecules or atoms.
The chemical reactions in the ALE process are self-limiting in that the available bonds (reactive sites) on the surface are consumed in their entirety. This limits the growth of the film to single layers of the reactant species. Through using the surface chemistry in the process, enhanced reactivity of the precursor may be expected at lower temperatures. The choice of the molecular species is based upon known surface chemistry in order to take advantage of the self-limiting reaction and lower growth temperatures. This includes choosing a precursor molecule on the basis of the reaction and lower growth temperatures. This also includes choosing a precursor molecule on the basis of the steric interactions of an adsorbed/reactant species, which permits an accurate control of surface coverage.
Two basic variants of ALE exist. A first such variant utilizes a direct ALE process whereby elemental constituents are deposited onto the substrate and direct chemical reactions ensue between these reactants and the outermost surface atoms. A second such variant process relies upon the sequential surface exchange reactions between the substrate surface atoms and the molecules of the reactants which are chemical compounds.
Typically, the vacuum chamber used in the ALE approach is backfilled with a gas phase molecule to result in high vacuum pressures on the order of 10 -5 Torr (relatively high pressure). The vacuum chamber is frequently purged with a non-reactive gas between exposures. These relatively high pressures can result in the introduction of impurities into the film due to the usual purging process.
Precision dosing techniques of single crystal surfaces with molecular species have also been understood for some time as noted by C. T. Campbell and S. M. Velone in Journal of Vacuum Science Technology, Vol 43, page 408 (1985) and by A. Winkler and J. T. Yates, Jr. in Journal of Vacuum Science Technology, Vol 46, page 2929 (1988) and have largely concentrated upon academic surface science experiments as noted by R. M. Wallace in Backscattering and Chemical Investigation of Semiconductor Surfaces, a Ph.D. dissertation, University of Pittsburgh (1988). The technique comprises a gas reservoir of high purity gas vapor, typically at pressures below 1 atmosphere. This reservoir is connected to the vacuum chamber used for exposing the substrate through a small conductance limiting orifice, on the order of a few microns in diameter. This permits precise control of the molecular flux into the system by manipulating the reservoir pressure. The flux of molecules is passed to an effusive capillary assembly, generally comprising an array of capillaries, and directed at the substrate.
As noted above, the purging step, which has been required by the prior art, introduces impurities into the system when operating on an atomic and/or molecular scale. It is therefore desirable to eliminate the purging step from the operation.
SUMMARY OF THE INVENTION
By using directed effusive molecular beams of the precursor gas and a suitable gas reservoir, a substrate is exposed with great precision to a gaseous precursor molecule to result in the formation of an epitaxial or amorphous single adsorbed layer (monolayer) at extremely low ambient pressures. The effusive beam is directed through the use of a suitable capillary array separated from the gas reservoir with a small conductance limiting orifice. The exposure of the substrate surface is controlled by shuttering the beam, manipulating the gas reservoir supply pressure or moving the substrate away from or out of the direct beam.
The use of precision, directed effusive molecular beams permits the exposure of the substrate surface to the precursor molecule of interest without the conventional ALE intermediate purging step, thus avoiding the introduction of impurities from the vacuum vessel walls. The local pressure in the vicinity of the substrate is on the order of 10 -7 to 10 -8 Torr, while the pressure in other portions of the chamber remains in the ultrahigh vacuum pressure regime of 10 -9 Torr and below. Purity is also maintained by using a separate gas dosing facility for each species of interest.
By controlling the gas pressure of the associated reservoir, the flux of molecules delivered through the conductance limiting orifice and thus to the substrate is controlled. By controlling the substrate-doser position, the coverage of the substrate surface by well established angular distribution calculations is controlled. Growth of the surface film is controlled by the ALE process and the use of shutters, pumps or crystal positioning. Control of shutters and substrate positioning is provided by computer control of a partial pressure monitor, such as a residual gas analyzer. Pumping valves may also be computer controlled. Precursor gas supply pressure is maintained through a pressure monitoring device and valves or mass flow controllers.
By performing exposures at extremely low pressures, purity of the films is improved over that of conventional atomic layer epitaxy. Additionally, material and dopant profiles are made to a monolayer thickness scale. Accelerated growth rates are provided because gas purging of the vacuum chamber is not required. Because of the vacuum pressures required, there is less chance of gas phase nucleation.
Smaller amounts of precursor chemicals/gases are required in comparison with the prior art, thus providing an economic advantage. Also, amounts of toxic materials for precursors, if required, are reduced and thus present less of a health risk and reduced disposal requirements.
The system and method in accordance with the present invention can be used in conjunction with conventional ultrahigh vacuum growth techniques, such as molecular beam epitaxy, to include the possibility of source species which are not easily rendered in gaseous form. Thus, through the combination of the methods, a wide number of chemical compounds can be produced in films.
BRIEF DESCRIPTION OF THE DRAWING
The FIGURE is a schematic diagram of a directed effusive beam atomic layer epitaxy system in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference to the FIGURE and the system set forth therein, any device that requires deposition of dielectrics and/or metals can be fabricated therein. Assuming that a semiconductor device is to be fabricated, there is provided an ultra-high vacuum chamber 1 with vacuum of from about 10 -9 to about 10 -11 Torr and below. An appropriate substrate 3, preferably a single crystal substrate such as, for example, silicon, a group III-V semiconductor compound such as gallium arsenide or the like, etc. is disposed within the chamber 1 and is movable in an x, y and z orientation (i.e., in three dimensions) and is also rotatable about an axis passing through the sample in standard manner, such as with a standard robotic wafer holder. The goal is to be able to place the substrate surface in line-of-sight of the doser assembly.
An appropriate gas or gases in predetermined amounts, as determined by the opening and closing of valves on a gas reservoir 5, are expelled from the gas reservoir through a conductance limiting orifice 9 having a diameter of from about 1 to about 5 microns and a capillary array doser 7, the latter preferably in the form of an orifice and directed at the substrate 3 from a location within the vacuum chamber from a location closely adjacent the substrate and into the vacuum chamber atmosphere. The doser assembly provides a means to deliver the gaseous precursor to the substrate surface in a spatially controlled manner. A doser is constructed, for example, from a cylindrical tube or in a more complicated array (shower head) of holes, as in a microcapillary array. The purpose of the orifice 9 is to provide a controlled, reproducible means to admit gaseous precursors from the precursor reservoir to the doser assembly and hence to the substrate. The size of the orifice is critical in controlling the flux of precursor molecules to an acceptable rate for reasonable growth rates to insure that the conductance is independent of reservoir pressure (i.e., molecular flow kinetics is appropriate) and maintaining the integrity of the vacuum chamber (and thus, film purity).
The pressure in the chamber will rise due to the entry of the gases thereinto, mainly in the vicinity of the substrate 3, and will then fall due to the breakdown and deposition of some of the gases onto the substrate. The pressure in the chamber 1 and particularly in the vicinity of the substrate 3 is monitored to determine when a sufficient amount of the gas in the chamber has deposited on the substrate 1. The pressure in the vicinity of the substrate is monitored, for example, indirectly through the use of a residual gas analyzer (RGA). The RGA is tuned to monitor the partial pressure of the precursor species being admitted into the doser assembly. A fraction of this flux of precursor intercepts the substrate 3 and subsequently reacts on the surface thereof. The remaining portion of precursor misses the substrate and becomes randomly scattered throughout the chamber. The RGA signal for the precursor serves as a measure of this random flux and thus, by mass conservation, serves as an indirect monitor of the local pressure near the substrate. A reservoir pumping system 11 removes the residual precursor species from the reservoir volume, excluding the source tanks at the gas reservoir 5 which are valved. The region between the orifice 9 and the doser assembly 7 is pumped by a chamber 1 pumping system. This is a small volume of gas and results in rapid removal of the gas from the vicinity of the sample. A second pumping/valve configuration can be provided in this small area between the orifice 9 and the doser assembly 7 to improve the temporal control of the flux. A shutter assembly also can serve in this capacity when placed between the doser assembly 7 and the substrate 3. The above described procedure is then repeated for the next atomic or molecular layer of the same or different material, this being repeated as many times as required to provide the final desired structure.
The gas reservoir 5 comprises a plurality of gas-containing tanks with a valve on each tank, the particular gas or gases required during each deposition step determining which of the gas containing tanks is opened. Furthermore, a known pressure is maintained in each of the gas containing tanks so that a known amount of gas is released upon the opening and closing of the valve on each of the tanks.
Assuming, for example, that a layer of doped gallium arsenide is now to be fabricated on the substrate 3, the substrate is selected to be clean, undoped crystalline gallium arsenide and the chamber 1 is evacuated to a vacuum of 10 -10 Torr with a conventional pumping system (not shown). The gases required for fabrication of a doped gallium arsenide layer are provided under pressure of from about 0.1 to about 10 Torr in the gas reservoir 5 which contains plural separate tanks of appropriate gases under pressure with a controlled valve on each tank (not shown) which permits the gas to escape from the associated tank. The orifice 9 has a constant leak rate for a given precursor in this pressure regime. Typical values are 10 12 to 10 13 molecules/second. The number required depends upon the number of reactive sites on the surface of the substrate 3. An estimate of this is, for example, about 10 15 sites Thus, a time period of 100 to 1000 seconds is required to completely consume the reactive surface sites through the chemical reaction with the precursor. The key concept is the self-limiting aspect of the ALE process. That is, one only need control the amount of the precursor gas crudely and the self-limiting surface reaction takes care of the rest of the work, by definition. Accordingly, arsine gas is expelled from one of the tanks 5 upon opening and closing for a known time period of the associated valve through a capillary array doser 7 and a conductance limiting orifice 9, which is preferably an orifice having a diameter of about 1 to 5 microns and preferably 3 microns into the evacuated chamber 1. The other precursor species (trimethyl gallium and silane dopant) are admitted in consecutive fashion using the pumping sequence described hereinabove. By admitting the precursors sequentially, one avoids undesirable gas phase reactions in the reservoir. This causes some build-up of pressure within the chamber 1, this pressure being monitored with a standard pressure measuring device (not shown) until the pressure has dropped back to a predetermined value caused by breakdown and/or deposit of material from the gaseous phase onto the substrate 3. The change in pressure is a measure of the amount of material deposited on the substrate surface. With the precursor gases containing gallium, arsenic and a dopant, doped gallium arsenide is deposited on the substrate 3.
Atomic layer epitaxy is based upon the use of precursors which are self-limiting in growth. The ideal precursors comprise species that deposit a single monolayer of the element of interest which will not react further without additional stimulation, or the presence of a second precursor species which will further react with the initial species. This technique can include more than two reactants and is ideally suited for the use of delta-doping (where a single monolayer of dopant is placed in the structure and each dopant is electrically active). A use of atomic layer epitaxy for the growth of silicon carbide (SiC) will now be described in a specific embodiment.
The silicon precursor used is SiCl 2 H 2 and the carbon precursor is CH 2 Cl 2 . Aluminum is a p-type dopant in SiC, thus the use of Al(CH 3 ) 3 as the aluminum precursor is appropriate. A SiC substrate is then exposed to a controlled amount of SiCl 2 H 2 , which bonds to the SiC surface, loosing two hydrogen atoms in the process. Once a monolayer is deposited, the substrate surface consists of Si--Cl 2 species thereon. This substrate surface is no longer reactive and therefore the Si deposition stops. The next step is to remove the chlorine in order to make the surface reactive again. There are several ways to accomplish this task. For example, the ideal solution comprises exposing the surface to a controlled amount of CH 2 CL 2 , apparently liberating the surface bound chlorine to the gas phase (as HCl and Cl 2 ) and thereby depositing carbon on the surface. Other solutions include (1) exposing the substrate surface to atomic hydrogen to form HCl, (2) exciting the substrate surface with ultra-violet radiation to break the Si-Cl bond and (3) heating the substrate surface to thermally break the Si--Cl bond. After the chlorine removal, the reactive silicon surface is exposed to the carbon-bearing precursor, CH 2 Cl 2 , resulting in a monolayer of deposited carbon. Again, the chlorine is removed as described above. The aluminum dopant is added in a similar manner at an appropriate point in the process, that is, when the layer in the structure is deposited wherein the dopant is required.
It is important to note that since the deposition is taking place at relatively low temperatures, the terminated surfaces are quite stable. Even if the use of intermediate reactants to remove terminating species is required (e.g., chlorine above), the use of controlled exposures through the effusive beam apparatus described hereinabove permits the growth of complex structures which would not be possible by other techniques. This is an important feature in that it separates the subject disclosure from the standard ALE or migration enhanced epitaxy.
The substrate 3 is generally at room temperature. However, it can be heated or cooled in standard manner, as required, to stimulate growth onto the substrate.
The reservoir pumping system 11 is utilized when gases in the chamber 1 are to be changed. In this case, with the gas reservoir 5 closed, any remaining gas in the conductance limiting orifice 9 and the capillary array doser 7 is pumped into the reservoir pumping system 11. One or more of the above described procedures for forming another monatomic or molecular layer are then repeated with the same or different precursor gases, as required, to build up the device being fabricated.
The valves (not shown) which control gas flow from the tanks of the gas reservoir 5 can be automated, such as under control of a computer, or hand operated.
In order to maintain the high vacuum conditions within the vacuum chamber 1, a load lock (not shown) can be coupled to the vacuum chamber so that a processed substrate or a substrate for processing can be entered into or removed from the chamber 1 to the load lock with little reduction of the vacuum within the chamber. This reduces the time required to obtain the high vacuum conditions required.
Though the invention has been described with respect to specific preferred embodiments thereof, many variations and modifications will immediately become apparent to those skilled in the art. It is therefore the intention that the appended claims be interpreted as broadly as possible in view of the prior art to include all such variations and modifications.
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A system and method for epitaxial growth of high purity materials on an atomic or molecular layer by layer basis wherein a substrate is placed in an evacuated chamber which is evacuated to a pressure of less than about 10 -9 Torr and predetermined amounts of predetermined precursor gases are injected into the chamber from a location in the chamber closely adjacent the substrate to form the atomic or molecular layer at the surface of the substrate while maintaining the pressure at less than about 10 -9 Torr in the chamber in regions thereof distant from the substrate. The precursor gases are provided from a plurality of tanks containing the precursor gases therein under predetermined pressure and predetermined ones of the tanks are opened to the chamber for predetermined time periods while maintaining the pressure in the tanks. A dose limiting structure is provided for directing predetermined amounts of the precursor gases principally at the substrate with a dose limiting directional structure.
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CROSS REFERENCE TO RELATED APPLICATION
This application claims the benefit of provisional patent application Ser. No. 61/750,149, filed on Jan. 8, 2013, and provisional patent application Ser. No. 61/833,084, filed on Jun. 10, 2013, the entire contents of which are incorporated herein by reference.
FIELD
The present invention relates generally to the field of excavation using a fluid and a system for recycling the fluid.
SUMMARY
The present invention is directed to a reclaimer located proximate an excavation site. The reclaimer comprises a screen assembly, a conduit for transporting excavation fluid from the excavation site to the screen assembly, a first vibrator operatively attached to the screen assembly, and a leveling assembly for adjusting an orientation of the screen assembly.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side perspective view of a fluid reclaimer system of the present invention with a soft excavation arm.
FIG. 2 is a back perspective view of an alternative embodiment of the fluid reclaimer system.
FIG. 3 is a perspective view of an airlock for use with the system of FIG. 1 .
FIG. 4 is a cross-section side view of the airlock of FIG. 3 .
FIG. 5 is a partial cross-section side view of the soft excavation unit for use with the system of FIG. 1 .
FIG. 6 is a top back perspective view of the embodiment of the fluid reclaimer system.
FIG. 7 is a side view of the fluid reclaimer system in use with a horizontal directional drilling system.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention is a reclaimer for regenerating excavation fluid to re-use the fluid in excavation operations. In ordinary excavation operations using horizontal directional drilling systems, drilling fluid is pumped through a drill string to a location proximate a drill head to lubricate the drill head and case the process of drilling. After fluid is used at the point of drilling, it travels back up the borehole, collecting particulate matter such as drilling spoils, environmental dirt, and metal along the way. The fluid, upon returning to the surface, would be better described as used drill fluid, or “spent mud”, unsuitable for reuse in the drill head due to the corrosive particles contained within it.
The reclaimer of the present invention provides a method for processing spent mud to remove particulate matter from the spent mud to reclaim drilling fluid for drilling operations. This decreases the amount of fluid required for an excavation operation.
With reference to the figures in general and FIG. 1 particularly, shown therein is a drilling fluid reclaimer system 10 in accordance with the present invention. The system 10 is shown on a trailer 12 . The trailer 12 comprises a hitch 14 , a frame 16 , and a plurality of ground engaging members 18 . The hitch 14 provides a connection to a vehicle (not shown) that pulls the system 10 to a job site. The frame 16 supports various components of the system 10 , which will be discussed in greater detail below. The ground engaging members 18 as shown, are wheels. One of ordinary skill can appreciate that tracks may alternatively be used as ground engaging members 18 , and that either wheels or tracks may be powered by a drive motor. Alternatively, the trailer 12 may be integrally formed with a self-powered truck.
The system 10 comprises a power pack 20 , a fluid tank 22 , a reclaimer 24 , and a mixer 26 . The system 10 further comprises a fluid delivery system 28 for transporting fluid to and from an excavation site. As shown, the fluid delivery system 28 comprises a soft excavation unit 30 , an airlock 32 , and a pump 34 . One skilled in the art will appreciate that other fluid delivery systems may be used with the reclaimer system 10 of the present invention, such as a system for delivering fluid to a downhole bit in a boring operation ( FIG. 7 ).
The power pack 20 provides power for operating the various electronic and hydraulic components of the reclaimer system 10 . The fluid tank 22 stores drilling fluid for use with the drilling fluid delivery system 28 . Preferably, as shown in FIG. 1 , the fluid tank 22 comprises multiple chambers 36 . Each of the chambers may contain a different fluid, such as water, unused fluid, and recovered fluid from operation of the reclaimer system 10 , as will be described in more detail below.
The fluid delivery system 28 further comprises a fluid delivery channel 40 and a fluid return channel 42 . The fluid delivery channel 40 may be a hose or other delivery device to accommodate fluid as it moves from the fluid tank 22 to an excavation site. As shown, the excavation site is a location for soft excavation by the soft excavation unit 30 . Fluid is moved from the fluid tank 22 , through the fluid delivery channel 42 to the soft excavation unit 30 . The fluid is then used to aid in soft excavation—the uncovering of a buried utility without the use of a bit.
The pump 34 provides a pressure to push new fluid and used fluid through the fluid delivery system. The pump 34 may be any commercially available pump suitable for pumping fluid used in excavation operations and may be operated by conventional means, such as hydraulic or electrical power.
As shown, the fluid delivery system may further comprise a vacuum system 44 for providing a vacuum pressure at the soft excavator 30 . This pressure pulls used fluid mixed with particulate matter such as dirt (called “spent mud”) into the fluid return channel 42 and into the airlock 32 . The airlock 32 separates air from spent mud, as the an is pushed through the vacuum system 44 . Spent mud leaves the airlock 32 and is applied to the reclaimer 24 .
The reclaimer 24 comprises a plurality of desilter cones 50 , a vibrator 52 , a screen assembly 54 , and a reclaimed fluid tank 55 . Spent mud is processed through the plurality of desilter cones 50 to remove fluid from the courser particulates. One skilled in the art will appreciate that desilter cones 50 accept the spent mud tangentially into its body. The centrifugal force induced by the flow causes the heavier solids and slurries to separate from lighter material. The heaviest solids are deposited out the bottom of the cones 50 to the screen assembly 54 and the lighter liquid removed out the top for reuse. The desilter cones 50 are located above the screen assembly 54 and deposit spent mud thereon.
The vibrator 52 is attached to the screen assembly 54 . Spent mud is processed on the screen assembly 54 by vibration of the vibrator 52 . The vibrator 52 may vibrate the entire screen assembly 54 at the same frequency, or may alternatively comprise a first vibrator and a second vibrator to vibrate different parts of the screen assembly at different frequencies.
The reclaimer 24 processes the spent mud to cause particulate matter to be separated from the drilling fluid, or slurry portion, as will be described in greater detail with reference to FIG. 2 below. The drilling fluid is dropped into the reclaimed fluid tank 55 and then returned to a chamber 36 of the fluid tank 22 . Particulate matter processed by the reclaimer 24 is dropped into the mixer 26 .
The mixer 26 allows the particulate matter removed from the reclaimer 24 to dry, or for drying agents to be added to the particulate matter to aid in drying. Dry particulate matter may be left on the ground, or removed to a secondary site for further drying and processing.
With reference now to FIG. 2 , the system 10 is shown in an alternative configuration without the mixer 26 ( FIG. 1 ) and with the fluid tank 22 located next to the reclaimer 24 . This alternative configuration may be used with a horizontal directional drill ( FIG. 7 ). The reclaimer 24 further comprises a chute 56 and a leveling assembly 58 . As shown, desilter cones 50 are located at a first end 60 of the reclaimer and the chute 56 is located at a second end 62 of the reclaimer. The vibrator 52 is centered over the screen assembly 54 to enable uniform vibration throughout the screen assembly, if desired. The screen assembly 54 comprises a first screen 64 and a second screen 66 . The first screen 64 is shown located above the second screen 66 . The second screen 66 thus may comprise a finer mesh such that smaller particulate matter that passes through the first screen 64 is filtered out of the fluid by the second screen.
The chute 56 allows filtered particulate matter falling off the first screen 64 and second screen 66 at the second end 62 of the reclaimer 24 to drop to the ground or into a mixer 26 ( FIG. 1 ) with a clearance between filtered particulate matter and the back of the trailer 12 . The chute 56 comprises a chute frame 70 . The chute frame 70 may be adjusted to change the angle of the chute 56 relative to the ground and thus the distance between the deposited particulate matter and the back of the trailer 12 .
The leveling assembly 58 adjusts the orientation of the screen assembly 54 and may comprise at least one cylinder 80 . As shown, the cylinder 80 is proximate the second end 62 of the reclaimer. As shown, the cylinder 80 adjusts an orientation of the screen assembly 54 relative to the reclaimed fluid tank 55 . The leveling assembly 58 may comprise more than one cylinder to enable a tilt adjustment of the first screen 64 and second screen 66 front-to-back and right-to-left. The leveling assembly 58 may alternatively comprise a pinned or slotted connection (not shown) between the screen assembly 54 and the reclaimed fluid tank 55 . It is generally desirable for the leveling assembly 58 to position the first screen 64 and second screen 66 higher at the front end than at a back end of the screen assembly, while maintaining a level orientation from side-to-side. Thus, if the trailer 12 is on uneven terrain, the screen assembly 54 can maintain a flat orientation. Further, moisture content and flowrate of the spent mud may make it advantageous for the spent mud to spend more or less time on the screen assembly 54 , which can be modified through front-to-back tilt of the screen assembly. A level sensor (not shown) may be provided to determine the front-to-back and side-to-side tilt of the screen assembly 54 . The first screen 64 may be locked with the second screen 66 in orientation. Alternatively, in some applications it may be advantageous to provide the first screen 64 and second screen 66 with different or variable front-to-back tilt to maximize the reclamation of drilling fluid due to differing composition of material at the first screen and at the second screen.
Fluid passing through both the first screen 64 and the second screen 66 is collected in the reclaimed fluid tank 55 , returned to the fluid tank 22 , and thus “reclaimed” by the system 10 for use in excavation operations. Fluid is then provided through the excavation operations as described above, either alone or combined with unused fluid.
With reference now to FIG. 3 , the airlock 32 is shown in more detail. The airlock 32 comprises an upper tank 90 and a lower tank 92 . The lower tank 92 comprises a sprocket 94 driven by a motor 95 for driving rotation of internally located impellers 112 ( FIG. 4 ).
As previously discussed, the fluid return channel 42 transports used fluid from the jobsite to the air lock 32 . Used fluid enters the airlock 32 from the fluid return channel 42 at the upper tank 90 . Air present in the fluid return channel 42 is removed from the airlock 32 through vacuum channel 96 located at the top of the upper tank. The vacuum channel 96 also provides maintenance of a vacuum pressure within the airlock 32 so that a vacuum pressure is delivered to the soft excavation unit 30 as will be described in more detail with reference to FIG. 5 . Spent mud that enters the airlock 32 at the fluid return channel 42 exits at the bottom of the lower tank 92 .
With reference now to FIG. 4 , internal components of the airlock 32 are shown. The upper tank 90 comprises a support bar 100 , a float comprising a float ball 102 , an inlet 104 and a vacuum exit 106 . Air and spent mud enter the upper tank 90 from the fluid return channel 42 ( FIG. 3 ) at the inlet 104 . The support bar 100 holds the float ball 102 in a position below the vacuum exit 106 . Spent mud is pulled toward the lower tank 92 due to gravitational force. The float ball 102 will float on the top surface of spent mud if the amount of in the upper tank 90 rises. Thus, before the spent mud threatens to exit the airlock 32 through the vacuum exit 106 , the float ball 102 will seal the vacuum exit, preventing mud from entering the vacuum system 44 ( FIG. 1 ).
The lower tank 92 comprises a mechanical flow regulator, such as an impeller 108 . The impeller 108 comprises a plurality of arms 112 , each with a flap 114 that contacts an inner surface 115 of the lower tank 92 . The motor 95 drives the sprocket 94 ( FIG. 3 ) which, in turn, rotates the impeller 108 . As the arms 112 of the impeller 108 rotate, spent mud is removed from the airlock 32 and allowed to move to the reclaimer 24 ( FIG. 1 ). The flaps 114 prevent the ambient pressure outside the airlock 32 from causing the upper tank 90 to lose vacuum pressure within the airlock 32 .
With reference now to FIG. 5 , the internal workings of the soft excavation unit 30 are in cross-section. The soft excavation unit 30 comprises a body 118 with an opening 119 , at least one jet 120 , an internal shaft 122 , and a rotating bit 124 . The at least one jet 120 directs drilling fluid 126 to a surface of the ground. The rotating bit 124 is driven by the internal shaft 122 and is located within the body 118 such that no portion of the rotating bit extends beyond the opening 119 of the soft excavation unit 30 . In this way, the rotating bit 124 is prevented from contacting an underground object and merely aids in displacing soil located within the perimeter of the opening 119 .
One skilled in the art will appreciate that a vacuum pressure may be provided proximate the opening 119 so that spent mud can be removed from the site of soft excavation. This vacuum pressure may be provided between the shaft 122 and the body 118 such that spent mud is removed by the soft excavation unit 30 itself. Alternatively, a separate fluid return channel 42 ( FIG. 1 ) may be provided at the site of soft excavation to remove spent mud. In either case, spent mud removed from the soft excavation location is directed to the airlock 32 ( FIG. 3 ).
With reference to FIG. 6 , the system 10 is shown with the mixer 26 located under the chute 56 . The mixer comprises at least one rotating arm 130 . Particulate matter in the mixer 26 may still be wet. In many locations, wet particulate matter may not be deposited on the ground or used to re-fill a pit used for drilling or a pothole created by the soft excavation unit 30 . Thus, particulate matter entering the mixer may be mixed with a drying agent and stirred by the rotating arms 130 or an auger (not shown) in order to dry the particulate matter such that it may be deposited at the job site rather than at a disposal facility.
While most of the figures above have shown the system 10 in use with a soft excavation unit 30 , the configuration shown in FIG. 7 may also be effective. With reference to FIG. 7 , the system 10 is shown in use with a horizontal directional drilling system 200 . The horizontal directional drilling system 200 comprises a carriage 202 , a drill string 204 and a bit 206 . The drill string 204 enters the ground at a drilling location 208 . The carriage 202 provides thrust and rotation to the bit 206 . Drilling fluid is provided from the fluid tank 22 of the system 10 to the horizontal directional drilling system 200 by way of fluid delivery channel 40 . This drilling fluid may travel down the drill string 204 for use at the bit 206 to aid in drilling operations. Thus, the drill string may comprise a conduit through which fluid is transported from the surface to the drill bit. Fluid is injected into the borehole surrounding the drill bit and mixes with dirt, metal shavings, and other particulate matter to form spent mud which returns up the bore hole in the space between the outside of the drill string and the surface of the borehole to the drilling location 208 . The spent mud may then be moved to the system 10 for processing by the reclaim 24 by way of the return channel 42 . A pump 210 may also be connected to the return channel 42 to help pump the spent and back into the system 10 .
One skilled in the art will appreciate the variations that may be effective in this invention. For example, auger boring, rock boring and vertical drilling operations which make use of drilling fluid may be adapted for the present invention such that drilling fluid can be reclaimed for repeated use.
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The present invention is directed to a drilling fluid reclaimer. The reclaimer has at least one adjustable screen assembly for providing a leveling filter for reclaimed drill fluid. Used drill fluid is placed at the screen assembly at the front the of the screen assembly. The at least one screen is vibrated to separate large particulate matter from liquid drilling fluid. A second screen is provided for additional filtering. Large particulate matter is expelled by a chute at the back of the screen assembly. Drilling fluid passing through the screen is “reclaimed” for use with a drilling system.
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PRIORITY CLAIM
[0001] This application is divisional of U.S. application Ser. No. 10/529,657 filed Nov. 28, 2006, which is a national stage application of PCT/AU03/01281 filed Sep. 30, 2003, which claims priority to AU 2002951685 filed Sep. 30, 2002.
[0002] The present invention relates to a demand responsive physiological control system and, more particularly, to such a system particularly suited for use with blood pumps and, even more particularly, those used to assist heart function such as, for example, ventricular assist devices.
BACKGROUND
[0003] With particular reference to physiological control systems in mammals and more particularly those of the human body it has been noted that the control systems which the body itself uses to control various organs are complex.
[0004] For example, the heart of a mammal may cause the amount of blood that is to be circulated through the body to change not just for what might be termed obvious reasons such as an increase in physical exertion by a person, but may also occur for example, as a result of anticipation of exertion. Furthermore the triggers which can cause changes in heart rate and pumped blood volume may derive from the nervous system directly or may derive from the action of hormones or other chemical releases within the body.
[0005] It follows, where mechanical aids are introduced into the body to assist the body's functions such as, for example, implantable rotary blood pumps used as ventricular assist devices that simplistic control mechanisms for these mechanical aids cannot hope to anticipate or mimic the commands which the body may pass to the heart.
[0006] For example, in early applications of ventricular assist devices the control mechanisms simply set the ventricular assist device to pump at a constant volume per unit time, adjusted at the time of initial installation to best suit the patient in whom the device has been installed.
[0007] Such systems use pump speed as the controlled variable. Unfortunately, a set pump speed bears no relation to actual physiological demand.
[0008] It is an object of the present invention to address or ameliorate one or more of the above mentioned disadvantages.
BRIEF DESCRIPTION OF INVENTION
[0009] Accordingly, in one broad form the invention there is provided a demand responsive physiological control system for use with a rotary blood pump; said system including a pump controller which is capable of controlling pump speed of said pump; said system further including a physiological controller, and wherein said physiological controller is adapted to analyze input data relating to physiological condition of a user of said pump; and wherein said physiological controller determines appropriate pumping speed and sends a speed control signal to said pump controller to adjust pump speed; said system further including a physiological state detector which provides said input data indicative of at least one physiological state of said user, in use, to said physiological controller.
[0010] Preferably said the physiological state detector includes an accelerometer to sense motion of the user, when in use.
[0011] Preferably said the accelerometer senses motion in at least one axis.
[0012] Preferably said the accelerometer senses motion in three orthogonal axes.
[0013] Preferably said system includes a pump monitor that detects information relating to voltage and current of the pump and delivers this information to said physiological controller.
[0014] Preferably said pump monitor detects an instantaneous pump impeller speed of the rotary blood pump through measurements.
[0015] Preferably said pump monitor detects non-invasively.
[0016] Preferably said physiological controller uses said information received from the pump monitor to derive mathematically an appropriate pump speed.
[0017] Preferably said physiological controller assesses flow dynamics and an average flow estimate, developed from speed and input power supplied to the pump by the pump controller.
[0018] Preferably said physiological controller mathematically determines a pumping state and if a deleterious state is determined the speed control signal is changed accordingly.
[0019] In a further broad form of the invention there is provided a physiological detector includes a means of detecting and quantifying a heart rate of the user, when in use.
[0020] Preferably said physiological detector includes a means of non-invasively detecting and quantifying a heart rate of the user, in use.
[0021] Preferably said physiological controller can determine a heart rate of the user by sensing speed of the pump.
[0022] Preferably said physiological controller can determine a heart rate of the user using power inputted to the pump.
[0023] Preferably said pump is internally implantable within the user.
[0024] Preferably said the pump is a ventricle assist device.
[0025] Preferably said the pump has a hydrodynamic bearing that produces a relatively flat pump head versus pump flow curve.
[0026] Preferably said physiological controller is capable of manual manipulation by the user.
[0027] Preferably said manual manipulation is within adjustable predefined limits.
[0028] Preferably said physiological controller is adapted for communication with a computer and wherein the physiological controller is adapted for manipulation by a software user interface.
[0029] Preferably said physiological controller includes an alarm.
[0030] In a further broad form of the invention there is provided a process for using physiological demand data to optimize pump speed of a rotary blood pump wherein the process comprises of the following steps: a heart rate of the user is non-invasively determined; a level of physiological exertion of the user is determined through non invasive means; an instantaneous pump speed and input power is used to calculate instantaneous blood flow rate; a pumping state is mathematically determined; the heart rate, pumping state and level of physical exertion are compared to the blood flow rate; and the pumping speed of the rotary blood pump is changed to appropriately supply the user with the correct blood flow rate.
[0031] In yet a further broad form of the invention there is provided a pump control system for a pump for use in a heart assist device; said system comprising data processing means which receives body motion information and heart rate information thereby to derive a speed control signal for impeller speed of an impeller of said pump.
[0032] Preferably said body motion information is derived from an accelerometer.
[0033] Preferably said accelerometer senses motion in a single axis.
[0034] Preferably said accelerometer senses motion in three orthogonal axes.
[0035] Preferably said heart rate information is derived from a non-invasive sensor.
[0036] Preferably said heart rate information is derived from voltage and current applied to an electric motor driving said impeller.
[0037] In yet a further broad form of the invention there is provided a method of control of pump speed of a blood pump; said method comprising establishing a base set point speed; said method further comprising establishing one or more criteria which, if satisfied, cause establishment of at least a second set point speed; said second set point speed higher than that of said base set point speed.
BRIEF DESCRIPTION OF DRAWINGS
[0038] Embodiments of the present invention will now be described with reference to the accompanying drawings wherein:
[0039] FIG. 1 is a diagram of a ventricular assist device installation within a human body suitable for control by embodiments of the present invention;
[0040] FIG. 2 is a block diagram of a physiological demand responsive of control system applicable to the system of FIG. 1 in accordance with a first preferred embodiment of the present invention;
[0041] FIG. 3 illustrates graphically the behavior of the control system of FIG. 2 under specified physiological conditions;
[0042] FIG. 4 is a graph of accelerometer behavior utilized as a basis for an input to the control algorithm of the first preferred embodiment;
[0043] FIG. 5 is a block diagram of a control system in accordance with a second preferred embodiment of the present invention;
[0044] FIG. 6 is a block diagram of a pumping state detection module for use with the second embodiment;
[0045] FIG. 7 is a flowchart for determining pump drive set point for the arrangement of the second embodiment;
[0046] FIG. 8 illustrates graphically an HQ curve for a preferred pump type particularly suited for use with the control system of FIG. 2 or FIG. 5 ; and
[0047] FIG. 9 is a diagram of a preferred embodiment of the present invention wherein said diagram shows preferred inputs and outputs.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0048] With initial reference to FIG. 1 there is illustrated in diagrammatic form a blood pump 10 installed within a human body 11 and arranged to function as a left ventricular assist device. The pump 10 is arranged to operate in parallel with blood flow passing through left ventricle 12 . This is effected by inserting an inlet cannula 13 into left ventricle 12 and directing blood flow through the inlet cannula into an inlet of blood pump 10 . Blood pump 10 , in operational mode, pumps the blood thus received into aorta 14 via outlet cannula 15 , as illustrated in FIG. 1 .
[0049] The blood pump 10 can take a number of forms and rely on a number of different pumping and drive technologies. Broadly, the pump technology can be based on axial or centrifugal rotary pump arrangements or on positive displacement technologies.
[0050] In particular, although not limiting forms, preferred pumping technologies for the control system to be described below include rotary pump technologies which rely on an impeller supported for rotation within a casing and which causes blood to be urged between an inlet and outlet of the casing as the impeller rotates therein. In more particular preferred forms a centrifugal form of pump can be utilized with the control system with the characteristics of the pump tailored to compliment or otherwise work particularly advantageously with the control system according to various embodiments of the present invention.
[0051] Typically the pump 10 is driven by an electrical power source, in this instance a battery pack 16 mounted externally of the body. Electrical power from the battery pack 16 is controlled by a controller unit 17 , also mounted externally of the body. In addition to communicating electrical power to the pump 10 the controller 17 can also communicate with an external programming source, in this case a personal computer 18 for the purposes of initial setup and ongoing periodic monitoring and recalibration of the pump and controller as customized for a specific patient.
[0052] Embodiments of a control system suited for use, although not exclusively, with the controller 17 of the arrangement described above and with reference to FIG. 1 will now be described.
DEFINITIONS
[0053] In the description which follows, the following definitions of various terms as referenced therein are to be utilized:
[0054] “non-invasive” is applied to the derivation of various physiological parameters of body 11 (including blood flow rates and the like) by means which do not require sensors to be placed (invasively) within the body.
[0055] “IRBP”—implantable rotary blood pump.
[0056] “LVAD”—left ventricular assist device.
[0057] “LVP”—left ventricular pressure.
[0058] “RMS” or “rms”—route mean square.
[0059] “V”—volts applied to pump motor.
[0060] “I”—current consumed by pump motor.
[0061] “SVR”—Systemic Vascular Resistance
[0062] “VR”—Venous Resistance
[0063] “H”—pump head pressure.
[0064] “N”—pump impeller rotation speed.
[0065] “Q”—flow rate of blood through pump.
[0066] “P” or “PWR”—pump power consumption.
[0067] “ω”—angular velocity of impeller.
[0068] “t”—time.
Pumping States
[0069] “TVC”—total ventricular collapse.
[0070] “PR”—pump regurgitation.
[0071] “PVC”—partial ventricular collapse.
[0072] “AC”—aortic valve closed.
[0073] “VE”—ventricle ejecting
First Embodiment
[0074] With initial reference to FIGS. 1-4 a first preferred embodiment of a control algorithm and control system is described below and by way of example.
[0075] In this embodiment the aim is to provide a pump controller which utilizes a control algorithm which takes as its two primary inputs for decision making firstly an indication of the degree of movement of body 11 per unit time as a coarse measure of exertion and hence pumping load required of the heart and particularly left ventricle 12 and secondly an indication of heart rate derived, in this instance, non-invasively by monitoring of electrical parameters driving pump 10 .
[0076] The system described with reference to FIGS. 1-4 exhibits the following characteristics:
[0077] 1. Allowing motor speed to vary and deriving control information from those time varying signals; and
[0078] 2. Concept of using control of power input or speed to the motor/pump.
[0079] The block diagram shown in FIG. 2 shows the signals that are derived (non-invasively) from pump motor power and speed. To detect these conditions the strategy is to measure speed instantaneously every revolution of the impeller as a digital signal from the motor commutation electronics. The haemo-dynamic controller electronics measure the frequency of this signal which is proportional to impeller speed. Using speed is an advantage since it is a digital signal, which in practice has been found to be an inherently less electrically noisy signal than that derived from measuring motor current or power. Both instantaneous speed and root mean square (rms) of speed are calculated. Also instantaneous pump input power and rms of pump input power are calculated.
[0080] Many researchers only discuss constant speed or speed set point. However the present control strategy allows impeller speed and pump input power to be freely modulated by ventricular contractions and uses the resulting dynamic information as feedback to the control system. The characteristics of centrifugal IRBPs mean that impeller speed is more sensitive to hydraulic load variations than for axial IRBPs. Furthermore, allowing impeller speed to vary in magnetically suspended IRBPs may affect suspension control. A preferred pump uses a hydro dynamically suspended impeller and therefore suspension controls are not needed.
Calculation of Instantaneous Impeller Speed N(t) and rms of Impeller Speed Nrms(t)
[0081] Each pulse from the commutation controller represents ⅙ th of a rotation of the impeller and is time stamped relative to a reference time base. Therefore the angular velocity ω of the impeller for each 60° of rotation is described by equation 1.
[0000]
ω
(
T
)
=
2
Π
6
[
(
Tn
+
1
)
-
Tn
]
equation
1
[0000] where Tn+1−Tn is the time difference between pulses (interrupts) in seconds. ω(t) is converted to speed N(t) in rpm by multiplying by 60/2II as-in equation 2
[0000]
N
(
t
)
=
60
ω
(
t
)
2
π
equation
2
[0000] Rms speed is calculated in equation 3 from a moving window of samples of N(t), the sample rate dependent on impeller speed. Each instantaneous speed sample is time stamped at t 1 to t n .
[0000]
Nrms
(
t
)
=
∑
o
n
[
N
(
t
)
]
2
n
equation
3
Calculation of Instantaneous and Rms Electrical Input Power Pin(t).
[0082] Calculation of pump electrical power is a direct way to monitor the power consumption of the pump. Since the pump power and speed is modulated by the heart which is an asymmetrical modulation (due to the ejection fraction not being 50% rms) calculation of both instantaneous power and speed is implemented. Power is calculated using equation 4.
[0000] P in( P )= Vm ( i )· Im ( t ) equation 4
[0000] Where Vm(t) and Im(t) are the “instantaneous” motor coil voltage and summed phase current respectively, sampled. A moving window of samples of Pin(t) is used to calculate P rms (t) using equation 5.
[0000]
P
rms
(
t
)
=
∑
o
n
[
Pin
(
t
)
]
2
n
equation
5
Second Embodiment
[0083] With reference to FIGS. 5 to 7 inclusive there will now be described a control system in accordance with a second preferred embodiment:
[0084] In relation to this second embodiment the control strategy is similar to that described with respect to the first embodiment but, in addition, includes as a further control input derived from non-invasively determined parameters the “pumping state” of pump 10 . This feature provides a safety-override mechanism as illustrated in the flowchart of FIG. 7 thereby to ensure that the basic control strategy described with reference to the first embodiment is less likely to put the patient at risk. Initially in the description which follows invasively derived parameters are discussed showing how the various pumping states have been defined and come to be identified. A method of non-invasively deriving the same parameters and pumping state determinations is then described with both forms of derivation being summarized in table 1.
[0085] With reference to FIG. 4 experimental data suggests that there is a correlation between heart rate and accelerometer output where at least a single axis accelerometer is attached to a patient and used as a measure of physical activity of the patient. This observation is used for the control algorithm now to be described.
[0086] FIG. 5 is a block diagram of the control arrangement wherein, in addition to the input variables described with reference to example 1 there is a “physical motion” input which can be derived from an accelerometer associated with a patient. In the simplest form the accelerometer can be a single axis accelerometer. In alternative forms multiple axes of accelerometer sensing can be utilized.
Detection of Physiologically Significant Pumping States
[0087] Physiologically critical pumping state detection methods are used based on the non-invasive system observers pump speed and electrical input power. Activity level is detected using heart rate (detected from pump impeller instantaneous speed) and motion by using an accelerometer although other measuring devices may be used without departing from the scope of the present invention. These non-invasive observers are utilized as inputs to a control algorithm for a rotary blood pump to seek to ensure that pump output is better adapted to patient rest and exercise states.
Identifying Pumping States
[0088] Methods were developed to detect pumping states based on instantaneous measured pump power and speed. The methods developed allow impeller speed and pump input power to be freely modulated by ventricular contractions. This dynamic information is utilized as feedback to the control system. Data from in-vitro and in-vivo experiments shows that states TVC (total ventricular collapse) and PR (pump regurgitation) produce low flow through the pump. State TVC produces non-pulsatile low flow while state PR produces pulsatile low flow less than 1 L/min. States PVC (Partial Ventricular Collapse), AC (Aortic valve Closed) and VE (Ventricle Ejecting) produce normal pump flows greater than IL/min. States PVC and PR can be differentiated from state AC since flow pulsatility is more evident. State PVC can be differentiated from state VE since the dynamic flow symmetry is different from all other states. The dynamic nature of the flow is reflected by pump speed and power. Instantaneous measured pump speed is used to indicate flow dynamics.
Detecting of State TVC, Ventricle Totally Collapsed Occluding the Inlet Cannula.
[0089] Examining the in-vitro and in-vivo data it has been found that state TVC can be consistently detected by fall in pump flow to near 0 L/min accompanied by a reduction of flow pulsatility. It has been observed Flow waveform symmetry may not be relevant for detection of this state.
[0000] Detecting State PVA, Ventricle not Ejecting and Beginning to Collapse onto the Cannula
[0090] The state PVC is indicated by a variation in symmetry of the instantaneous speed waveform given a level of pulsatility. Given that normal flow rates can still be observed during this state and that flow pulsatility is large, the only parameter distinguishing this state from the VE state is the flow symmetry.
State AC Ventricle not Ejecting and Positive Pump Flow.
[0091] By analyzing the cardiac cycle with the pump it has been was found that there may be a portion of state AC where the aortic valve remains closed, whilst however the pump flow is still pulsatile. Assistance beyond this point causes pump flow pulsatility to reduce. At high perfusion demands, as in exercise, the failed ventricle may be supplemented to such an extent that the flow through the pump is pulse-less. Theoretically if no left ventricle contraction occurs then implantable rotary blood plump flow will be non pulsatile. Contraction of the left ventricle with the pump connected means that pump head is proportional to the difference between the aortic pressure and the left ventricular pressure (LVP). If the pump power is increased beyond the point that the left ventricle is doing no work (the aortic valve no longer opens) maximum LVP begins to decrease. This means that minimum instantaneous pump differential pressure will begin to rise relative to the RMS of the pump differential pressure over the cardiac cycle. If the ventricle is weakened through heart failure this will occur at relatively lower pump speeds and the mitral valve will still continue to open and LVP maximum will decrease towards zero with increasing speeds. During this interval the mitral valve will open and close. Steady flow occurs when there is no pulsatility in the speed signal and the mitral valve never closes. The target speed at which this occurs will increase with SVR or VR and cardiac contractility. Continuing to increase the pump power will cause the transition from pulsatile to non pulsatile flow. This means detection of the state VE and state AC can only be achieved dynamically by considering the maximum instantaneous speed Nmax(t) and the rms of instantaneous speed Nrms(t) for the nth and (n-l)th cardiac cycle. A significant change occurs only if there is a change in average pump speed set point, after load or pre load. A method of detecting the AC state without relying on transitions has been chosen which uses peak to peak flow rate given that pump flow is greater than 1 L/min.
[0000] Detecting State VE, Ventricle Ejecting with Positive Pump Flow
[0092] State VE may be identified non invasively by pump flow rate being larger than 1 L/min and peak to peak instantaneous voltage (flow) being greater than a threshold value and the flow symmetry being greater than that for the PVC state.
[0000] Detecting State PR: The Point at which Pump Flow Rate is Less than Zero
[0093] The PR state may be indicated when the pump flow falls below the lower flow limits Qmin which is set to be 1 L/min. This level of Qmin is set at 1 L/min although not “0 L/min” may be was considered a safe limit to be classed as retrograde flow.
Pumping State Detection Using Non-Invasive Pump Parameters
[0094] By analyzing pump parameters deriving from invasive-derived parameters it is postulated that flow, flow amplitude and waveform symmetry appear to be good indicators of pumping state using only non-invasively-derived pump parameters. These variables can be detected non-invasively using estimated pump flow (Qest), peak to peak instantaneous speed Npp(n) and symmetry Nsym(n). Table 1 shows the relationship of physiological parameters to non-invasive pump parameters for each of the physiologically identified pumping states which have been taken from in-vitro and in-vivo data sets (n=3).
[0000]
TABLE 1
A summary of physiological (invasive) and pump (non-invasive)
parameters used as the criteria to identify pumping states.
Identifying Parameter
Non-invasive via pump
Invasion (Physiological)
(from speed and power)
AoP
Pulse Press.
LVP max
Qav
Q estRMS (t)
Npp(n)
State
mmHg
(mmHg)
(mmHg)
(L/min)
(L/min)
Q sym (n)
(rpm)
TVC
<40
<10
<40
<1
<1
—
<30
PVC
60-180
>10
60-180
<1
>1
<0.4
>30
AC
60-180
<10
<AoP
<1
>1
—
<30
VE
60-180
>10
>AoP
>1
>1
>0.4
>30
PR
60-180
>10
>AoP
>1
<1
>0.4
>30
[0095] Estimated pump flow Q est is derived from N rms (t) and PWR rms (t). The RMS of instantaneous pump speed N rms (t) and power PWR rms t) are derived from instantaneous speed N(t) and power PWR(t). The haemo-dynamic controller electronics measure the frequency of the speed signal, which is proportional to impeller speed. Using speed rather than power as an observer for dynamic changes is an advantage since it is a digital signal, substantially free from electrical noise which may contribute to error.
Detecting Low Flow
[0096] Equation 6 is used to model low and normal flow rate through the pump based on RMS impeller speed and electrical input power.
[0000] Q est αK +speed+Pwr+(Pwr) 2 +(Pwr) 3 equation 6
[0097] A flow Index, Q p Index, shown in equation 7 is developed to distinguish between low flow rates and normal flow rates. by incorporating Q est . If Q p Index>50 this corresponds in this example to a flow rate greater than 1 L/min. A Q p Index<50 means that flow is less than 1 L/min or “low flow”
[0000] Q p Index=50 ·Q est equation 7
[0098] Both the TVC and the PR pumping states defined and discussed produce low pump flow rates. States PVC, AC and VE produce “normal” flow rates where the circulation is not compromised.
Detecting Pulsatile Flow
[0099] States TVC and AC produce near non pulsatile pump flow. The difference between these states is that state AC occurs when the circulation is supported and state TVC when it is not. These states can be differentiated by comparing Q est Index. States PVC, VE and PR produces pulsatile flow. States PVC and VE produce flow which supports the circulation whereas state PR compromises the circulation due to back flow through the pump. It has been shown that instantaneous speed amplitude is proportional to pump flow amplitude. The flow pulsatility index Q p.p Index (equation 9) is developed based on instantaneous speed amplitude N p-p (n) (equation 8) which is equal to the difference between the maximum and the minimum instantaneous impeller speed N max (n) and N min (n) for the n th cardiac cycle. The index outputs a value greater than 50 for pulsatile flow and less than 50 for non pulsatile flow.
[0000] N p-p ( n )= N max ( n )− N min ( n ) equation 8
[0000]
Q
p
-
p
Index
=
50
·
Q
p
-
p
min
N
p
-
p
(
n
)
equation
9
Detecting Variations in Flow Symmetry
[0100] The in-vitro and in-vivo data show that instantaneous speed reflects the inverse symmetry of pump flow whilst current reflects the same symmetry, although speed exhibits less electrical noise. Thus it is postulated that the symmetry of flow can be estimated by using the inverted symmetry of instantaneous speed.
[0101] States PVC and VE both produce flow rates which support the circulation and a degree of pulsatility. Differentiating between states can be achieved by considering the symmetry of the flow wave form which is reflected in instantaneous speed. The symmetry of flow rate is an inversion of the instantaneous speed signal. The flow symmetry index Q sym Index (equation 11) is developed by using the inverted speed waveform symmetry defined by equation 10 with the symmetry threshold Q sym MAX set at 0. The index is set so that if the flow symmetry falls below 0.3 (speed symmetry rises above 0.7) its output is less than 50.
[0000]
N
sym
=
(
N
nrms
(
n
)
-
N
min
(
n
)
N
p
-
p
(
n
)
equation
10
Q
sym
Index
=
50
Q
sym
max
.
N
sym
equation
11
Determining the Current Pumping State From Non-Invasive Indicators
[0102] The block diagram shown in FIG. 5 shows the module that combines the detection methods discussed above derived from instantaneous power and speed. The current state is determined by the logic table shown in FIG. 6 where flow, flow pulsatility and symmetry are used to decide the present pumping state.
Detection of Heart Rate Using Pump Speed
[0103] [While pulsatile flow is detected, the heart rate is calculated by using the array of speed samples. For the entire speed array N[t 1 -t n ] of samples the frequency of speed is calculated by using the derivative of speed and detecting the time of the speed maxima and minima. The derivative of speed is defined in equation 12.
[0000]
N
(
t
n
)
t
=
N
(
t
n
)
-
N
(
t
n
-
1
)
Δ
t
equation
12
[0104] HR is then calculated by time stamping the maxima and minima of the speed signal given by HRa and HRb in is equations 13 and 14. The average is then computed and used as HR using equation 15. Speed maxima are detected by dN(t n )/dt changing from a positive to a negative value. Speed minima are detected by dN(t n )/dt changing from a negative to a positive value. T max(n) , t max(n-1) , t min(n) , t min(n-1) are the time stamps for the maximum and minimum values of instantaneous speed.
[0000]
HRa
=
60
[
t
max
(
n
)
-
t
max
(
n
-
1
)
]
equation
13
HRb
=
60
[
t
min
(
n
)
-
t
min
(
n
-
1
)
]
equation
14
Detection of Physical Motion
[0105] An accelerometer is mounted in the controller electronics and used to detect physical motion. The accelerometer output is amplified by a differential amplifier and integrated to provide a signal level indicating continuous physical motion.
[0106] A preferred embodiment of the present invention of the physiological demand responsive controller is suited for used with implantable third generation LVASs. Also, a further embodiment of the present invention is designed to cooperate with a Ventrassist™ left ventricle assist system (LVAS).
[0107] One of the preferred embodiments may automatically adjust the pumping speed of an implanted third generation blood pump to an optimal level for the varying physiological needs of the implanted patient. The preferred embodiment may achieve this by periodically iteratively changing the speed setpoint of the pump. When the control system detects increased physiological demand by the patient (e.g. by physical exertion) the controller will increase the pumping speed accordingly. The pumping state of the patient's heart and physiological demand of the patient will be computed by the control system. in real time as functions of the pump's motor power and speed setpoint of the pump. Additionally, the physiological demand of the patient may also be detected by the use of a three axis accelerometer.
[0108] This accelerometer may be able to detect the instantaneous motion of the patient. Preferably, this instantaneous motion may also be indicative of the relative motion of the patient. The output of the accelerometer may preferably be directed into a conditioning circuit to digitize and filter the output signal of said accelerometer. This signal will then be passed from the conditioning circuit to a computational module which derives a physiological demand state (e.g. resting, sleeping, exercising, or patient collapse) as a numerically represented version of the state (e.g. 1=resting; 2=sleeping etc). The numerically represented version of the physiological demand state may then be inputted into the control system for a pumping device or medical device. The pumping speed of the implantable blood pump may then be altered in respect of the predetermined range for physiological demand for a particular patient.
[0109] Preferably, the predetermined ranges of pumping speeds will be set by a specialist doctor at the time of implantation of the blood pump. Additionally, it may be preferable to allow doctors to amend the predetermined range as they see fit.
[0110] Preferably in an embodiment of the present invention the control system may include a specialized algorithm. This algorithm may include a mathematical model of ideal pumping speed of an implantable blood pump for suitable physiological conditions of the patient. This algorithm may receive input or data included within three broad areas of data. These areas of data may include pump power, instantaneous pump speed and physical motion. The algorithm within the controller system (see FIG. 9 ) may use these areas of data to predict certain patient data. This patient data may include blood flow rate, heart rate, flow profile, pulsatility and physiological demand. The algorithm will then output the preferred pump speed and the remainder of the controller system will use this information to set a speed setpoint for the blood pump.
[0111] Preferably, an embodiment of the present invention will be such that iterative changes will be able to be made in timely manner.
[0112] In a further embodiment of the present invention, a preferred physiological demand responsive controller system may be adapted for use with a radial off flow type centrifugal blood pump.
[0113] The above describes only some embodiments of the present invention and modifications, obvious to those skilled in the art, can be made thereto without departing from the scope and spirit of the present invention.
[0114] The system is particularly suited for use with pumps which exhibit a relatively flat HQ curve as described with reference to FIG. 8 . In particular, but not exclusively, pumps of the radial off flow type as, for example, described in International Patent Application PCT/AU98/00725 can exhibit this relatively flat characteristic. The description of PCT/AU98/00725 is incorporated herein by cross-reference.
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A demand responsive physiological control system for use with a rotary blood pump; said system including a pump controller which is capable of controlling pump speed of said pump; said system further including a physiological controller, and wherein said physiological controller is adapted to analyze input data relating to physiological condition of a user of said pump; and wherein said physiological controller determines appropriate pumping speed and sends a speed control signal to said pump controller to adjust pump speed; said system further including a physiological state detector which provides said input data indicative of at least one physiological state of said user, in use, to said physiological controller.
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This is a continuation-in-part of our U.S. patent application Ser. No. 298,773, filed Sept. 2, 1981, now abandoned incorporated by reference.
FIELD OF THE INVENTION
This invention relates to surgical devices designed for the draining of cerebrospinal fluid, and more particularly to an indwelling valve for in-utero treatment of hydrocephalic fetuses.
BACKGROUND OF THE INVENTION
There are many prior art devices relating to various types of valves permitting the drainage of fluid for the treatment of hydrocephalus. However, these prior art devices are all used for the treatment of the already born, and are not suitable for the treatment of a hydrocephalic fetus. Examples of such prior art devices are shown in the following prior U.S. patents, found as a result of a preliminary search:
Holter et al, U.S. Pat. No. 2,969,066, Schwartz, U.S. Pat. No. 3,109,429, Hakim, U.S. Pat. No. 3,288,142, Kuffer et al, U.S. Pat. No. 3,674,050, Hakim, U.S. Pat. No. 3,924,635, Hakim, U.S. Pat. No. 4,106,510, and Hildebrandt et al, U.S. Pat. No. 4,156,422.
SUMMARY OF THE INVENTION
The present invention comprises prosthesis and devices for the treatment of the hydrocephalic fetus. It involves a prosthesis suitable for non-traumatic surgical placement or implantation in the fetus, while still in the womb. A particularly unique feature derives from its avoidance of extensive surgery for placement of existing prosthesis in "born" children or adults, where the shunt assembly vents cerebrospinal fluid (CSF) into the thoracic or abdominal cavity. Another highly important feature is the prevention of permanent brain damage and physical malformation to the fetus, which otherwise would be caused by the untreated intrauterine growth of a hydrocephalic fetus.
A particular problem resulting to the treatment of the unborn fetus is its relative inaccesibility in utero. A device according to the present invention can be used under conditions providing the barest access to the unborn fetus at fetoscopy. In contrast, existing prostheses for treating fetal hydrocephalus risk far more extensive uterine trauma, making premature labor, delivery and fetal death a likely sequel.
A hydrocephalic drainage valve according to one embodiment of the present invention consists of a hollow shank with a pointed enlarged conical tip, forming a shoulder. The shank has an intake port adjacent the shoulder. A ball check valve in the shank is urged by a coiled spring toward closing relationship with the port. A hollow set screw is adjustable in the shank to vary the biasing force on the ball. A sleeve is slidably engaged on the shank, extends adjacent the shoulder, has a centrally apertured head, and has implantation threads near the head. The head has aligned opposite radial grooves, or equivalent recess structure, engageable by an insertion tool. In other embodiments, the valve is adapted to be inserted by fluid pressure means and to be held in place by fetal skin-penetrating washer means carried on and lockingly engageable with the hollow valve shank, avoiding the use of implantation threads.
The invention is described in more detail in the attached articles by Hodgen entitled "Antenatal Diagnosis and Treatment of Fetal Skeletal Malformations with Emphasis on In Utero Surgery for Neural Tube Defects and Limb Bud Regeneration", and Michejda et al, entitled "In Utero Diagnosis and Treatment of Fetal Skeletal Anomalies: I--Hydrocephalus", both published in Volume 246, No. 10, 1981 issued of the Journal of the American Medical Association, pages 1079-1083 and 1093-1097, respectively. The contents of these two attached articles are incorporated by reference.
Accordingly, a main object of the invention is to provide a novel and improved method and apparatus for the treatment of the hydrocephalic fetus, which overcome the deficiencies and disadvantages of the prior known hydrocephalus treatments.
A further important object of the present invention is to provide an improved drainage valve device for the in utero treatment of a hydrocephalic fetus, said device being relatively easy to calibrate, being safe to use, and being usable even under conditions providing the barest access to the fetus at fetoscopy.
A still further object of the invention is to provide an improved technique and apparatus for treating hydrocephalus in a fetus by implanting a suitably calibrated cerebrospinal fluid drainage valve in the skull of the fetus to relieve hydrocephalic pressure and thereby to prevent permanent brain damage and physical malformation which would otherwise be caused by untreated intrauterine growth of the hydrocephalic fetus.
BRIEF DESCRIPTION OF THE DRAWINGS
Further objects and advantages of the invention will become apparent from the following description and claims, and from the accompanying drawings, wherein:
FIG. 1 is an exploded view of a hydrocephalus drain valve device in accordance with the present invention.
FIG. 2 is an enlarged elevational view of the assembled valve device of FIG. 1, shown in open position.
FIG. 3 is an enlarged elevational view of the assembled device of FIG. 1, shown in closed position.
FIG. 4 is a further enlarged longitudinal cross-sectional view taken substantially on line 4--4 of FIG. 2.
FIG. 5 is a schematic diagram showing the device of FIGS. 1 to 4 in operative position in the fetus, draining fluid directly to the uterus.
FIG. 6 is a schematic view of an insertion tool for a valve of the type shown in FIGS. 1 to 5, in accordance with the present invention.
FIG. 7 is a diagrammatic view showing a system for calibration of the implant valve of the present invention.
FIG. 8 is an enlarged fragmentary elevational view, partly in cross-section, showing how the valve is secured in the calibration system of FIG. 7.
FIG. 9 is a diagrammatic view showing an apparatus for implanting a modified form of drainage valve according to the present invention.
FIG. 10 is an enlarged fragmentary vertical cross-sectional view taken through the implant tube of the apparatus of FIG. 9, showing how the drainage valve is positioned therein for implantation.
FIG. 11 is a horizontal cross-sectional view taken substantially on line 11--11 of FIG. 10.
FIG. 12 is a further enlarged horizontal cross-sectional view taken substantially on line 12--12 of FIG. 10.
FIG. 13 is a fragmentary vertical cross-sectional view taken substantially on line 13--13 of FIG. 12.
FIG. 14 is an enlarged perspective view showing a further modification of an implantable hydrocephalic drainage valve according to the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to the drawings, and more particularly to FIGS. 1 to 6, a first typical embodiment of a pressure relief valve according to the present invention, called a "HAVIT" (meaning hydrocephalic antenatal vent for intrauterine treatment), is shown generally at 20. The relief valve device 20 is formed of five components, as best seen in FIG. 1, comprising a sleeve-like valve body 21, a hollow set screw 22, a coiled spring 23, a valve ball 24, and a valve element 25 in the form of a hollow shank having an enlarged solid integral conical tip 26 defining an annular shoulder 27. The parts 21, 22, 23 and 25 are all preferably fabricated from low carbon super alloy steel, such as Hastelloy C or 316 L stainless steel. The ball 24 is preferably fabricated from synthetic ruby, and typically is 0.047 inch in diameter. The hollow set screw 22 is hexagonally recessed at 28 (see FIGS. 4 and 11) for driving engagement by a conventional Allen wrench.
The sleeve-like valve body 21 is integrally formed with a spherically rounded head 29 and external implantation threads 30 adjacent said head. The head 29 has diametrically opposite radial grooves 31, 31 adapted to drivingly receive the spaced end prongs 32, 32 of a driving tool 33, shown in FIG. 6.
As shown in FIG. 4, the shank member 25 is formed adjacent shoulder 27 with a transverse bore 34 which communicates with an axial bore 35 leading to an annular ball seat 36 in the hollow shank 25. The main axial cavity 37 contains the biasing spring 23, which bears between the valve ball 24 and the inner rim of set screw 22, which is threadedly engaged in cavity 37 and which is adjustable by means of an Allen wrench so as to vary the biasing force exerted by the spring 23 on the ball 24. The sleeve 21 is slidably engaged on the shank 25 and may be moved from a closed position thereon, as shown in FIG. 3, abutting the shoulder 27, to an open position shown in FIG. 2, by exerting a pushing inward axial force on the outer shank end 38, as will be presently described. When the valve assembly is in its open position, shown in FIGS. 2 and 4, a predetermined limiting hydrocephalic fluid pressure acting at passage 34 will unseat ball 24 and allow the fluid to flow out through the cavity 37 and the hollow set screw 22, thereby preventing the hydrocephalic pressure from rising above the preset limiting pressure value.
Referring to FIGS. 7 and 8, a typical calibration of the valve device 20 may comprise the following steps:
1. The shank assembly comprising the shank member 25 and the parts contained therein (the assembly of FIGS. 2, 3 and 4 with the sleeve member 21 removed) is inserted through the reduced end 39 of a transparent flexible tube 40 to the position shown in FIGS. 7 and 8, the reduced tube portion 39 being sufficiently resilient to allow the enlarged conical tip 26 to pass therethrough. The inside diameter of the main portion of tubing 40 is large enough to allow water pressure in the tube 40 to act freely on the transverse inlet bore 34.
2. The reduced tube portion 39 is sealingly clamped around shank 25 by means of a suitable clamp 41.
3. The opposite end of flexible tube 40 is suitably connected to one branch conduit 42 of a 3-way valve 43.
4. A syringe 44, filled with water, is connected to the inlet branch conduit 45 of the 3-way valve 43.
5. A manometer 46 is connected to the other conduit branch 47 of valve 43, via a small piece of tubing 48.
6. Using an Allen wrench engaged through the end 38 of shank 25, the set screw 22 is rotated counterclockwise to relieve the spring tension on ball 24. When no more spring tension can be felt on the set screw, the spring and ball are set free of tension.
7. The control lever 49 of 3-way valve 43 is turned to a position communicatively connecting branch 45 to branch 43 so that water will flow from the syringe 44 to the valve shank 25.
8. Water is injected from the syringe 44 into the shank 25 and is allowed to bleed through freely until no air bubbles can be seen in the transparent tube 40.
9. Using the Allen wrench, the set screw 22 is turned clockwise to close or tighten the ball 24 into its seat 36.
10. Lever 49 on 3-way valve 43 is turned to a position sealing off branch 42 (leading to tube 40 and shank 25) andd communicatively connecting branch 45 to branch 47, thereby connecting syringe 44 to manometer 46.
11. Water is injected by syringe 44 into manometer 46 to a pressure greater than the pressure setting desired for valve shank 25.
12. Lever 49 is then turned to a position shutting off the syringe 44 and communicatively connecting branch 47 to branch 42, thereby connecting manometer 46 to valve shank 25.
13. Using the Allen wrench, the implant valve shank 25 is slowly opened by turning the Allen wrench in a counterclockwise direction. As water starts to bleed out of the valve shank 25, the indicated pressure level in the manometer 46 will start to drop.
14. The spring tension in the valve shank 25 may then be adjusted to whatever pressure setting is desired.
To assure accurate pressure readings, the outlet end 38 of the implant valve shank 25 must be at the same level as the zero reading mark on the manometer 46 when calibrating.
As will be presently described, in the surgical placement of the relief valve device 20, the fetal head, shown at 50 in FIG. 5, is carefully exposed and punctured at a suitable chosen location, and the device 20 is inserted by threaded engagement in the puncture, using the insertion tool 33 of FIG. 6. The tool 33 has an elongated shank 51 formed with the spaced end prongs 32, 32 which are engaged in the radial grooves 31, 31, with the sleeve 21 in the closed position of FIG. 3, namely, abutting the shoulder 27. The top end of the shank 25 is received in the notch 52 defined between the prongs 32, 32. The tool 33 has opposing inwardly curved spring arms 53, 53 engageable beneath the head 29, the top ends of the spring arms being secured to the shank 51, and the shank being provided with a slidable locking ring 54 movable downwardly to releasably lock the arms 53, 53 in gripping positions. With the device 20 thus locked to the tool shank 51, the device 20 is engaged through the puncture and rotated to cause the threads 30 to bite into and threadedly interengage with the wall of the puncture, achieving the position substantially shown in FIG. 5. With this position achieved, the ring 54 is retracted, allowing the arms 53, 53 to spread and disengage from beneath the head 29. The top end of the shank 25 is then pushed downwardly to expose the intake passage 34, namely, to the open position of FIG. 2.
EXAMPLES
Manifestations of Hydrocephaly in Utero
Hydrocephaly was diagnosed prior to mid-gestation by following the course of abnormal ventricular dilation through sonographic images and maternal serum AFP. Upon reaching the 3rd trimester, hysterotomy provided nearly unrestricted accessibility to measure ventricular CSF pressures and perform surgical reparations. Whereas normal fetuses gave readings in the range of 45 to 55 mm of H 2 O, hydrocephalus was sometimes associated with pressure of more than 100 mm of water. These definitive measurements were confirmed by visual symptoms, such as bulging of the eyes, retarded ossification of cranial sutures, and disproportionate enlargement of frontal aspects of the fetal skull. Frequently, the hydrocephaly caused protrusion of an encephalocele whenever crania bifidia was present.
Postnatal Outcome (Treated versus nontreated animals)
Untreated hydrocephalic neonates manifested intrauterine growth retardation (retarded 310 g±58, N=10; control 470 g±52, X±SE) and usually died within 10 to 14 days after delivery; during this time they continued with severe hydrocephaly, progressive muscular weakness with delayed motor responses and frequent seizures accompanied by gastrointestinal and respiratory distress. In marked contrast, most infant monkeys that had been treated with the HAVIT in utero averted demise, demonstrated progressive physical dexterity and grew at near normal rates in the postnatal interval. Although their encephaloceles subsided in part, crania bifida remained, due to persistent hypoplasia of the occipital bones.
Procedures Applied to Intrauterine Placement of HAVIT
Access to the fetal cranium was obtained at hysterotomy between gestation 115-125 (term=167 days) and the pathway of the HAVIT, relative to the lateral ventricles, was applied uniformly in all surgical procedures.
The surgery included:
(1) a ventral midline incision, extending from the umbilicus to the pubis and an incision 3-5 cm long made through the uterus and amnion over the head of the fetus and outside the limits of the placental girdle.
(2) Careful exposure of the fetal head was followed by puncture and placement of HAVIT in the cranial vault 3 mm lateral to the anterior fontanelle, with penetration 12-14 mm into the anterior horn of the ventricular cavity.
(3) The fetal head was placed back in the uterus. The amniotic sac was closed, when possible, with a simple continuous row of 3-0 Vicryl (Ethicon, Somerville, N.J.). The uterus was closed with a simple continuous row of 2-0 Vicryl and reinforced with a continuous Lambert suture. The abdominal wall was closed with simple interrupted sutures of 2-0 Vicryl. The skin edges were approximated with a continuous subcuticular suture and the skin closed with simple interrupted 2-0 Vicryl.
Roentgenographic observations followed the surgical insertion of the HAVIT. The security of the prosthesis in situ and the process of cranial configuration among hydrocephalic fetuses was monitored by X-ray at 4-6 week intervals until term.
FIG. 9 diagrammatically illustrates another system for implanting modified forms of drainage valves according to the present invention, shown in detail in FIGS. 10 to 13 and FIG. 14, respectively. The modified drainage valves are adapted to be implanted by employing a suitable fluid pressure source, such as a compressed air cylinder 54, to drive the valve into operative position in the fetal head 50 via a rigid guide tube 55 forming part of an insertion assembly, shown generally at 56. The assembly 56 includes a conventional fetoscope 57 optically coupled to the interior of the fetal head 50 via optical transmission means, such as fiber optic elements contained in a rigid tube 58 secured adjacent and parallel to the valve guide tube 55. The assembly 56 includes conventional solenoid valve means 59 controlled by a trigger switch 60 for opening the solenoid valve means to allow compressed air from tank 54 to be delivered to guide tube 55. The air pressure cylinder 54 and fetoscope 57 are commercially available.
The fetal head 50 is surgically positioned to permit the fetoscope to approach the anterior surface (mid-parietal area) with the guide tube perpendicular. The fetoscope 57 provides a means of viewing the cranial area into which the intake end of the drainage valve is to be introduced.
In the embodiment of FIGS. 10 to 13, the drainage valve, designated generally at 61, comprises a hollow shank member 62 with an inner cavity 37 and a ball valve element 24 on a valve seat 36 communicating with a transverse bore 34, and having an integral conical tip 63. A hollow set screw 22 is threadedly engaged in cavity 37 and bears on the top end of a coiled spring 64. Spring 64 has a reduced lower end portion 65 which bears on the valve ball 24. The tension of spring 64 can be adjusted by means of hollow set screw 22 in the same manner as described above, employing a calibration apparatus similar to that shown in FIGS. 7 and 8.
Shank 62 is provided with a suitably vented integral circular head 66 adapted to be positioned slidably in guide tube 55 and acting as a vented driving piston for the shank member 62.
Surrounding and slidably engaging shank member 62 is an implantation drivable washer member 67 provided with a plurality of evenly spaced peripheral straight depending barb elements 68 directed downwardly. The washer member 67 is slidable in the guide tube 55, said washer member 67 being drivingly engageable by the piston element 66 when it is driven downwardly by the compressed air from tank 54. The driving force causes the barbs 68 to penetrate the skin of the fetal head 50 and to lock the washer member 67 to the fetal head. Washer member 67 has a plurality of downwardly and inwardly inclined, evenly spaced, inner locking lugs 69 engaging shank member 62 (see FIG. 13) and locking the shank member in its downwardly driven position after the piston 66 has acted on the washer member 67 to drive the barbs 68 into the fetal skin. This secures the drain valve 61 in operative position in the fetal skull.
After the drain valve 61 has been implanted, its position can be optically checked by the fetoscope 57. The apparatus 56 can be thereafter disengaged, and the HAVIT remains secured to the skin over the ventricle until its removal sometime after birth.
The retaining water or ring 67 also serves to stabilize the movement of the HAVIT as it travels from within the tube 55 to its target.
FIG. 14 illustrates another form of drainage valve, similar to that shown in FIGS. 10 to 13 and designated generally at 70. The valve assembly 70 comprises a shank member 71 generally similar to the previously described shank member 62 but having a peripheral locking rib 72 located subjacent to the integral piston element 66. The slidable locking washer, shown at 67', is formed at its peripheral portion with evenly spaced, integral resilient downwardly-directed barbed hook members 68' which are penetrable into the fetal skin in the same manner as barbs 68 in the embodiment of FIGS. 10 to 13, responsive to the downward driving force imparted by the piston member 66. When the shank 71 is driven downwardly, the peripheral rib 72 snaps past the inner central opening 73 of washer 67' and locks the shank 71 in its lowered position in the fetal skull, with the barbed hook members 68' embedded in the fetal skin, thus holding the drainage valve 70 in operative position. The drainage valve is removed sometime after birth.
As in the embodiment of FIGS. 10 to 13, the retaining washer or ring 67' also serves to stabilize the HAVIT 70 as it travels from within the tube 55 to its target.
While certain specific embodiments of improved hydrocephalic drainage valves have been disclosed in the foregoing description, it will be understood that various modifications within the scope of the invention may occur to those skilled in the art. Therefore it is intended that adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments.
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A hydrocephalic drainage valve consisting of a hollow shank with a pointed conical tip. The shank has an intake port adjacent the conical tip. A ball check valve in the shank is urged by a coiled spring toward closing relationship with the port. A hollow set screw is adjustably mounted in the shank to vary the biasing force on the valve ball. In one form, for manual implantation, a sleeve is slidably mounted on the shank, has a centrally apertured enlarged head and has implantation enlarged threads near the head. The head has aligned opposite radial grooves which are engageable by a manual insertion tool. In other forms, for pneumatic insertion, the shank has an enlarged head, employed as a driving piston in a pneumatic insertion tube. A washer member with implantation barbs is slidably mounted on the shank and is arranged to be locked to the shank subjacent the head responsive to the pneumatic driving action, with its barbs embedded in the fetal skin around the implantation puncture, thus holding the shank in operating position with the intake port exposed in the cranial vault.
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BACKGROUND OF THE INVENTION
The present invention relates to a method of cleaning a surface of a substrate using hydrochlorofluorocarbons having 3 to 5 carbon atoms.
Vapor degreasing and solvent cleaning with fluorocarbon based solvents have found widespread use in industry for the degreasing and otherwise cleaning of solid surfaces, especially intricate parts and difficult to remove soils.
In its simplest form, vapor degreasing or solvent cleaning consists of exposing a room-temperature object to be cleaned to the vapors of a boiling solvent. Vapors condensing on the object provide clean distilled solvent to wash away grease or other contamination. Final evaporation of solvent from the object leaves behind no residue as would be the case where the object is simply washed in liquid solvent.
For soils which are difficult to remove, where elevated temperature is necessary to improve the cleaning action of the solvent, or for large volume assembly line operations where the cleaning of metal parts and assemblies must be done efficiently and quickly, the conventional operation of a vapor degreaser consists of immersing the part to be cleaned in a sump of boiling solvent which removes the bulk of the soil, thereafter immersing the part in a sump containing freshly distilled solvent near room temperature, and finally exposing the part to solvent vapors over the boiling sump which condense on the cleaned part. In addition, the part can also be sprayed with distilled solvent before final rinsing.
Vapor degreasers suitable in the above-described operations are well known in the art. For example, Sherliker et al. in U.S. Pat. No. 3,085,918 disclose such suitable vapor degreasers comprising a boiling sump, a clean sump, a water separator, and other ancilliary equipment.
Cold cleaning is another application where a number of solvents are used. In most cold cleaning applications, the soiled part is either immersed in the fluid or wiped with rags or similar objects soaked in solvents.
In cold cleaning applications, the use of the aerosol packaging concept has long been found to be a convenient and cost effective means of dispensing solvents. Aerosol products utilize a propellant gas or mixture of propellant gases, preferably in a liquified gas rather than a compressed gas state, to generate sufficient pressure to expel the active ingredients, i.e. product concentrates such as solvents, from the container upon opening of the aerosol valve. The propellants may be in direct contact with the solvent, as in most conventional aerosol systems, or may be isolated from the solvent, as in barrier-type aerosol systems.
Chlorofluorocarbon solvents, such as trichlorotrifluoroethane, have attained widespread use in recent years as effective, nontoxic, and nonflammable agents useful in degreasing applications and other solvent cleaning applications. Trichlorotrifluoroethane has been found to have satisfactory solvent power for greases, oils, waxes and the like. It has therefore found widespread use for cleaning electric motors, compressors, heavy metal parts, delicate precision metal parts, printed circuit boards, gyroscopes, guidance systems, aerospace and missile hardware, aluminum parts and the like. Trichlorotrifluoroethane has two isomers: 1,1,2-trichloro-1,2,2-trifluoroethane (known in the art as CFC-113) and 1,1,1-trichloro-2,2,2-trifluoroethane (known in the art as CFC-113a). CFC-113 has a boiling point of about 47° C. and has been found to have satisfactory solvent power for greases, oils, waxes, and the like.
Another commonly used solvent is chloroform (known in the art as HCC-20) which has a boiling point of about 63° C. Perchloroethylene is a commonly used dry cleaning and vapor degreasing solvent which has a boiling point of about 121° C. These compounds are disadvantageous for use as solvents because they are toxic; also, chloroform causes liver damage when inhaled in excess.
Although chlorine is known to contribute to the solvency capability of a compound, fully halogenated chlorofluorocarbons and hydrochlorofluorocarbons are suspected of causing environmental problems in connection with the earth's protective ozone layer. Thus, the art is seeking new compounds which do not contribute to environmental problems but yet provide the solvency properties of CFC-113.
Chlorofluorocarbons (CFCs) such as CFC-113 are suspected of causing environmental problems in connection with the ozone layer. Under the Clean Air Act, CFC-113 is being phased-out of production.
In response to the need for stratospherically safe materials, substitutes have been developed and continue to be developed. Research Disclosure 14623 (June 1978) reports that 1,1-dichloro-2,2,2-trifluoroethane (known in the art as HCFC-123) is a useful solvent for degreasing and defluxing substrates. In the EPA "Findings of the Chlorofluorocarbon Chemical Substitutes International Committee", EPA-600/9-88-009 (April 1988), it was reported that HCFC-123 and 1,1-dichloro-1-fluoroethane (known in the art as HCFC-141b) have potential as replacements for CFC-113 as cleaning agents.
Commonly assigned U.S. Pat. No. 4,947,881 teaches a method of cleaning using hydrochlorofluoropropanes having 2 chlorine atoms and a difluoromethylene group. European Publication 347,924 published Dec. 27, 1989 teaches hydrochlorofluoropropanes having a difluoromethylene group. International Publication Number WO 90/08814 published Aug. 9, 1990 teaches azeotropes having at least one hydrochlorofluoropropane having a difluoromethylene group.
A wide variety of consumer parts is produced on an annual basis in the United States and abroad. Many of these parts have to be cleaned during various manufacturing stages in order to remove undesirable contaminants. These parts are produced in large quantities and as a result, substantial quantities of solvents are used to clean them. It is apparent that the solvent used must be compatible with the material to be cleaned.
Other advantages of the invention will become apparent from the following description.
SUMMARY OF THE INVENTION
The present invention provides a method of cleaning a surface of a substrate which comprises treating the surface with a solvent which is a straight chain or branched hydrochlorofluorocarbon having 3 to 5 carbon atoms. The straight chain hydrochlorofluorocarbons having 3 carbon atoms are listed in Table I below.
TABLE I______________________________________Number Chemical Formula______________________________________HCFC-234ab CFH.sub.2 CCl.sub.2 CF.sub.3HCFC-234bb CF.sub.3 CFClCClH.sub.2HCFC-234bc CFH.sub.2 CFClCF.sub.2 ClHCFC-234fa CF.sub.2 ClCH.sub.2 CF.sub.2 ClHCFC-234fb CF.sub.3 CH.sub.2 CFCl.sub.2HCFC-243ec CF.sub.2 ClCFHCClH.sub.2HCFC-244ba CFH.sub.2 CFClCF.sub.2 HHCFC-244da CF.sub.2 HCClHCF.sub.2 HHCFC-244ea CF.sub.2 HCFHCFClHHCFC-244ec CFH.sub.2 CFHCF.sub.2 ClHCFC-244fa CFClHCH.sub.2 CF.sub.3HCFC-244fb CF.sub.2 HCH.sub.2 CF.sub.2 ClHCFC-252dc CH.sub.3 CClHCF.sub.2 ClHCFC-253bb CH.sub.3 CFClCF.sub.2 HHCFC-253ea CF.sub.2 HCFHCClH.sub.2HCFC-253ec CH.sub.3 CFHCF.sub.2 ClHCFC-253fa CF.sub.2 HCH.sub.2 CFClHHCFC-253fc CFH.sub.2 CH.sub.2 CF.sub.2 ClHCFC-262fa CF.sub.2 HCH.sub.2 CClH.sub.2HCFC-271b CH.sub.3 CFClCH.sub.3HCFC-271fb CH.sub.3 CH.sub.2 CFClH______________________________________
Known methods for making fluorinated compounds can be modified in order to form the straight chain hydrochlorofluorocarbons having 3 carbon atoms of the present invention.
For example, Haszeldine, Nature 165, 152 (1950) teaches the reaction of trifluoroiodomethane and acetylene to prepare 3,3,3-trifluoro-1-iodopropene which is then dehydroiodinated to form 3,3,3-trifluoropropyne. By using 3,3,3-trifluoropropyne as a starting material, CF 3 CFClCClH 2 (HCFC-234bb) may be prepared as follows. Commercially available trifluoromethyl iodide may be reacted with acetylene to prepare 3,3,3-trifluoro-1-iodopropene which is then dehydroiodinated to form 3,3,3-trifluoropropyne. The 3,3,3-trifluoropropyne may then be reacted with commercially available hydrogen fluoride to form 2,3,3,3-tetrafluoro-1-propene which is then chlorinated to form 1,2-dichloro-2,3,3,3-tetrafluoropropane.
E. T. McBee et al., "Fluorinated Derivatives of Propane", J. of Amer. Chem Soc. 69, 944 (1947) teach a method for the preparation of CClF 2 CHClCH 3 (HCFC-252dc). Commercially available 1,1-dichloropropene is reacted with commercially available commercially available hydrogen chloride to form 1,1,1-trichloropropane. The 1,1,1-trichloropropane is then reacted with commercially available hydrogen fluoride to form 1-chloro-1,1-difluoropropane which is then chlorinated to form 1,2-dichloro-1,1-difluoropropane.
CF 2 ClCFHCClH 2 (HCFC-243ec) may be prepared as follows. Commercially available 1,1,3-trichloropropene may be dehydrohalogenated to form 1,3-dichloro-1-propyne. The 1,3-dichloro-1-propyne may then be fluorinated to form 1,3-dichloro-1,2-difluoro-1-propene which may then be reacted with commercially available hydrogen fluoride to form 1,3-dichloro-1,1,2-trifluoropropane.
CFH 2 CFClCF 2 H (HCFC-244ba) may be prepared as follows. Commercially available 1,3-difluoro-2-propanol may be dehydrated to form 1,3-difluoro-1-propene which may then be dehydrohalogenated to form 3-fluoro-1-propyne. The 3-fluoro-1-propyne may then be fluorinated, chlorinated, and fluorinated to form 1,1,2,3-tetrafluoro-2-chloropropane.
CFH 2 CFHCF 2 Cl (HCFC-244ec) may be prepared as follows. Commercially available 1,1,3-trichloropropene may be fluorinated to form 1,1-dichloro-3-fluoro-1-propene which may then be dehydrohalogenated to form 1-chloro-3-fluoro-1-propyne. The 1-chloro-3-fluoro-1-propyne may then be fluorinated to form 1-chloro-1,2,3-trifluoro-1-propene which may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1,1,2,3-tetrafluoropropane.
CFClHCH 2 CF 3 (HCFC-244fa) may be prepared as follows. Commercially available 1,1,3-trichloropropene may be fluorinated to form 1,1,1,2,3-pentafluoropropane. The 1,1,1,2,3-pentafluoropropane may then be dehydrohalogenated to form 1,3,3,3-tetrafluoro-1-propene which may then be reacted with commercially available hydrogen chloride to form 1-chloro-1,3,3,3-tetrafluoropropane.
CF 2 HCH 2 CF 2 Cl (HCFC-244fb) may be prepared as follows. Commercially available 2,2,3,3-tetrafluoro-1-propanol may be fluorinated to form 1,1,1,2,2,3-hexafluoropropane which may then be dehydrohalogenated to form 1,3,3-trifluoro-1-propyne. The 1,3,3-trifluoro-1-propyne may then be reacted with commercially available hydrogen chloride to form 1-chloro-1,3,3-trifluoro-1-propene which may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1,1,3,3-tetrafluoropropane.
CH 3 CFClCF 2 H (HCFC-253bb) may be prepared as follows. Commercially available 1,2-dibromopropane may be dehydrohalogenated to form propyne. The propyne may then be fluorinated, chlorinated, and fluorinated to form 2-chloro-1,1,2-trifluoropropane.
CH 3 CFHCF 2 Cl (HCFC-253ec) may be prepared as follows. Commercially available 1,2-dichloropropane may be dehydrohalogenated to form 1-chloro-1-propene which may then be dehydrogenated to form 1-chloro-1propyne. The 1-chloro-1-propyne may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1-fluoro-1-propene which may then be fluorinated to form 1-chloro-1,1,2-trifluoropropane.
The preferred straight chain hydrochlorofluorocarbons having 3 carbon atoms are CF 2 ClCFHCClH 2 , CFH 2 CFClCF 2 H, CFH 2 CFHCF 2 Cl, CFClHCH 2 CF 3 , CF 2 HCH 2 CF 2 Cl, CH 3 CFClCF 2 H, and CH 3 CFHCF 2 Cl.
The straight chain hydrochlorofluorocarbons having 4 carbon atoms are listed in Table II below.
TABLE II______________________________________Number Chemical Formula______________________________________HCFC-354lbes CH.sub.3 CHFCClFCF.sub.2 ClHCFC-354lcd CH.sub.3 CClHCF.sub.2 CF.sub.2 ClHCFC-354mbd CH.sub.3 CClHCFClCF.sub.3HCFC-355lcf CFH.sub.2 CH.sub.2 CF.sub.2 CF.sub.2 ClHCFC-355lec CH.sub.3 CF.sub.2 CFHCF.sub.2 ClHCFC-355lef CF.sub.2 HCH.sub.2 CFHCF.sub.2 ClHCFC-355lff CF.sub.3 CH.sub.2 CH.sub.2 CF.sub.2 ClHCFC-355mbf CFH.sub.2 CH.sub.2 CFClCF.sub.3HCFC-355mcf CF.sub.3 CF.sub.2 CH.sub.2 CClH.sub.2HCFC-355mdc CH.sub.3 CF.sub.2 CClHCF.sub.3HCFC-355mdf CF.sub.2 HCH.sub.2 CClHCF.sub.3HCFC-355meb CH.sub.3 CFClCFHCF.sub.3HCFC-355med CFH.sub.2 CClHCFHCF.sub.3HCFC-355mfb CFH.sub.2 CFClCH.sub.2 CF.sub.3HCFC-355mfc CF.sub.3 CH.sub.2 CF.sub.2 CClH.sub.2HCFC-355mfd CF.sub.2 HCClHCH.sub.2 CF.sub.3HCFC-355mfe CFClHCFHCH.sub.2 CF.sub.3HCFC-355pcb CH.sub.3 CFClCF.sub.2 CF.sub.2 HHCFC-355rcc CH.sub.3 CF.sub.2 CF.sub.2 CFClHHCFC-364med CH.sub.3 CClHCFHCF.sub.3HCFC-364mff CFClHCH.sub.2 CH.sub.2 CF.sub.3HCFC-373lef CH.sub.3 CH.sub.2 CFHCF.sub.2 ClHCFC-373mfd CH.sub.3 CClHCH.sub.2 CF.sub.3HCFC-373mff CF.sub.3 CH.sub.2 CH.sub.2 CClH.sub.2HCFC-391rff CH.sub.3 CH.sub.2 CH.sub.2 CFClHHCFC-391sbf CH.sub.3 CH.sub.2 CFClCH.sub. 3______________________________________
Known methods for making fluorinated compounds can be modified in order to form the straight chain hydrochlorofluorocarbons having 4 carbon atoms of the present invention.
For example, R. N. Haszeldine et al., "Addition of Free Radicals to Unsaturated Systems. Part XIII. Direction of Radical Addition to Chloro-1:1-difluoroethylene", J. of Amer. Chem. Soc., 2193 (1957) teach the reaction of trifluoroiodomethane with chloro-1:1-difluoroethylene to prepare 3-chloro-1:1:1:2:2-pentafluoro-3-iodopropane which is then chlorinated to form 1,1-dichloro-2,2,3,3,3-pentafluoropropane (known in the art as HCFC-225ca). This known method can be modified to form CF 3 CF 2 CH 2 CClH 2 (HCFC-355mcf) as follows. Commercially available perfluoroethyl iodide can be reacted with commercially available ethylene to prepare 1,1,1,2,2-pentafluoro-4-iodobutane which is then chlorinated to form 1,1,1,2,2-pentafluoro-4-chlorobutane.
CH 3 CF 2 CFHCF 2 Cl (HCFC-3551ec) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be fluorinated to form 1-chloro-2,3,3-trifluorobutane which may then be dehydrohalogenated to form 1-chloro-3,3-difluoro-1-butene. The 1-chloro-3,3-difluoro-1-butene may then be dehydrogenated to form 1-chloro-3,3-difluoro-1-propyne which may then be fluorinated to form 1-chloro-1,2,3,3-tetrafluoro-1-butene which may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1,1,2,3,3-pentafluorobutane.
CF 3 CH 2 CH 2 CF 2 Cl (HCFC-3551ff) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be dechlorinated to form hexafluoro-2-butyne. The hexafluoro-2-butyne may be hydrogenated to form 1,1,1,4,4,4-hexafluorobutane which may be chlorinated to form 1-chloro-1,1,4,4,4-pentafluorobutane.
CFH 2 CH 2 CFClCF 3 (HCFC-355mbf) may be prepared as follows. Commercially available 1,4-dichloro-2-butyne may be reacted with commercially available hydrogen fluoride to form 1,4-dichloro-2-fluoro-2-butene which may be fluorinated to form 1,2,4-trifluoro-2-butene. The 1,2,4-trifluoro-2-butene may be reacted with commercially available hydrogen chloride to form 2-chloro-1,2,4-trifluorobutane which may be dehydrohalogenated, fluorinated, dehydrohalogenated, and fluorinated to form 2-chloro-1,1,1,2,4-pentafluorobutane.
CH 3 CF.sub. CClHCF 3 (HCFC-355mdc) may be prepared as follows. Commercially available 3,4-dichloro-1-butene may be dehydrogenated to form 3,4-dichloro-1-butyne which may be reacted with commercially available hydrogen fluoride to form 1,2-dichloro-3,3-difluorobutane. The 1,2-dichloro-3,3-difluorobutane may be dehydrogenated to form 1,2-dichloro-3,3-difluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 2-chloro-1,1,3,3-tetrafluorobutane. The 2-chloro -1,1,3,3-tetrafluorobutane may be dehydrogenated to form 2-chloro-1,1,3,3-tetrafluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 2-chloro-1,1,1,3,3-pentafluorobutane.
CH 3 CFClCFHCF 3 (HCFC-355meb) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be fluorinated to form 2-chloro-2,3,4-trifluorobutane which may be dehydrohalogenated to form 3-chloro-1,3-difluoro-1-butene. The 3-chloro -1,3-difluoro-1-butene may be fluorinated to form 2-chloro-2,3,4,4-tetrafluorobutane which may be dehydrohalogenated to form 3-chloro-1,1,3-trifluoro-1-butene. The 3-chloro-1,1,3-trifluoro-1-butene may be fluorinated to form 2-chloro-2,3,4,4,4-pentafluorobutane.
CH 3 CFClCF 2 CF 2 H (HCFC-355pcb) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be fluorinated to form 2-chloro-2,3,4-trifluorobutane which may be dehydrogenated to form 3-chloro-1,2,3-trifluoro-1-butene. The 3-chloro -1,2,3-trifluoro-1-butene may be fluorinated to form 2-chloro-2,3,3,4,4-pentafluorobutane.
CH 3 CF 2 CF 2 CFClH (HCFC-355rcc) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be fluorinated to form 1-chloro-2,3,3-trifluorobutane which may be dehydrogenated to form 1-chloro-2,3,3-trifluoro-1-butene. The 1-chloro -2,3,3-trifluoro-1-butene may be fluorinated to form 1-chloro-1,2,2,3,3-pentafluorobutane.
CH 3 CClHCFHCF 3 (HCFC-364med) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be reacted with commercially available hydrogen fluoride to form 1,3-dichloro-2-fluorobutane which may be dehydrohalogenated to form 1,3-dichloro-1-butene. The 1,3-dichloro-1-butene may be fluorinated to form 2-chloro-3,4,4-trifluorobutane which may be dehydrohalogenated to form 3-chloro-1,1-difluoro-1-butene. The 3-chloro-1,1-difluoro-1-butene may be fluorinated to form 2-chloro-3,4,4,4-tetrafluorobutane.
The preferred straight chain hydrochlorofluorocarbons having 4 carbon atoms are CH 3 CF 2 CFHCF 2 Cl, CF 3 CH 2 CH 2 CF 2 Cl, CFH 2 CH 2 CFClCF 3 , CH 3 CF 2 CClHCF 3 , CH 3 CFClCFHCF 3 , CH 3 CFClCF 2 CF 2 H, CH 3 CF 2 CF 2 CFClH, and CH 3 CClHCFHCF 3 .
The branched chain hydrochlorofluorocarbons having 4 carbon atoms are listed in Table III below.
TABLE III______________________________________Number Chemical Formula______________________________________HCFC-345kms CH.sub.3 C(CF.sub.3)FCFCl.sub.2HCFC-345lls CH.sub.3 C(CF.sub.2 Cl)FCF.sub.2 ClHCFC-355lms CH.sub.3 C(CF.sub.3)HCF.sub.2 ClHCFC-355mop CF.sub.2 HC(CClH.sub.2)HCF.sub.3HCFC-355mps CH.sub.3 C(CF.sub.2 H)ClCF.sub.3HCFC-355mrs CH.sub.3 C(CFClH)FCF.sub.3HCFC-373mss CH.sub.3 C(CH.sub.3)ClCF.sub.3______________________________________
Known methods for making fluorinated compounds can be modified in order to form the branched hydrochlorofluorocarbons having 4 carbon atoms of the present invention.
CH 3 C(CF 3 )HCF 2 Cl (HCFC-3551ms) may be prepared as follows. Commercially available 1-chloro-2-methylpropene may be fluorinated to form 1-chloro-1,2-difluoro-2-methylpropane which may be dehydrohalogenated to form 1-chloro-1-fluoro-2-methylpropene. The 1-chloro-1-fluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,2-trifluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-3,3-difluoro-2-methylpropene. The 3-chloro-3,3-difluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,2,3-tetrafluoro-2-methylpropane which may be dehydrogenated to form 3-chloro-1,3,3-trifluoro-2-methylpropene. The 3-chloro-1,3,3-trifluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,2,3,3-pentafluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-1,1,3,3-tetrafluoro-2-methylpropene. The 3-chloro-1,1,3,3-tetrafluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,3,3,3-pentafluoro-2-methylpropane.
CH 3 C(CF 2 H)ClCF 3 (HCFC-355mps) may be prepared as follows. Commercially available 1-chloro-2-methylpropene may be fluorinated to form 1,1,2-trifluoro-2-methylpropane which may be dehydrohalogenated to form 3,3-difluoro-2-methylpropene. The 3,3-difluoro-2-methylpropene may be fluorinated to form 1,1,2,3-tetrafluoro-2-methylpropane which may be dehydrohalogenated to form 1,3,3-trifluoro-2-methylpropene. The 1,3,3-trifluoro-2-methylpropene may be fluorinated to form 1,1,2,3,3-pentafluoro-2-methylpropane which may be dehydrohalogenated to form 1,1,3,3-tetrafluoro-2-methylpropene. The 1,1,3,3-tetrafluoro-2-methylpropene may be chlorinated to form 1,2-dichloro-1,1,4,4-tetrafluoro-2-methylpropane which may be fluorinated to form 2-chloro-1,1,1,3,3-pentafluoro-2-methylpropane.
CH 3 C(CFClH)FCF 3 (HCFC-355mrs) may be prepared as follows. Commercially available 1-chloro-2-methylpropene may be fluorinated to form 1-chloro-1,2-difluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-3-fluoro-2-methylpropene. The 3-chloro-3-fluoro-2-methylpropene may be fluorinated to form 1-chloro-1,2,3-trifluoro -2-methylpropane which may be dehydrohalogenated to form 3-chloro-1,3-difluoro-2-methylpropene. The 3-chloro -1,3-difluoro-2-methylpropene may be fluorinated to form 1-chloro-1,2,3,3-tetrafluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-1,1,3-trifluoro -2-methylpropene. The 3-chloro-1,1,3-trifluoro-2-methylpropene may be fluorinated to form 1-chloro -1,2,3,3,3-pentafluoro-2-methylpropane.
The preferred branched hydrochlorofluorocarbons having 4 carbon atoms are CH 3 C(CF 3 )HCF 2 Cl, CH 3 C(CF 2 H)ClCF 3 , and CH 3 C(CFClH)FCF 3 .
The branched hydrochlorofluorocarbons having 5 carbon atoms are listed in Table IV below.
TABLE IV______________________________________Number Chemical Formula______________________________________HCFC-356mlfq CFH.sub.2 CH.sub.2 C(CF.sub.2 Cl)FCF.sub.3HCFC-357lcsp CF.sub.2 ClCF.sub.2 C(CH.sub.3)FCF.sub.2 HHCFC-357lmps CH.sub.3 C(CF.sub.3)(CF.sub.2 H)CF.sub.2 ClHCFC-357lsem CF.sub.3 CFHC(CH.sub.3)FCF.sub.2 ClHCFC-357mbsp CF.sub.3 CFClC(CH.sub.3)FCF.sub.2 HHCFC-357mcpo CF.sub.3 CF.sub.2 C(CF.sub.2 H)HCClH.sub.2HCFC-357mcsp CF.sub.3 CF.sub.2 C(CH.sub.3)ClCF.sub.2 HHCFC-357mcsr CF.sub.3 CF.sub.2 C(CH.sub.3)FCFClHHCFC-357mlcs CH.sub.3 CF.sub.2 C(CF.sub.2 Cl)HCF.sub.3HCFC-357mmbs CH.sub.3 CFClC(CF.sub.3)HCF.sub.3HCFC-357mmel CF.sub.2 ClCHFC(CH.sub.3)FCF.sub.3HCFC-357mmfo CH.sub.2 ClCH.sub.2 C(CF.sub.3)FCF.sub.3HCFC-357mmfq CFH.sub.2 CH.sub.2 C(CF.sub.3)ClCF.sub.3HCFC-357mmfr CFClHCH.sub.2 C(CF.sub.3)HCF.sub.3HCFC-357mofm CF.sub.3 CH.sub.2 C(CClH.sub.2)FCF.sub.3HCFC-357msem CF.sub.3 CFHC(CH.sub.3)ClCF.sub.3HCFC-358mcsr CF.sub.3 CF.sub.2 C(CH.sub.3)FCClFHHCFC-366mmds CH.sub.3 CClHC(CF.sub.3)HCF.sub.3HCFC-366mmfo CClH.sub.2 CH.sub.2 C(CF.sub.3)HCF.sub.3HCFC-375lcss CF.sub.2 ClCF.sub.2 C(CH.sub.3)FCH.sub.3HCFC-375mbss CF.sub.3 CFClC(CH.sub.3)FCH.sub.3HCFC-393less CF.sub.2 ClCFHC(CH.sub.3)HCH.sub.3HCFC-393mdss CF.sub.3 CClHC(CH.sub.3)HCH.sub. 3HCFC-393sfms CH.sub.3 CH.sub.2 C(CF.sub.3)ClCH.sub.3HCFC-3-11-1rfss CFClHCH.sub.2 C(CH.sub.3)HCH.sub.3______________________________________
Known methods for making fluorinated compounds can be modified in order to form the branched hydrochlorofluorocarbons having 5 carbon atoms of the present invention.
CFH 2 CH 2 C(CF 2 Cl)FCF 3 (HCFC-356mlfq) may be prepared as follows. Commercially available 1,4-dichloro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 1,4-dichloro-2-trifluoromethyl-3-iodobutane which may be dehydrohalogenated to form 1,4-dichloro-3-trifluoromethyl-1-butene. The 1,4-dichloro-3-trifluoromethyl-1-butene may be hydrogenated to form 1,4-dichloro-2-trifluoromethylbutane which may be fluorinated to form 1-chloro-2-trifluoromethyl-4-fluorobutane. The 1-chloro-2-trifluoromethyl-4-fluorobutane may be dehydrogenated to form 1-chloro-2-trifluoromethyl-4-fluoro-1-butene which may be fluorinated to form 1-chloro-2-trifluoromethyl-1,2,4-trifluorobutane. The 1-chloro-2-trifluoromethyl-1,2,4-trifluorobutane may be dehydrohalogenated to form 1-chloro-2-trifluoromethyl-1,4-difluoro-1-butene which may be fluorinated to form 1-chloro-2-trifluoromethyl-1,1,2,4-tetrafluorobutane.
CH 3 C(CF 3 )(CF 2 H)CF 2 Cl (HCFC-3571mps) may be prepared as follows. Commercially available 1,1-dichloropropene may be reacted with commercially available trifluoromethyl iodide to form 1,1-dichloro-1-iodo-2-trifluoromethylpropane which may be dehydrohalogenated to form 1,1-dichloro-2-trifluoromethyl-1-propene. The 1,1-dichloro-2-trifluoromethyl-1-propene may be hydrogenated to form 1,1-dichloro-2-trifluoromethylpropane which may be fluorinated to form l,1-difluoro-2-trifluoromethylpropane. The 1,1-difluoro-2-trifluoromethylpropane may be dehydrogenated to form 1,1-difluoro-2-trifluoromethy-1-propene which may be reacted with commercially available trifluoromethyl iodide to form 1,1-difluoro-1-iodo-2,2-trifluoromethylpropane. The 1,1-difluoro-1-iodo-2,2-trifluoromethylpropane may be chlorinated to form 1-chloro-1,1-difluoro-2,2-trifluoromethylpropane which may be hydrogenated to form 1-chloro-1,1-difluoro-2-difluoromethyl-2-trifluoromethylpropane.
CF 3 CFHC(CH 3 )FCF 2 Cl (HCFC-3571sem) may be prepared as follows. Commercially available 1,4-dichloro-2-butene may be reacted with commercially available iodomethane to form 1,4-dichloro-3-iodo-2-methylbutane which may be dehydrohalogenated to form 1,4-dichloro-3-methyl-1-butene. The 1,4-dichloro-3-methyl-1-butene may be fluorinated to form 1-chloro-2-methyl-3,4,4-trifluorobutane which may be dehydrohalogenated to form 1,1-difluoro-3-methyl-4-chloro-1-butene. The 1,1-difluoro-3-methyl-4-chloro-1-butene may be fluorinated to form 1-chloro-2-methyl-3,4,4,4-tetrafluorobutane which may be dehydrogenated to form 1-chloro-2-methyl-3,4,4,4-tetrafluoro-1-butene. The 1-chloro-2-methyl-3,4,4,4-tetrafluoro-1-butene may be fluorinated to form 1-chloro-2-methyl-1,2,3,4,4,4-hexafluorobutane which may be dehydrohalogenated to form 1-chloro-2-methyl-1,3,4,4,4-pentafluoro-1-butene. The 1-chloro-2-methyl-1,3,4,4,4-pentafluoro-1-butene may be fluorinated to form 1-chloro-2-methyl-1,1,2,3,4,4,4-heptafluorobutane.
CF 3 CFClC(CH 3 )FCF 2 H (HCFC-357mbsp) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3-dichloro-3-iodo-2-methyl-1,1,1,4,4,4-hexafluoropropane which may be fluorinated to form 2-methyl-3-chloro-1,1,1,2,3,4,4-heptafluorobutane. The 2-methyl-3-chloro-1,1,1,2,3,4,4-heptafluorobutane may be dehalogenated to form 3-chloro-2-methyl-1,1,3,4,4,4-hexafluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 3-chloro-2-methyl-1,1,2,3,4,4,4-heptafluorobutane.
CF 3 CF 2 C(CH 3 )ClCF 2 H (HCFC-357mcsp) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with iodomethane to form 2-methyl-2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluorobutane which may be fluorinated to form 2-methyl-1,1,1,2,3,3,4,4,4-nonafluorobutane. The 2-methyl-1,1,1,2,3,3,4,4,4-nonafluorobutane may be dehalogenated to form 2-methyl-1,1,3,3,4,4,4-heptafluoro-1-butene which may be reacted with commercially available hydrogen chloride to form 2-chloro-2-methyl-1,1,3,3,4,4,4-heptafluorobutane.
CH 3 CF 2 C(CF 2 Cl)HCF 3 (HCFC-357mlcs) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 1,3-dichloro-2-trifluoromethyl-3-iodobutane which may be fluorinated to form 1,3,3-trifluoro-2-trifluoromethylbutane. The 1,3,3-trifluoro-2-trifluoromethylbutane may be dehydrogenated to form 1,3,3-trifluoro-2-trifluoromethyl-1-butene which may be fluorinated to form 1,1,2,3,3-pentafluoro-2-trifluoromethylbutane. The 1,1,2,3,3-pentafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 1,1,3,3-tetrafluoro-2-trifluoromethyl-1-butene which may be reacted with commercially available hydrogen chloride to form 1-chloro-1,1,3,3-tetrafluoro-2-trifluoromethylbutane.
CH 3 CFClC(CF 3 )HCF 3 (HCFC-357mmbs) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-2-trifluoromethyl-1,1,1,4,4,4-hexafluorobutane which may be fluorinated to form 2-trifluoromethyl-1,1,1,2,3,3,4,4,4-nonafluorobutane. The 2-trifluoromethyl-1,1,1,2,3,3,4,4,4-nonafluorobutane may be dehalogenated to form 3-trifluoromethyl-1,1,2,3,4,4,4-heptafluoro-1-butene which may be hydrogenated to form 2-trifluoromethyl-1,1,1,2,3,4,4-heptafluorobutane. The 2-trifluoromethyl-1,1,1,2,3,4,4-heptafluorobutane may be dehydrohalogenated to form 3-trifluoromethyl-1,2,3,4,4,4-hexafluoro-1-butene which may be hydrogenated to form 3-trifluoromethyl-1,2,3,4,4,4-hexafluorobutane. The 3-trifluoromethyl-1,2,3,4,4,4-hexafluorobutane may be dehydrohalogenated to form 3-trifluoromethyl-2,3,4,4,4-pentafluoro-1-butene which may be reacted with commercially available hydrogen chloride to form 3-chloro-2-trifluoromethyl-1,1,1,2,3-pentafluorobutane. The 3-chloro-2-trifluoromethyl -1,1,1,2,3-pentafluorobutane may be dehalogenated to form 3-chloro-2-trifluoromethyl-1,1,3-trifluoro -1-butene which may be reacted with commercially available hydrogen fluoride to form 3-chloro-2-trifluoromethyl -1,1,1,3-tetrafluorobutane.
CF 2 ClCHFC(CH 3 )FCF 3 (HCFC-357mmel) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2-methylbutane which may be fluorinated to form 2-methylperfluorobutane. The 2-methylperfluorobutane may be dehalogenated to form 1,1,2,3,4,4,4-heptafluoro-3-methyl-1-butene which may be reacted with commercially available hydrogen chloride to form 4-chloro-1,1,1,2,3,4,4-heptafluoro-2-methylbutane.
The method of R. N. Haszeldine et al., supra, can be modified to form CH 2 ClCH 2 C(CF 3 )FCF 3 (HCFC-357 mmfo) as follows. Commercially available perfluoroisopropyl iodide may be reacted with commercially available ethylene to prepare 2-trifluoromethyl-1,1,1,2-tetrafluoro-4-iodobutane which may then be chlorinated to form 2-trifluoromethyl-1,1,1,2-tetrafluoro-4-chlorobutane.
CFH 2 CH 2 C(CF 3 )ClCF 3 (HCFC-357mmfq) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2-trifluoromethylbutane which may be fluorinated to form 2-chloro-2-trifluoromethyl-perfluorobutane. The 2-chloro-2-trifluoromethyl-perfluorobutane may be dehalogenated to form 3-chloro-3-trifluoromethyl-1,1,2,4,4,4-hexafluoro-1-butene which may be hydrogenated to form 2-chloro-2-trifluoromethyl-1,1,1,3,4,4-hexafluorobutane. The 2-chloro-2-trifluoromethyl-1,1,1,3,4,4-hexafluorobutane may be fluorinated to form 3-chloro-3-trifluoromethyl-1,4,4,4-tetrafluoro-1-butene which may then be hydrogenated to form 2-chloro-2-trifluoromethyl-1,1,1,4-tetrafluorobutane.
CF 3 CFHC(CH 3 )ClCF 3 (HCFC-357msem) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2-methylbutane which may be chlorinated to form 2,3,3-trichloro-1,1,4,4,4-hexafluoro-2-methylbutane. The 2,3,3-trichloro-1,1,1,4,4,4-hexafluoro-2-methylbutane may be dehalogenated to form 3-chloro-1,1,1,4,4,4-hexafluoro-2-methyl-2-butene which may be reacted with commercially available hydrogen fluoride to form 3-chloro-1,1,1,3,4,4,4-heptafluoro-2-methylbutane. The 3-chloro-1,1,1,3,4,4,4-heptafluoro-2-methylbutane may be dehydrohalogenated to form 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene which may be reacted with commercially available hydrogen chloride to form 2-chloro-1,1,1,3,4,4,4-heptafluoro-2-methylbutane.
CF 3 CF 2 C(CH 3 )FCClFH (HCFC-358mcsr) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2-methylbutane which may be fluorinated to form 2-methylperfluorobutane. The 2-methyl-perfluorobutane may be dehalogenated to form 2-methyl-perfluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 1,1,2,3,3,4,4,4-octafluoro-2-methylbutane. The 1,1,2,3,3,4,4,4-octafluoro-2-methylbutane may be dehalogenated to form 1,3,3,4,4,4-hexafluoro-2-methyl-1-butene which may be chlorinated to form 1,2-dichloro-1,3,3,4,4,4-hexafluoro-2-methylbutane. The 1,2-dichloro-1,3,3,4,4,4-hexafluoro -2-methylbutane may be dehydrohalogenated to form 1-chloro-1,3,3,4,4,4-hexafluoro-2-methyl-1-butene which may be reacted with commercially available hydrogen fluoride to form 1-chloro-1,2,3,3,4,4,4-heptafluoro-2-methylbutane.
CH 3 CClHC(CF 3 )HCF 3 (HCFC-366mmds) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with trifluoromethyl iodide to form 2,3-dichloro-3-iodo-1,1,1,4,4,4 -hexafluoro-2-trifluoromethylbutane which may be chlorinated to form 3-iodo-1,1,1,4,4,4-hexafluoro-2-methyl-2-butene. The 3-iodo-1,1,1,4,4,4-hexafluoro-2-trifluoromethyl-2-butene may be hydrogenated to form 3-iodo-1,1,1,4,4,4-hexafluoro-2-trifluoromethylbutane which may be dehydrohalogenated to form 2-iodo-1,1,4,4,4-pentafluoro-3-trifluoromethyl-1-butene. The 2-iodo-1,1,4,4,4-pentafluoro-3-trifluoromethyl-1-butene may be hydrogenated to form 3-iodo-1,1,1,4,4-pentafluoro-2-trifluoromethylbutane which may be chlorinated to form 3-chloro-1,1,1,4,4-pentafluoro-2-trifluoromethylbutane. The 3-chloro-1,1,1,4,4-pentafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 2-chloro-1,4,4,4-tetrafluoro-3-trifluoromethyl-1-butene which may be hydrogenated to form 3-chloro-1,1,1,4-tetrafluoro-2-trifluoromethylbutane. The 3-chloro-1,1,1,4-tetrafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 2-chloro-4,4,4-trifluoro-3-trifluoromethyl-1-butene which may be hydrogenated to form 3-chloro-1,1,1-trifluoro-2-trifluoromethylbutane.
The preferred branched hydrochlorofluorocarbons having 5 carbon atoms are CFH 2 CH 2 C(CF 2 Cl)FCF 3 , CH 3 C(CF 3 )(CF 2 H)CF 2 Cl, CF 3 CFHC(CH 3 )FCF 2 Cl, CF 3 CFClC(CH 3 )FCF 2 H, CF 3 CF 2 C(CH 3 )ClCF 2 H, CH 3 CF 2 C(CF 2 Cl)HCF 3 , CH 3 CFClC(CF 3 )HCF 3 , CF 2 ClCHFC(CH 3 )FCF 3 , CH 2 ClCH 2 C(CF 3 )FCF 3 , CFH 2 CH 2 C(CF 3 )ClCF 3 , CF 3 CFHC(CH 3 )ClCF 3 , CF 3 CF 2 C(CH 3 )FCClFH, and CH 3 CClHC(CF 3 )HCF 3 .
The present method is advantageous because the solvents have low atmospheric lifetimes.
Other advantages of the invention will become apparent from the following description.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Known solvents may be blended with the solvents of the present method. Examples of useful known solvents are listed in Table V below.
TABLE V______________________________________Number Chemical Formula______________________________________HCFC-234cc CF.sub.2 ClCF.sub.2 CClH.sub.2HCFC-234cd CH.sub.2 FCF.sub.2 CFCl.sub.2HCFC-244ca CF.sub.2 HCF.sub.2 CClH.sub.2HCFC-244cb CFH.sub.2 CF.sub.2 CFClHHCFC-253ca CFH.sub.2 CF.sub.2 CClH.sub.2HCFC-253cb CH.sub.3 CF.sub.2 CFClH______________________________________
HCFC-234cc may be formed by any known method such as the reaction of 1,1,1,2,2,3-hexachloropropane with antimony pentachloride and hydrogen fluoride at 100° C. HCFC-234cd may be formed by any known method such as the reaction of 1,1,1-trichloro-2,2,3-trifluoropropane with antimony pentachloride and hydrogen fluoride at 120° C.
HCFC-244ca may be formed by any known method such as the reaction of 1,1,2,2,3-pentachloropropane with antimony pentachloride and hydrogen fluoride at 100° C. HCFC-244cb may be formed by any known method such as the reaction of 1-chloro-1,1,2,2-tetrafluoropropane with cesium fluoride and tetrabutylammonium bromide at 150° C.
HCFC-253ca may be formed by any known method such as the reaction of 1,2,3-trichloro-2-fluoropropane with niobium pentachloride and hydrogen fluoride at 100° C. HCFC-253cb may be formed by any known method such as the reaction of 1,1,2,2-tetrachloropropane with tantalum pentafluoride and hydrogen fluoride at 130° C.
The present method removes most contaminants from the surface of a substrate. For example, the present method removes organic contaminants such as mineral oils from the surface of a substrate. Under the term "mineral oils", both petroleum-based and petroleum-derived oils are included. Lubricants such as engine oil, machine oil, and cutting oil are examples of petroleum-derived oils.
The present method also removes water from surface of a substrate. The method may be used in the single-stage or multi-stage drying of objects.
The present method may be used to clean the surface of inorganic substrates and some organic substrates. Examples of inorganic substrates include metallic substrates, ceramic substrates, and glass substrates. Examples of organic substrates include polymeric substrates such as polycarbonate, polystyrene, and acrylonitrile-butadiene-styrene. The method also may be used to clean the surface of natural fabrics such as cotton, silk, fur, suede, leather, linen, and wool. The method also may be used to clean the surface of synthetic fabrics such as polyester, rayon, acrylics, nylon, and blends thereof, and blends of synthetic and natural fabrics. It should also be understood that composites of the foregoing materials may be cleaned by the present method.
The present method may be used in vapor degreasing, solvent cleaning, cold cleaning, dewatering, and dry cleaning. In these uses, the object to be cleaned is immersed in one or more stages in the liquid and/or vaporized solvent or is sprayed with the liquid solvent. Elevated temperatures, ultrasonic energy, and/or agitation may be used to intensify the cleaning effect.
The present invention is more fully illustrated by the following non-limiting Examples.
EXAMPLES 1-85
Each solvent listed in Tables I through IV are added to mineral oil in a weight ratio of 50:50 at 27° C. Each solvent is miscible in the mineral oil.
Having described the invention in detail and by reference to preferred embodiments thereof, it will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims.
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A method of cleaning a surface of a substrate is provided. The solvent is selected from a group consisting of hydrochlorofluorocarbons having 3 to 5 carbon atoms and a maximum of two chlorine atoms. The environmental lifetime of the solvent is expected to be less than one year.
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FIELD OF THE INVENTION
The present invention relates to a system for deactivating a firing device for an airbag installed in a vehicle, circuit means being provided which prevent a current flow through the firing device during a desired deactivation time.
BACKGROUND INFORMATION
In the past, there have been a number of cases in which children who were sitting on the front passenger seat of the vehicle in a child seat directed backwards have suffered fatal injuries due to the triggering of the passenger-side airbag. These accidents could have been prevented by deactivating the passenger-side airbag. In general, there are situations in which activation of the passenger-side airbag is superfluous, for example, when the front passenger seat is not occupied by a person at all, but rather some object such as a piece of luggage is placed on it. There are systems and devices already known, which are mentioned in German Patent No. 197 24 344 C1, for detecting such situations in which the passenger-side airbag should be deactivated. Image-processing systems, which can detect whether the front passenger seat is occupied by a child seat or a person or an object and what distance the person is from the passenger-side airbag so that in critical occupancy situations the airbag can be deactivated, are very costly. Another device for detecting seat occupancy is composed of a mat, integrated into the front passenger seat, which changes its electrical resistance or its capacitance as a function of a force or pressure influence. Thus, this mat has the function of a weight sensor to determine whether the seat is occupied by a grown person or a child.
Furthermore, there are sensors which detect the presence of a backward-facing child seat on the front passenger seat. Among these are sensors which are based on an electromagnetic transponder principle, transmitters and receivers being disposed on the child seat and in the front passenger seat. European Patent No. 06 037 33 B1 describes an arresting device, also known under the name ISOFIX, for a child seat on the front passenger seat of a vehicle. The child seat is located in position by detent elements, present on the child seat, which can engage with a fixing device on the front passenger seat. A sensor detects the engagement of the detent elements and, in so doing, emits a pulse which is supplied to a control unit for deactivating the passenger-side airbag.
The simplest device for deactivating a passenger-side airbag is a manually operable switch which, as is derived from German Patent No. 197 24 344 C1 and U.S. Pat. No. 5,544,914, has a first switching position for activating and a second switching position for deactivating the firing device of the airbag.
All these indicated systems function such that they interrupt the electric circuit of the firing device to deactivate the passenger-side airbag. However, there have also been situations in which the passenger-side airbag has been triggered, even though it has been deactivated by software-programmed interruption of the firing circuit. Causes to be considered are possible malfunctions of a microcontroller in the airbag control unit, or even a direct irradiation of sufficiently great electromagnetic energy from outside into the supply lines of the firing devices. In the same way, short circuits to plus and minus of the battery voltage due to vehicle-body deformations caused by impacts could be responsible for triggering the airbag.
Therefore, an object of the present invention is to provide a system of the type indicated at the outset, which reliably ensures that under no circumstances can an unwanted triggering of the airbag occur.
SUMMARY OF THE INVENTION
According to the present invention, the firing device is bypassed with the aid of a switch, electrically controllable by the circuit means, which short-circuits the electric circuit of the firing device during the deactivation time. The result of this short-circuiting switch bypassing the firing device is that no current causing a triggering of the firing device, regardless of how this current is formed, can flow through the firing device.
Particularly to deactivate the passenger-side airbag when the front passenger seat is occupied in the ways mentioned at the outset, means are provided that signal such situations in which the firing device must not be triggered. For example, these means advantageously include a switch, operable by hand, or a sensory mechanism which detects the manner in which the seat is occupied. Or the means interact with a detent device with which a child seat is located in position on the front passenger seat of a vehicle, the means signaling a non-triggering case when the detent device is engaged.
Very great security against a false airbag triggering is ensured in that the circuit means keep the switch closed continuously, so that the firing device is short-circuited, and that the circuit means only open the switch when either a triggering or a diagnosis of the firing device is to be carried out.
For a diagnosis of the firing device, the switch is preferably opened at predefined time intervals for a duration of approximately 20 μs. This time is less than the minimal firing lag time, which the firing device normally needs in response to a current flow, in order to trigger.
The electrically controllable switch is advantageously a field-effect transistor.
A first visual display can be provided which lights up in response to a short circuit of the electric circuit of the firing device, and a second display can be provided which lights up in response to a malfunction of the short-circuiting switch.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a block diagram of a first embodiment for driving the firing device of an airbag.
FIG. 2 shows deactivation circuit means for the case when a child seat is directed backwards.
FIG. 3 shows a block diagram of a second embodiment for driving the firing device of an airbag.
DETAILED DESCRIPTION
Circuit block DS shown in FIG. 1 symbolizes deactivation circuit means which emit a deactivation signal a when the seat occupancy on the front passenger seat forbids activation of the passenger-side airbag in the event of a crash. As already mentioned at the outset, among these are, for example, the occupancy of the front passenger seat by a backward-directed child seat, or when no person is on the front passenger seat. In the simplest case, deactivation circuit means DS can be composed of a switch operable by hand, or a sensory mechanism which detects the type of seat occupancy, particularly a backward-facing child seat. Several known sensor systems were set forth in the introduction.
Deactivation signal a, emitted by circuit block DS, is supplied to a control unit ECU. In dependence on acceleration-sensor signals, with the aid of a suitable algorithm, this control unit ECU decides whether or not firing device ZV for the passenger-side airbag should be triggered in the event of a vehicle crash. When a passenger-side airbag is spoken of here and in the following, also meant by this are all other airbags (e.g. side airbags, knee bags, head airbags and the like) which are installed to protect the front-seat passenger in the vehicle.
With deactivation signal a, control unit ECU receives the information that a non-triggering case exists for the passenger-side airbag. Control unit ECU triggers a driver circuit TR for firing device ZV accordingly. Firing device ZV is bypassed by an electrically controllable short-circuiting switch KS, preferably a field-effect transistor (MOSFET). In the non-triggering case, driver circuit TR generates a control signal b for short-circuiting switch KS, which thereby switches into the conductive state and consequently short-circuits the electric circuit of firing device ZV. Thus, if a current, for whatever reasons, is flowing in the electric circuit of firing device ZV, it is shunted via short-circuiting switch KS. As a result, a triggering of firing device ZV can therefore not occur. The passenger-side airbag would thus be reliably deactivated for this case.
Control unit ECU receives deactivation signal a via a signal path which is completely independent of a signal path via which a triggering signal, conditioned upon an impact, is supplied by a microcontroller.
As soon as control unit ECU signals to driver circuit TR that short-circuiting switch KS is to be closed for deactivating the passenger-side airbag, driver circuit TR activates a display A 1 , whereby the deactivation state of the passenger-side airbag is displayed in the vehicle.
As a rule, control unit ECU carries out a functional diagnosis of firing device ZV. This diagnosis lies in periodically measuring the resistance of the firing device. If this resistance deviates by a specific amount from a predefined reference value, then a second display A 2 , connected to driver circuit TR, is activated to indicate such a fault case. If the firing circuit is short-circuited via short-circuiting switch KS, control unit ECU would have to determine a resistance of approximately 0 Ω in the diagnosis. Should short-circuiting switch KS be defective, then a resistance deviating from 0 Ω would be measured. Thus, a diagnosis of short-circuiting switch KS can be carried out by control unit ECU, as well. Should a fault be detected in short-circuiting switch KS, then display A 2 would likewise be activated.
FIG. 2 shows schematically a special example for deactivation circuit means DS. In the case of this deactivation circuit means DS, the assumption is a backward-directed child seat which, as described in European Patent No. EP 06 037 33 B1, is equipped with two detent elements that are able to engage with a fixing device on the front passenger seat. Each of the two detent elements is provided with a switch S 1 , S 2 which closes when the corresponding detent element on the child seat engages with the fixing device on the front passenger seat. With the closing of switches S 1 , S 2 , a deactivation signal a is emitted for control unit ECU. Since it can happen by mistake that only one of the two detent elements on the child seat is properly engaged with the fixing device on the front passenger seat, but the fact that a child seat is on the front passenger seat must be detectable for this case as well, provision is made in circuit block DS for an OR gate OD which already emits a deactivation signal a when only one of the two switches S 1 , S 2 is closed.
As can be seen in a further exemplary embodiment shown in FIG. 3, in addition to the circuit blocks already described, further circuit means SC are provided which trigger short-circuiting switch KS instead of driver circuit TR. This circuit means SC keeps short-circuiting switch KS closed continuously, so that firing device ZV is short-circuited and no current can flow across firing device ZV.
There are only two situations in which circuit means SC opens short-circuiting switch KS. The one situation is when circuit means SC receives information from control unit ECU that, because of a vehicle crash, the airbag should be triggered. However, if information a from deactivation means DS exists in control unit ECU that, because of a special type of seat occupancy, the airbag must not be triggered, then the short circuit of firing device ZV is maintained in this case, as well. The second situation in which short-circuiting switch KS is opened by circuit means SC is when control unit ECU carries out a diagnosis of firing device ZV. To that end, at predefined time intervals of, for example, 1s, short-circuiting switch KS is opened for a duration of approximately 20 μs. This time is shorter than the minimal preferred time which the firing device needs to trigger in response to the flow of a sufficiently large current. Therefore, given a short circuit on a line of firing device ZV to ground and full firing current of 1.75 A of unknown origin, an unwanted triggering cannot occur.
In addition to the described driving for the firing device, circuit means SC can also have the function of a triggering-plausibility verification.
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So that, given a desired deactivation of an airbag, a triggering cannot take place under any circumstances, a firing device of the airbag is bypassed using an electrically controllable switch. This switch short-circuits the electric circuit of the firing device during the deactivation time.
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This patent application is a continuation-in-part of U.S. application Ser. No. 13/507,285 filed Jun. 19, 2012, which claims the benefit of U.S. Provisional Application No. 61/571,105 filed Jun. 21, 2011. The patent application also claims the benefit of U.S. Provisional Application No. 61/961,457 filed Oct. 15, 2013. Each application identified above is hereby incorporated by reference in its entirety to provide continuity of disclosure.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally relates to access to enclosures, such as batting cages, and, more particularly, is concerned with access door unit.
2. Description of the Prior Art
Enclosures, for example batting cages, typically do not come with or have a conventional or regular style door, one that opens, closes, latches, and allows users with baseball equipment to entry and exit easily to and from the batting cage. There are some batting cages that have what is called a “flap door”, built into the net of the batting cage. The flap door typically is an overlapped piece of the net configured to form a flap that covers an opening in the netting. To enter or exit the batting cage the user has to fold back the flap and navigate through the opening usually while carrying baseball equipment. The flap door typically is cumbersome to manipulate and does not open wide enough for easy passage with equipment. Additionally, they are difficult to see and thus find in that they do not appear distinct from the net. Thus, they are neither easy nor convenient to use.
Many batting cages require users to lift a net wall of the batting cage to enter and exit. Lifting the cage wall can be difficult for many users in that a user has to stoup over or bend down. Furthermore, requiring that a wall be capable of being lifted for allowing entry or exit can also prevent the batting cage user from safely anchoring or “staking or weighting” the bottom edges of the batting cage walls to prevent passage of balls from the cage.
U.S. Patent No. Des. 276,466 to Giovagnoli discloses a batting cage with access doors to its batting compartments. The batting cage appears to be constructed by an extended framework supporting a net so as to define a plurality of side-by-side batting compartments. The extended framework appears to incorporate and support a doorway frame portion in a front wall of each batting compartment that extends from a corner thereof. The access doors to the batting compartments appear to be pivotally supported by the doorway frame portions. The approach of this design patent would appear to be dependent on and limited to the batting cages having the particular arrangement of the extended framework.
SUMMARY OF THE INVENTION
The present invention provides an access door unit designed to overcome the above-described drawbacks and satisfy the need for versatile, convenient and easy access to inside an enclosure, such as a batting cage. Specifically, the access door unit provides a doorway structure and a door which can be easily assembled and installed to provide the access door unit in a self-supporting relationship to the batting cage at any one of various different locations about the perimeter of the batting cage. The doorway structure has its own base support members which allow the unit to be self-standing, or free-standing, and thus installable in the self-supporting relationship at any of the different locations. Also, in one exemplary embodiment the door utilizes a double layer sock net which is easy to assemble on a peripheral door frame to form a closure panel of the door.
Accordingly, the present invention is directed to an access door unit which includes a door and a doorway structure. The door has a periphery and includes a peripheral frame defining the periphery and an interior open area of the door, and a closure panel attachable to the peripheral frame so as to extend across the interior open area of the peripheral frame.
The doorway structure has an outer perimeter frame and a support base. The outer perimeter frame includes right and left upright side portions and top and bottom portions extending between and interconnecting the right and left upright side portions so to define a passage through the outer perimeter frame being surrounded in continuous fashion by the outer perimeter frame and enough larger than the periphery of the door so that that door can fit within the passage of the doorway structure.
The support base is affixed on the outer perimeter frame. The support base includes right and left support members spaced apart from one another and extending in transverse relation to and outwardly in opposite fore and aft directions from the bottom portion of the outer perimeter frame such that the right and left support members are adapted to rest on a generally level support surface with the outer perimeter frame extending upright from the support base enabling the doorway structure, due solely to the right and left support members of the support base resting on the support surface, and solely to the outer perimeter frame extending upright from the support base, to assume a free-standing, self-supporting orientation on the support surface without any additional support from any other structure.
The access door unit also includes a plurality of elements for enabling the door to be pivotally moved toward and away from the passage of the outer perimeter frame of the doorway structure to permit entry or exit through the passage of the doorway structure.
In one embodiment, the closure panel of the door extends the full length of the interior open area of the peripheral frame of the door. In another embodiment, the closure panel of the door is a protective screen that extends approximately half of the length of the interior open area of the door and is pivotally convertible between up and down positions relative to the door and doorway structure in accordance with corresponding use for protecting softball and baseball pitchers. In further embodiment, the door is a protective screen that extends approximately half of the length of the passage of the doorway structure and is movably convertible between up and down positions relative to the doorway structure in accordance with corresponding use for protecting softball and baseball pitchers.
These and other features and advantages of the present invention will become apparent to those skilled in the art upon a reading of the following detailed description when taken in conjunction with the drawings wherein there is shown and described an illustrative embodiment of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
In the following detailed description, reference will be made to the attached drawings in which:
FIG. 1 is an elevational view of an exemplary embodiment of an access door unit installed in a batting cage in accordance with the present invention, showing a user initiating the opening of a door of the unit, the view also containing an enlarged fragmentary view to show the strands of a double layer sock net forming a closure panel of the door.
FIG. 2 is an elevational view similar to that of FIG. 1 , now showing the user entering the batting cage through an access opening defined through a doorway structure of the unit after the door of the unit has been opened.
FIG. 3 is a perspective assembled view of an exemplary embodiment of the doorway structure of the access door unit which provides the unit with a self-standing, or free-standing, capability enabling it to be self-supporting relative to the batting cage.
FIG. 4 is a perspective disassembled view of doorway structure of FIG. 4 .
FIGS. 5-11 are a succession of views illustrating an exemplary embodiment of a sequence of steps in a method of installing the assembled doorway structure 18 of FIG. 3 in the net 12 of the batting cage 10 .
FIG. 12 is a perspective assembled view of an exemplary embodiment of a peripheral frame of the door of the access door unit.
FIG. 13 is a perspective disassembled view of the peripheral frame of the door of the unit.
FIGS. 14-16 are a succession of views of an exemplary embodiment of a sequence of steps in a method of installing the sock net over the assembled peripheral frame of the door of FIG. 12 .
FIG. 17 is an elevational view of one exemplary embodiment of a hinge used to pivotally attach the door to the doorway structure of the access door unit.
FIG. 18 is an elevational view of another exemplary embodiment of a hinge used to pivotally attach the door to the doorway structure of the access door unit.
FIGS. 19-22 are respective perspective and elevational views of an exemplary embodiment of components of a latch mechanism used to latch the door to doorway structure of the access door unit.
FIG. 23 is a perspective view of a top door stop affixed to a top portion of the door of the access door unit.
FIG. 24 is a perspective view of a bottom door stop affixed to a bottom portion of the door of the access door unit.
FIG. 25 is an elevational view of another exemplary embodiment of an access door unit adapted for use as a protective screen for a softball pitcher.
FIG. 26 is an elevational view of the access door unit of FIG. 25 now converted for use as a protective screen for a baseball pitcher.
FIG. 27 is a side elevational view of the access door unit showing converting of its protective screen between an “up” position for softball and a “down” position for baseball.
FIG. 28 is an elevational view of still another exemplary embodiment of an access door unit adapted for use as a protective screen for a softball pitcher.
FIG. 29 is an elevational view of the access door unit of FIG. 28 now converted for use as a protective screen for a baseball pitcher.
FIG. 30 is an elevational view of the doorway structure of the unit of FIGS. 28 and 29 .
FIG. 31 is an elevational view of the screen panel of the unit of FIGS. 28 and 29 .
DETAILED DESCRIPTION OF THE INVENTION
Referring to the drawings, and particularly to FIGS. 1 and 2 , there is illustrated a wall of a conventional batting cage 10 formed by a vertically suspended or hanging net 12 unattached or free at its lower edge. (In various of the figures portions of the net 12 have been omitted for purposes of clarity and convenience in illustration.) The net 12 may be fabricated from strands of any suitable, preferably flexible, material, such as fabric, plastic or metallic woven cord or wire. Also shown is an exemplary embodiment of an access door unit 14 , which constitutes one aspect of the present invention, installed or built into the net 12 of the batting cage 10 . The access door unit 14 permits easy and convenient entry into and exit from the batting cage 10 , as shown in FIGS. 1 and 2 . While the access door unit 14 is disclosed herein installed into the wall or net 12 of the batting cage 10 , it should be understood that the unit 14 also may be installed in a wall of a tent or various other types of enclosures.
As seen in FIGS. 1 and 2 , the access door unit 14 basically includes a door 16 , and a stationary self-standing doorway structure 18 surrounding the door 16 (when the door 16 is closed) and pivotally supporting the door 16 by an outer perimeter frame 30 of the doorway structure 18 which also defines a passage 20 through the doorway structure 18 . The door 16 basically includes a peripheral frame 22 of generally rectangular configuration defining a periphery of the door 16 . The door 16 also includes a closure panel 24 attached to and extending across an interior open area 26 defined by the peripheral frame 22 . The doorway structure 18 basically includes a base 28 and the outer perimeter frame 30 of generally rectangular configuration attached on and extending upright from the base 28 . The outer perimeter frame 30 of the doorway structure 18 is enough larger in circumference than the peripheral frame 22 of the door 16 that the latter can fit within the passage 20 of the former. To enter or exit the batting cage 10 a user unlatches the door 16 , pivots the door 16 from a closed position to an opened position located away from the doorway structure 18 , and then walks through its passage 20 . The door 16 may then be returned to its closed position, either automatically or manually, and latched to the doorway structure 18 when it reaches the closed position.
More clearly, FIGS. 3 and 4 show an exemplary embodiment of the doorway structure 18 that provides the access door unit 14 with a self-standing, self-supporting capability. This capability frees the access door unit 14 of the need for additional support from any structural frame component of the batting cage 10 . It also allows the unit 14 to be quickly and easily installed in association only with the net 12 of the batting cage 10 . With the access door unit 10 so installed self-standing on a substantially level flat surface 32 , which also supports the batting cage 10 , the net 12 of the batting cage 10 need not be disturbed. Instead, since entry and exit by users will now be through the passage 20 of the doorway structure 18 by use of the door 16 , the bottom of the net 12 may be permanently staked or anchored to the support surface 32 in order to prevent balls from escaping the confinement of the batting cage 10 . Furthermore, the access door unit 14 may be installed either in a new or (retrofitted in) an existing batting cage used either indoors or outdoors.
FIGS. 3 and 4 show the doorway structure 18 of the access door unit 14 by itself. (It should be noted here that the orientation of the doorway structure 18 shown in FIG. 3 is the reverse of that shown in FIGS. 1 and 2 . It should be further noted that parts of the doorway structure 18 hereinafter identified as “right” and “left” are labeled in reference to their orientation in the doorway structure 18 as shown in FIGS. 3 and 5-11 , and not as shown in FIGS. 1 and 2 .) The doorway structure 18 may be assembled from a plurality 34 of parts, for example, four pairs of parts or eight parts in total, into the base 28 and an outer perimeter frame 30 . The plurality 34 of parts may be constructed from widely-available metal tubing, for example steel or aluminum, by using well-known fabrication techniques. The plurality 34 of parts may be marketed disassembled in a package and then fitted and assembled, at the site of the batting cage 10 , to one another, for example, at mateable male and female ends. The assembled parts are then secured together by use of fasteners, such as bolts and nuts (which are included in the disassembled parts package), applied to the mated ends in preparation for installing the doorway structure 18 into the net 12 of the hitting cage 10 . In an exemplary embodiment, the doorway structure parts of each pair may be substantially identical to one another but different from the doorway structure parts of the other pairs.
In the exemplary embodiment shown in FIG. 4 , the plurality 34 of parts for assembling the doorway structure 18 may include:
(1) lower right and left leg parts 34 A, 34 B arranged in a mirror image relationship to one another, both having respective fore-and-aft extending legs 34 A- 1 , 34 B- 1 , horizontal posts 34 A- 2 , 34 B- 2 and vertical posts 34 A- 3 , 34 B- 3 such that the horizontal and vertical posts are rigidly affixed on each of the respective legs at approximately midway between the opposite ends of the legs; (2) upper right and left corner parts 34 C, 34 D also arranged in a mirror image relationship to one another and each having a substantially right angle configuration; (3) right and left side parts 34 E, 34 F of substantially straight configurations and disposed between and interconnecting corresponding upper right and left corner parts 34 C, 34 D with the respective vertical posts 34 A- 3 , 34 B- 3 of the lower right and left leg parts 34 A, 34 B; and (4) top and bottom parts 34 G, 34 H of substantially straight configurations, the top part 34 G disposed between and interconnecting the upper right and left corner parts 34 C, 34 D with one another, the bottom part 34 H disposed between and interconnecting the respective horizontal posts 34 A- 2 , 34 B- 2 of the lower right and left leg parts 34 A, 34 B with one another.
The fore-and-aft extending leg 34 A- 1 , 34 B- 1 and horizontal posts 34 A- 2 , 34 B- 2 of the lower right and left leg parts 34 A, 34 B in conjunction with the bottom part 34 H, which interconnects the horizontal posts 34 A- 2 , 34 B- 2 , constitute the base 28 of the doorway structure 18 . The upper right and left corner parts 34 C, 34 D, the vertical and horizontal posts 34 A- 3 , 34 B- 3 and 34 A- 2 , 34 B- 2 of the lower right and left leg parts 34 A, 34 B and the bottom part 34 H, which interconnects the horizontal posts 34 A- 2 , 34 B- 2 , constitute the outer perimeter frame 30 of the doorway structure 18 . In addition, upper and lower hinges 36 A, 36 B are included in the disassembled parts package already attached to the upper left corner part 34 D and left side part 34 F of the doorway structure 18 . The hinges 36 A, 36 B per se may be widely-available self-closing spring door types. The hinges 36 A, 36 B as shown in FIGS. 3 and 17 and hinges 60 , 62 , as shown in FIG. 18 , are examples of suitable hinges that can be used. A door latch receiver 38 is also included in the disassembled parts package already attached to the right side part 34 E approximately midway along the right vertical side 18 A of the doorway structure 18 .
FIGS. 5-11 show an exemplary embodiment of a sequence of steps in a method of installing the assembled doorway structure 18 in the net 12 of the batting cage 10 , which method constitutes another aspect of the present invention. FIG. 5 shows the doorway structure 18 placed adjacent the net 12 in the desired location where the access door unit 14 will be installed. FIGS. 6 and 7 show an initial sequence of steps taken to cut a generally centrally-located, vertically-elongated, rectangular-shaped hole 40 into a portion of the net 12 located within the outer perimeter frame 30 of the doorway structure 18 . This is done in order to start to open the net 12 to provide the doorway passage 20 through it. FIGS. 7-9 show right, left and top marginal portions 12 A- 12 C of the net 12 left untrimmed to allow their subsequent attachment respectively along the right vertical side 18 A, left vertical side 18 B and horizontal top 18 C of the doorway structure 18 . The horizontal bottom 18 D of the doorway structure 18 which bounds the bottom of the passage 20 is, of course, left unattached to the net 12 . FIG. 8 shows slits 42 cut in the net 12 at approximately diagonal angles that intersect upper right and left corners 18 E, 18 F of the outer perimeter frame 30 . The slits 42 facilitate folding the right, left and top marginal portions 12 A- 12 C of the net 12 over and about the right and left vertical sides 18 A, 18 B and horizontal top 18 C of the doorway structure 18 and then attaching the marginal portions 12 A- 12 C to portions of the net, in a final sequence of steps shown in FIGS. 9 and 10 . The attaching step involves lacing or securing the marginal portions 12 A- 12 C of the net 12 to the adjacent portions around the exterior of the outer perimeter frame 30 using strands 44 of flexible string, core or rope of appropriate lengths. FIG. 11 shows the completed installation of the doorway structure 18 in a freestanding orientation after the cage net 12 has been secured to the right and left vertical sides 18 A, 18 B and horizontal top 18 C of the doorway structure 18 .
FIGS. 12 and 13 show the peripheral frame 22 of the door 16 of the access door unit 14 by itself. (It should be noted here that the orientation of the door 16 shown in FIGS. 12 and 14-16 is the same of that shown in FIGS. 1 and 2 ). The peripheral frame 22 of the door 16 may be assembled from a plurality 46 of parts, for example, four pairs of parts or eight parts in total, into the peripheral frame 22 . The plurality 46 of parts may be constructed from widely-available metal tubing, for example steel or aluminum, by using well-known fabrication techniques. The plurality 46 of parts may be marketed disassembled in a package and then fitted and assembled to one another, for example, at mateable male and female ends. The assembled parts are then secured together by use of fasteners, such as bolts and nuts (which are included in the disassembled parts package), applied to the mated ends. The closure panel 24 of the door 16 attached to and extending across the interior open area 26 defined by the peripheral frame 22 may be constituted, for example, by a double layer of netting (see FIG. 1 ) formed into a sock net 48 (which also is included in the disassembled parts package). It is combined with the assembled parts of the peripheral frame 22 by sliding it over the assembled parts so that the sock net 48 extends across and covers the interior open area 26 bounded by the assembled parts of the peripheral frame 22 , before mounting the door 16 to the doorway structure 18 via the upper and lower hinges 36 A, 36 B shown in FIG. 3 . An alternative to the sock net 48 is a single layer of netting to form the closure panel 24 which could be employed by lacing the single layer of netting onto the peripheral frame 22 of the door 16 . The use of the sock net 48 , however, provides added convenience and is more durable in its ability of absorb impacts from balls. In an exemplary embodiment, the door parts of each pair may be substantially identical to one another but different from the door parts of the other pairs.
In the exemplary embodiment shown in FIG. 13 , the plurality 46 of parts for assembling the peripheral frame 22 of the door 16 may include:
(1) lower right and left corners parts 46 A, 46 B arranged in a mirror image relationship to one another and each having a substantially right angle configuration; (2) upper right and left corner parts 46 C, 46 D also arranged in a mirror image relationship to one another and each having a substantially right angle configuration; (3) right and left side parts 46 E, 46 F of substantially straight configurations disposed between and interconnecting corresponding upper right and left corner parts 46 C, 46 D with lower right and left corner parts 46 A, 46 B; and (4) top and bottom parts 46 G, 46 H of substantially straight configurations and disposed between and interconnecting corresponding upper right and left corner parts 46 C, 46 D with one another and lower right and left corner parts 46 A, 46 B with one another.
In addition, a pivotal door latch 50 seen in FIG. 12 is included in the disassembled parts package already pivotally attached to the left side part 46 F. The location of the door latch 50 is approximately midway along the midway along the left vertical side 16 C of the door 16 .
FIGS. 14-16 show an exemplary embodiment of a sequence of steps in a method of installing the sock net 48 over the assembled door 16 , which method constitutes yet another aspect of the present invention. FIG. 14 shows the sock net 48 closed at what will become it top end 48 A and opened at what will become its bottom end 48 B after it is applied to the door 16 as shown in FIG. 1 . FIGS. 15 and 16 show the sock net 48 at its open bottom end 48 B placed over the horizontal top 16 A of the door 16 and slid down the right and left vertical sides 16 B, 16 C of the door 16 until the sock net 48 fully covers the interior open area 26 (see FIG. 12 ) bounded by the door 16 . FIG. 1 shows the door 16 installed in the doorway structure 18 after the sock net 48 has been applied and the bottom end 48 B of the sock net 48 tied in place to the bottom 16 D of the door 16 .
As shown in FIG. 1 , the door 16 is attached to the doorway structure 18 via the upper and lower hinges 36 A, 36 B, which are better seen FIGS. 3 and 17 . Also, FIG. 17 shows close-up details of the hinge 36 A, 36 B pivotally attaching the door 16 to the doorway structure 18 . FIGS. 12 and 3 respectively show one exemplary embodiment of components of a latch mechanism having the pivotal door latch 50 on the door 16 and the latch receiver 38 on the doorway structure 18 . As the door 16 is moved to within the passage 20 of the doorway structure 18 the latch 50 rides up a ramp defined on the receiver 38 until it reaches an upwardly open notch. The latch 50 rotates and drops into the notch such that the door 16 is now latched in the closed position. By the user standing at the outside of the door 16 as shown in FIG. 1 , after lifting the latch 50 from the notch the user can then pull on the door 16 to swing it open. A tab may be affixed to the door 16 so as to protrude from below the latch 50 and hold or supports the latch 50 in a horizontal position in which it will engage the ramp and ride up the ramp and fall into the notch merely by the closing movement of the door which is automatically caused by the self-closing hinges 36 A, 36 B. This capability ensures that the door 16 closes after each use. The user standing at the inside of the door 16 can reach a finger through the net 12 and engage and lift the latch 50 from receiver 38 in order to push open the door 16 .
FIGS. 19-22 show another embodiment of components of a latch mechanism having double latches 54 and double receivers 56 which can be used on the door 16 and doorway structure 18 . The double latches 54 are pivotally mounted at the front and rear (or outside and inside) of the right vertical side 16 B of the door 16 . The arms 58 may be separate from one another so as to be pivotally movable independently of one another or may be connected together so as to be pivotally movable in unison or together. In either case, they move toward and away from the double receivers 56 which are affixed at front and rear (or outside and inside) of the right vertical side 18 A of the doorway structure 18 .
FIG. 18 shows one hinge of a pair thereof of a different type (than that of FIG. 17 ), which can be used to pivotally mount the door 16 to the doorway structure 18 , replacing the upper and lower hinges 36 A, 36 B seen in both FIGS. 3 and 17 . Each hinge includes an upper tubular part 60 affixed to the door 16 , a lower tubular part 62 affixed to the doorway structure 18 , and a hinge pin 64 which inserts from above downward first through the upper tubular piece 60 and then through the lower tubular piece 62 .
FIGS. 23 and 24 show top and bottom door stops 66 , 68 affixed to the top 16 A and bottom 16 B of the door 16 . The top and bottom door stops 66 , 68 may take the form of straight parts which respectively extend upwardly from the top 16 A and downwardly from the bottom 16 D of the door 16 through sufficient distances to respectively engage the top 18 C and bottom 18 D of the doorway structure 18 so as to prevent the door 16 from swinging through the doorway structure 18 and instead restrict its pivotal movement toward and away from the doorway structure 18 to either at the front or rear of the doorway structure 18 , depending upon whether the door stops 66 , 68 are affixed to the front or rear of the door 16 .
Referring now to FIGS. 25-27 , there is illustrated another exemplary embodiment of an access door unit, generally designated 70 adapted for free-standing use as a protective screen structure for a softball pitcher. FIGS. 25 and 26 show the door unit 70 having a doorway structure 72 and a door 74 , as described hereinbefore with respect to door unit 14 except that the door 74 has a closure panel in the form of a protective screen 76 that extends about half the length of the interior open area 80 of the door 74 and thus of the passage of the doorway structure 72 . The protective screen 76 is mounted to a transverse shaft 78 which extend across the interior open area 80 of the door 74 and is attached to right and left upright side portions 82 , 84 of the outer peripheral frame 86 of the door 74 about midway between the top and bottom thereof. In such manner, the protective screen 76 is mounted to be pivotally converted, as shown in FIG. 27 , between an upper position shown in FIG. 25 and a lower position shown in FIG. 26 . In the upper or “up” position of FIG. 25 the protective screen is deployed for screening the upper portion of the interior open area 80 and thereby protecting a softball pitcher who will deliver the softball through the lower open portion 88 of the interior open area 80 of the door 74 . In the lower or “down” position of FIG. 26 the protective screen is deployed for screening the lower portion of the interior open area 80 and thereby protecting a baseball pitcher who will deliver the baseball through the upper open portion 89 of the interior open area 80 of the door 74 .
Referring to FIGS. 28-31 , there is illustrated still another exemplary embodiment of an access door unit, generally designated 90 . FIGS. 28 and 29 show the door unit 90 having a doorway structure 92 and a door 94 . The doorway structure 92 is as described hereinbefore with respect to door unit 14 . The door 94 and its closure panel in the form of a protective screen 95 is now about half the length of the passage 96 of the doorway structure 92 , instead of the full length as in the case of door units 14 and 70 , so as to adapt the door 94 for use as a protective screen for a softball pitcher throwing the softball underhand when in the “up” position of FIG. 28 and for a baseball pitcher throwing the baseball overhand when in the “down” position of FIG. 29 . FIGS. 30 and 31 respectively show the doorway structure 92 and door 94 of the door unit 90 of FIGS. 28 and 29 with the sets of spaced apart hinges 98 A, 98 B and 100 and latches 102 A, 102 B and 104 on the outer perimeter frame 106 of the doorway structure 92 and the peripheral frame 108 of the door 94 . To convert the door 94 between the “up” position of FIG. 29 and the “down” position of FIG. 29 , it may be lifted off one set of the hinges 98 A, 98 B on the doorway structure 92 and dropped onto the other set of hinges 98 A, 98 B on the doorway structure 92 . On either set of hinges of the doorway structure 92 , the door 94 is pivotally supported by the doorway structure 92 so as to be pivotally movable between a closed condition, wherein the door 94 is secured to the doorway structure 92 by either of latches 102 A and 102 B on the doorway structure 92 and the latch 104 on the door 94 , and an opened condition, permitting entry or exit through the passage of the doorway structure 92 .
To summarize, the above-described access door unit 14 is a self-supporting and self-standing door assembly that allows a buyer to quickly and easily install the unit in the net wall or end of the batting cage 10 . The unit 14 may be advantageously marketed as a disassembled kit with conventional metal components or hardware to assemble the door 16 and doorway structure 18 and also with the netting for providing the sock net 48 to form the closure 24 of the door 16 . The unit 14 gives the consumer the option to buy, assemble and install the unit into an existing batting cage 10 . Thus, the unit 14 can be retrofitted to existing batting cages as well as installed with new batting cages. Also, the unit 14 can be used on indoor or outdoor batting cages. The unit 14 needs to be installed on a flat level indoor or outdoor surface so that the unit can stand alone without tilting or tipping over. Also, the access door units 70 , 90 are self-supporting and self-standing and may be advantageously marketed as a disassembled kit in the same fashion as the access door unit 14 .
It is thought that the present invention and its advantages will be understood from the foregoing description and it will be apparent that various changes may be made thereto without departing from the spirit and scope of the invention or sacrificing all of its material advantages, the forms hereinbefore described being merely exemplary embodiments thereof.
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An access door unit includes a door, doorway structure, and elements for pivotally attaching the door to the doorway structure. The doorway structure has an outer perimeter frame and base affixed thereon. The base has support members extending in transverse relation to and outwardly fore and aft from the outer perimeter frame and adapted to rest on a generally level support surface such that the outer perimeter frame extends upright from the base enabling the doorway structure to assume a free-standing, self-supporting orientation on the support surface. The outer perimeter frame of the doorway structure defines a passage large enough to fit the door and permit entry or exit through the passage when the door is opened. A closure panel of the door may be full or half length in accordance with the different uses being made of the access door unit.
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FIELD OF THE INVENTION
[0001] This invention relates to product packaging and product display, and more particularly to methods and devices for providing low cost product retainment during shipping and enhanced display characteristics at retailer.
BACKGROUND
[0002] Retailing or shopping as a concept extends at least as far back as ancient Greece, where the agora served as a marketplace for merchants to sell their goods. In ancient Rome a similar marketplace known as the forum existed. Throughout history fairs and markets have a long history that started when humans felt the desire to exchange goods and services where people would shop. Such markets are frequently weekly whilst fairs were typically less frequent. Subsequently, shops began to be permanently established when market traders stayed in one location and were traditionally specialized, e.g. a bakery, a butchery, a grocer, where the customer would be served by the shopkeeper, who would retrieve all the goods on their shopping list. Shops would often deliver the goods to the customers' homes.
[0003] Then in the 1930s supermarkets appeared in the United States during the Great Depression as customers became price sensitive in a manner never seen before. In supermarkets, and their larger cousins the hypermarkets, customers select goods, retrieve them off the shelves using self-service, and may even scan the items to generate their bill and pack their own goods. Customers deliver their own goods. Subsequently, online retailing has been added to the options for customers via the Internet where after selection and purchase the goods are delivered to their homes.
[0004] Within each of these different retailing models, be it individual retailers, supermarkets, or online retailing operations, there exists another retailing concept, business-to-business (B2B) retailing wherein one business acts as the customer to another business. For example, a supermarket, such as Krogers, Safeway, Wal-Mart etc, sources the products it sells either directly from multiple producers such as PepsiCo, Nestlé, Unilever, Kraft, and General Mills or from food distributors such as Sysco Corporation who purchase and manage logistics for the retailer.
[0005] Since the Industrial Revolution products have been shipped in bulk from a manufacturer to a retailer in a variety of packaging display vehicles. The package display vehicles need to be attractive, stand up to the rigors of shipment, requiring minimal handling at the retail level and provide easy access to the product. They also need to be cost effective. With the recent drastic changes in the retail environment over the past few years with low cost supermarkets/hypermarkets and big box retailers these retailers no longer want to even cut cases for display or unpack goods onto the shelves. Excess protective packaging such as increase board strength, using double wall versus single wall, dividers, corner boards, slip sheets, layer pads or trays between layers of packages, all add additional material, labor and freight costs to the manufacturer, retailer and the consumer. These cost variables can frequently be overlooked but can add to significant excess costs. The constant competitive pressure to drive costs down on the manufacturing and retail sides, while, at a minimum, maintaining profitability present challenges which the embodiments of the invention address.
[0006] At the same time retailers demand packaging that facilitates high sales turnover within the allocated space in the shortest amount of time. They demand that the products be ready to shop once the pallet hits the retail floor and any perimeter protective packaging is removed. The next time they want to touch the packaging display vehicle is to recycle it once empty. To compound matters, many of the large retailers and warehouse clubs, have varying requirements for special promotions, graphics, packages, sizes, and counts etc. which make long production runs less feasible. Adding to these factors, there is constant pressure to reduce the costs to retailers and as the life cycles of a product package size, structure, quantity, graphics, merchandising, etc. become shorter then these reduce the feasibility for long term packaging machinery expenditures by the manufacturer. In many instances, the retailer does not want to do anything more than remove part of the packaging the products are shipped in to yield the product display the customer interacts with.
[0007] At the same time retailers and customers alike do not want products that have been damaged in transit, storage or on display as well as ensuring other problems are overcome to avoid deleterious effects on the product that, in turn, might impair its marketability. Likewise, retailers and manufacturers alike do not want the costs associated with returns where the product has been damaged even if the packaging appears unaffected. This has tended to result in increased packaging around the product in order to attain the necessary strength and rigidity. Of the packaging display vehicles used for such packaging, it has heretofore been necessary, in many instances, for them to be formed of heavy gauge costly material and/or to utilize special reinforcing inserts to be positioned within the packaging display vehicle. Numerous multiple 90 and 180 degree folds are required to lock reinforcement features in place adding additional labor costs, production displays and additional opportunities for repetitive stress injuries to occur.
[0008] Further, the weight and current designs of the superimposed stacked arrangement of product packaging in storage, display, shipment, etc. certain external packaging is subjected to substantial compressive forces leading to use of thicker cardboard etc. in packaging in order to avoid the collapse or distortion of the lower packaging sometimes nesting inside the container it was supposed to be superimposed and stacked on, resulting in sidewall deflection, tearing of adjoining interlocking supports and panels, accidental exposure of product and in some cases, pallet loads collapsing. To overcome this, some packaging designs use display trays with smaller footprints and a smaller number of products per display in order to minimize twisting, torque and other disfigurement resulting from excessive stress when extra products are added. This results in an increased unit cost per package as the cost of the display and assembly is prorated over fewer pieces.
[0009] Most prior art packaging efforts focus on getting the product safely from the plant, to the retailers' distribution center and ultimately to the retail floor. In some cases, minimal effort seems to be placed on designing a package that will withstand the rigors of how it is actually shopped on to the retail floor. At this stage, the removal of product(s) from the packaging should leave the remainder intact and presenting an appealing image to the customer. The retailer does not want to pay employees to individually reposition each product item on display in a manner that is both appealing to the customer and safe for the product nor do customers want to rummage through a product display to ascertain the product in front of them or find one that appeals to them. Accordingly, many products are packaged in packaging formats that provide a stable base but result in increased packaging volume and therefore reduced product count per package. Embodiments of the invention address these issues.
[0010] At the same time, lead times are continuing to shrink such that varying product packaging requires manufacturers can mix-and-match a small number of elements to provide the desired flexibility in packaging options and desired response time of retailers Embodiments of the invention address these issues.
[0011] Within the prior art there are a large number of patents that address different aspects of product packaging but none address all of the issues identified above nor do any of these prior art packaging approaches provide an adequate solution to retailers evolving demands. Further, most of these prior art approaches tend to address products that are small, lightweight, and approximately constant in their three dimensions. Solutions for high aspect ratio products are far less common.
[0012] Accordingly, there is a need for a packaging solution that allows a common package footprint to handle multiple different products.
[0013] There is further a need in the art for a container with improved strength characteristics to withstand the collapsing or lateral deflection of vertical container walls which may result when forces are applied to such containers without requiring complex assembly or design.
[0014] There is further a need for a container that is optimally adapted for pallet-type marketing, namely retail sale of products displayed in bulk in the containers in which they are shipped in bulk.
[0015] There is a further a need for a container which is easy to manipulate and easy to assemble.
[0016] Other aspects and features of the present invention will become apparent to those ordinarily skilled in the art upon review of the following description of specific embodiments of the invention in conjunction with the accompanying figures.
SUMMARY
[0017] It is an object of the present invention to mitigate limitations within the prior art relating to product packaging and product display, and more particularly to methods and devices for providing low cost product retainment during shipping and enhanced display characteristics at retailer.
[0018] In accordance with an embodiment of the invention there is provided a method comprising;
providing a first packaging support comprising a predetermined first count of first platforms, each first platform being defined by a predetermined width; providing a second packaging support comprising a predetermined second count of second platforms, each second platform being defined by a predetermined width; inserting the first and second packaging supports into an outer carton; inserting a predetermined third count of products into the outer carton, wherein the first and second packaging supports provide for stable positioning of the predetermined third count of products during shipment to and display at a retailer's establishment.
In accordance with an embodiment of the invention there is provided a method comprising;
receiving a product of a plurality of products at a location for display within a shipment carton, the shipment carton comprising:
a first packaging support comprising a predetermined first count of first platforms, each first platform being defined by a predetermined width; a second packaging support comprising a predetermined second count of second platforms, each second platform being defined by a predetermined width; an outer shell;
displaying the product of the plurality of products at the location within a display carton, wherein the product of the plurality of products are inserted within the outer shell and are restrained by the first and second packaging supports and the first and second packaging supports provide for stable positioning of the product of the plurality of products during shipment and display.
[0030] Other aspects and features of the present invention will become apparent to those ordinarily skilled in the art upon review of the following description of specific embodiments of the invention in conjunction with the accompanying figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Embodiments of the present invention will now be described, by way of example only, with reference to the attached Figures, wherein:
[0032] FIGS. 1 and 2 depict a prior art approach to product packaging according to U.S. Pat. No. 6,386,366;
[0033] FIG. 3 depicts a prior art approach to product packaging according to U.S. Pat. No. 7,004,379;
[0034] FIGS. 4A and 4B depict typical packaging formats within the prior art;
[0035] FIG. 4C depicts a typical retailer shelf for products with high aspect ratio,
[0036] FIG. 5 depicts a packaging methodology according to an embodiment of the invention;
[0037] FIG. 6 depicts a packaging methodology according to an embodiment of the invention;
[0038] FIGS. 7A and 7B depict packaging methodologies according to embodiments of the invention;
[0039] FIG. 8 depicts packaging methodologies according to embodiments of the invention;
[0040] FIG. 9 depicts packaging methodologies according to embodiments of the invention;
[0041] FIG. 10 depicts packaging methodologies according to embodiments of the invention;
[0042] FIG. 11 depicts packaging methodologies according to embodiments of the invention; and
[0043] FIG. 12 depicts packaging methodologies according to embodiments of the invention.
DETAILED DESCRIPTION
[0044] The present invention is directed to product packaging and product display, and more particularly to methods and devices for providing low cost product retainment during shipping and enhanced display characteristics at retailer.
[0045] The ensuing description provides exemplary embodiment(s) only, and is not intended to limit the scope, applicability or configuration of the disclosure. Rather, the ensuing description of the exemplary embodiment(s) will provide those skilled in the art with an enabling description for implementing an exemplary embodiment. It being understood that various changes may be made in the function and arrangement of elements without departing from the spirit and scope as set forth in the appended claims.
[0046] A “package,” “box,” “container,” or “carton” as used herein and throughout this disclosure, refers to an outer packaging employed in the packaging, shipment, storage, and display of products which are packaged or unpackaged within.
[0047] Referring to FIG. 1 there is depicted a prior art packaging approach as disclosed within U.S. Pat. No. 6,386,366. As depicted a container 101 which is currently used to transport and store several individually packaged products P is depicted. The container 101 includes a body 102 having a bottom panel 103 and two side panels 104 extending upward from opposite sides of the bottom panel 103 . Openings 105 are provided in opposite sides of the body 102 and permit limited viewing of one face of the packaged products P. The container 101 also includes a removable lid 106 . In order to display the packaged products P loaded within the container 101 , the lid 106 is removed. Thereafter, each individually packaged product P must be removed from the body 102 and properly positioned in a display location. This, however, is a labor-intensive process, as previously described.
[0048] Alternatively, after the lid 106 is removed, the body 102 , with the packaged products P loaded therein, can be positioned in a display location. In order to permit access to the packaged products P by a consumer, a bottom flap 107 and side flaps 108 of the body 102 must also be opened. In this state, however, the body 102 , appears unkempt and only permits limited viewing of one face of the packaged products P. In addition, when the bottom flap 107 and the side flaps 108 are opened, the body 102 no longer provides adequate support for the packaged products P. For example, if the packaged products P are packaged as individual bags or soft-side packages, the side flaps 108 and, especially, the bottom flap 107 no longer provide vertical or lateral support for the packaged products P. The packaged products P, therefore, can easily fall through one of the openings 105 . Consequently, positioning of the body 102 in a display location, with the packaged products P loaded therein, results in a product display which is generally unappealing and unattractive to a consumer.
[0049] An embodiment of a prior art shipping and display container 100 according to the prior art packaging approach according to embodiments of the invention as disclosed within U.S. Pat. No. 6,386,366 are depicted in FIG. 2 . As shown in FIG. 2 , the tray 100 of the shipping and display container includes a bottom panel 110 , a back panel 120 extending upward from the bottom panel 110 along a back edge thereof, a front panel 130 extending upward from the bottom panel 110 along a front edge thereof, and a pair of bottom side flaps 112 extending from opposite sides of the bottom panel 110 . The back panel 120 and the front panel 130 are each preferably oriented generally perpendicular to the bottom panel 110 . The bottom side flaps 112 extend upward from the bottom panel 110 and are also preferably oriented generally perpendicular to the bottom panel 110 . As such, the tray 100 is generally L-shaped.
[0050] Further, as shown in FIG. 2 , an upper edge 114 of the respective bottom side flaps 112 is preferably linear, extending generally parallel with a lower edge 116 , such that the bottom side flaps 112 are relatively uniform in height. Alternatively, however, the upper edge 114 can assume other configurations, either linear or non-linear, such that the bottom side flaps 112 can have shapes, either regular or irregular, other than that shown in FIG. 2 . The tray 100 also includes a pair of back side flaps 122 extending from opposite sides of the back panel 120 and a pair of front side flaps 132 extending from opposite sides of the front panel 130 . The back side flaps 122 extend forward from the back panel 120 and are preferably oriented generally perpendicular to the back panel 120 . The front side flaps 132 extend rearward from the front panel 130 and are preferably oriented generally perpendicular to the front panel 130 . As such, each of the bottom side flaps 112 are secured to an adjacent one of the back side flaps 122 and the front side flaps 132 . The bottom side flaps 112 can be secured to the back side flaps 122 and the front side flaps 132 by, for example, adhesive, tape, or staples.
[0051] The front panel 130 includes a back face (not shown) facing toward the back panel 120 and a front face 134 facing away from the back panel 120 opposite the back face. As shown in FIG. 5 , the front face 134 provides a display area adapted to receive indicia 136 thereon. The indicia 136 generally includes information identifying the packaged products P positioned on the tray 100 and can be, for example, printed directly on the front face 134 or a label affixed to the front face 134 . Also as shown in FIG. 2 , the cover 200 includes a top panel 210 and a front panel 220 extending downward from the top panel 210 along a front edge thereof. The front panel 220 is preferably oriented generally perpendicular to the top panel 210 . As such, the cover 200 is also generally L-shaped.
[0052] The cover 200 also includes a pair of top side flaps 212 extending from opposite sides of the top panel 210 , a back flap 214 extending from a back edge of the top panel 210 , and a pair of front side flaps 222 extending from opposite sides of the front panel 220 . The top side flaps 212 extend downward from the top panel 210 and are preferably oriented generally perpendicular to the top panel 210 . The back flap 214 is configured to extend generally downward from the top panel 210 and is pivotable relative to the top panel 210 about the back edge thereof. The front side flaps 222 extend rearward from the front panel 220 and are preferably oriented generally perpendicular to the front panel 220 . As such, each of the top side flaps 212 are secured to an adjacent one of the front side flaps 222 by, for example, adhesive, tape, or staples.
[0053] Referring to FIG. 3 there is depicted a prior art approach to product packaging according to U.S. Pat. No. 7,004,379 wherein the folded and glued preform after the automatic folding and gluing steps and prior to shipment are depicted by assemblies 310 as well as prior to folding and gluing with preform 320 . The preform 320 employs multiple panels that form the corner posts which are folded over each other about fold lines in order to form a corner comprised of two layers of sheet material. The fold line, however, extends from the top of the corner to approximately three-quarters of the way down the corner and is then cut to form a foot. Thus, when the panel is folded over to overlay another panel, the foot remains extending outward. Also when the panel is folded over so as to overlie the other panel, a smaller panel at the free end of the corner panels overlies the edge of the inner surface of the side wall and is glued thereto to form a side corner wall and the main portion of panel overlying the other panel forms a front corner wall. Each of the other corners is formed in the identical manner. Shoulder forming panels and positioning tabs are pre-cut and formed at the uppermost part of the panel forming the side walls and include old lines and die-cut sections. At the manufacturer, the top end of the panel forming the side wall is folded over along a fold line and the inner surface of the panel is glued to the inner surface of the side wall. Once assembled the assembly 310 allows for robust stacking of assemblies 310 for shipment etc but poor display options to the customer as the assemblies 310 must be displayed transversely for ease of access.
[0054] However, both prior art packaging solutions as depicted in FIGS. 1 through 3 are typical of those within the prior art and address the provisioning of packaging shells within which discrete product packages are presented to the customer, where as depicted in FIG. 4A , such prior art packaging options exploit packages for each individual product that are inherently stable due to their exploitation of packaging dimensions that are approximately constant in each axis and have large bases upon which each individual product package sits. Referring to FIG. 4B a prior art packaging technique is depicted wherein the outer shell of the packaging incorporates a series of slots within which the cardboard back sheet of the product packaging are inserted. However, as evident, the manufacturer does not exploit this for all of their products and a typical display of products without large product package bases is depicted in area 430 with product packages lying down. Each display package is designed specifically to the product displayed and accordingly first display package 410 for 3 packs of halogen lights is different to second display package 420 for single pack incandescent lights. Similarly, FIG. 4C shows a typical display within a big box retailer for decorative floor registers for air conditioning vents wherein each display package simply has the floor registers leaning against the back wall of the display package initially until customers remove one or more wherein they may lean forward, slide down, etc.
[0055] Accordingly, referring to FIG. 5 , there is depicted a packaging methodology according to an embodiment of the invention for products wherein a standard box 520 when assembled has product unit 510 inserted within it which is then sealed to yield shipment box 530 . At the retailer, the first to fourth flaps 520 A to 520 D may be removed leaving carton 520 E with product unit 510 visible, allowing the customer to remove each product 510 A. Once all product 510 A is removed, the carton 520 E and Packaging Supports 510 B may be disposed off. Optionally, Packaging Supports 510 B may be recycled along with carton 520 E as they are both based upon similar materials, e.g. paper based or plastic, or they may be recycled separately as they are formed from different materials, e.g. a cardboard box for carton 520 E and plastic Packaging Supports 510 B. Alternatively, the manufacturer may work with the retailer to recover the Packaging Supports 510 B by collecting these at the next delivery of further products. Now referring to FIG. 6 there is depicted a product unit 510 in expanded view with first and second Packaging Supports 610 A and 610 B at two ends of a set of products 620 . Whilst FIGS. 5 and 6 depict a packaging methodology according to an embodiment of the invention for shipment and retail display it would be evident that the concept may also be used solely for shipment with the retailer removing products from the packaging prior to display or cutting off the front of the box 520 and merely removing the four flaps 520 A to 520 D and Packaging Support 610 A for display.
[0056] Referring to FIGS. 7A and 7B there are depicted packaging methodologies according to embodiments of the invention. As depicted in FIG. 7A a perspective view of Packaging Support 700 is shown comprising a base plate 730 with a plurality of platforms 720 which define between them a plurality of zones 710 which are dimensioned to fit one end of a product to be packaged for shipment and retail display. FIG. 7B depicts plan and front elevation views of Packaging Support 700 . As depicted, the number of platforms 720 may be varied for a given base plate 730 to suit the product being packaged. In this manner, the manufacturer may standardize the carton within which the Packaging Supports 700 and products are assembled such that all aspects of palletization, shipments, display are consistent irrespective of whether the product being shipped is for example a thin vent grill or a deep floor register.
[0057] This being evident in FIG. 8 wherein first and second Packaging Supports 800 A and 800 B according to embodiments of the invention are depicted. First Packaging Support 800 A comprising M platforms of width W 1 with zones G 1 between them. Second Packaging Support 800 B comprising N platforms of width W 2 with zones G 2 between them. As depicted in FIG. 9 , first and second Packaging Supports 900 A and 900 B are depicted in cross-section showing that the platforms may be solid or formed from a sheet so that the platforms are hollow. Beneficially, the second Packaging Support 900 B allows a large number of Packaging Supports to be stacked and shipped to the manufacturer for use from their supplier. As discussed supra, a Packaging Support may be formed from a variety of materials including, but not limited to, stamped cardboard, cut-and-folded cardboard, molded paper pulp, molded fiber, expanded polystyrene, vacuum formed polyethylene terephthalate (PET) and polyvinyl chloride (PVC), polyethylene, polypropylene, as well as molded and/or shaped foams. In some embodiments of the invention the Packaging Supports may be metal should the product warrant it through considerations such as cost, weight, etc. Cardboard and molded pulp variants may be made waterproof through the spray application of a wax, for example. In other embodiments of the invention the Packaging Support may be machined, laser cut etc from a pre-form.
[0058] Now referring to FIG. 10 , there are depicted packaging methodologies according to embodiments of the invention with first to third Packaging Supports 1000 A to 1000 C. As depicted with first and second Packaging Supports 1000 A and 1000 B respectively, the platforms may be offset at a predetermined angle to an axis of the first and second Packaging Supports 1000 A and 1000 B respectively. Accordingly, upon the retailer shelving the first and second Packaging Supports, 1000 A and 1000 B respectively provide for the products 1110 to sit against the rear of the carton 1120 such as depicted in first retailer cross-section 1100 A in FIG. 11 or the bottom of the carton 1120 and be sloped slightly such as depicted in second retailer cross-section 1100 B in FIG. 11 . Alternatively, when displaying products vertically no angle may be employed.
[0059] Third Packaging Support 1000 C in contrast is designed to engage with large products within a carton, e.g. air filters which are large surface area but thin, large area grills, and other products. As depicted in FIG. 12 with first and second cross-sections 1200 A and 1200 B respectively, a Packaging Support 1210 may be employed with thin product 1220 and thick product 1230 . If the spacing of the platforms within the Packaging Support 1210 is greater than the thickness of the product then each zone between the platforms may be employed to hold a product. In other embodiments of the invention only a portion of the zones between the platforms may be employed such that for example the same Packaging Support 1210 is employed with a range of products for packaging, shipment and display.
[0060] Within the foregoing descriptions of embodiments of the invention in respect of FIGS. 5 through 12 it may have been assumed by the reader that the Packaging Supports at either end are identical. However, they may be different in order to accommodate the particular product packaging. It would also be evident that multiple sets of Packaging Supports may be employed within a single container or carton with or without additional flat sheet or shaped dividers. Similarly, a Packaging Support may according to the requirements of the manufacturer or retailer have platforms of different dimensions within a single Packaging Support. For example, a product may require 2 elements, e.g. a floor register and air filter which have different dimensions. Rather than these being disposed in adjacent cartons with, for example 20 registers in a first carton and 80 filters in a second carton the display packaging may comprise 16 registers with 16 filters alternating within the same carton. Accordingly, this may provide for reduced waste and/or eased inventory management at the retailer. In other embodiments a product may exploit two or more zones within a Packaging Support at one side of the product and a different number of zones in a Packaging Support at the other side of the product.
[0061] Within embodiments of the invention the Packaging Supports have been described as separate to the box within which the products are shipped and/or displayed. However, it would be evident that within other embodiments of the invention the Packaging Supports may be integral to the box either through attachment prior to insertion of the products, e.g. by glue, tape, staples, etc, or integrally formed within the box at its manufacture.
[0062] The foregoing disclosure of the exemplary embodiments of the present 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 forms disclosed. Many variations and modifications of the embodiments described herein will be apparent to one of ordinary skill in the art in light of the above disclosure. The scope of the invention is to be defined only by the claims appended hereto, and by their equivalents.
[0063] Further, in describing representative embodiments of the present invention, the specification may have presented the method and/or process of the present invention as a particular sequence of steps. However, to the extent that the method or process does not rely on the particular order of steps set forth herein, the method or process should not be limited to the particular sequence of steps described. As one of ordinary skill in the art would appreciate, other sequences of steps may be possible. Therefore, the particular order of the steps set forth in the specification should not be construed as limitations on the claims. In addition, the claims directed to the method and/or process of the present invention should not be limited to the performance of their steps in the order written, and one skilled in the art can readily appreciate that the sequences may be varied and still remain within the spirit and scope of the present invention.
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A method is provided, including providing a first packaging support having a predetermined first count of first platforms, each first platform being defined by a predetermined width; providing a second packaging support having a predetermined second count of second platforms, each second platform being defined by a predetermined width; inserting the first and second packaging supports into an outer carton; inserting a predetermined third count of products into the outer carton, wherein the first and second packaging supports provide for stable positioning of the predetermined third count of products during shipment to and display at a retailer's establishment.
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BACKGROUND OF THE INVENTION
This invention relates to a process for preparing primary aminoorganosilanes. More particularly, the present invention relates to a process for preparing a primary aminoorganosilane by the catalyzed reaction of a cyanoorganosilane with hydrogen.
A process of the foregoing type is described in U.S. Pat. No. 5,117,024. In accordance with this process, a cyanoorganosilane is reacted with hydrogen gas in the presence of a supported cobalt catalyst at a temperature of from about 100EC to 200EC and a pressure within a range of from about 200 psig to 2000 psig. The process is said to provide near quantitative selectivity for the desired primary aminoorganosilane without the production of hydrogen chloride and without the addition of ammonia and solvent systems as in then prior known processes.
A significant disadvantage to the process for making primary aminoorganosilanes described in U.S. Pat. No. 5,117,024 lies in its use of a supported cobalt catalyst. Such a catalyst is typically supplied in the passivated state, i.e., the cobalt particles are covered with a layer of oxide, in order to reduce the hazard of spontaneous combustion of the metal in an oxygen-containing environment such as air. Before the catalyst can be used, it must be activated, generally by reduction with hydrogen at fairly high temperatures, e.g., 500EC and even higher.
SUMMARY OF THE INVENTION
In accordance with the present invention, a process for preparing a primary aminoorganosilane is provided which comprises reacting a cyanoorganosilane with hydrogen under hydrogenation conditions and in the substantial absence of water in the presence of a catalytically effective amount of sponge cobalt to produce the primary aminoorganosilane.
In contrast to a process which employs a passivated cobalt catalyst which is believed to be the case with the process of U.S. Pat. No. 5,117,024 discussed supra, there is no need to activate the sponge cobalt catalyst employed in the process of this invention. Thus, the process of this invention utilizes the catalyst directly and without any need for a prior treatment which would only add to the complexity and expense of the process.
It is further a feature of the invention to conduct the hydrogenation of a cyanoorganosilane to provide the corresponding primary aminoorganosilane employing any suitable catalyst wherein an alkali metal alkoxide is present in the reaction medium to inhibit or suppress the formation of secondary aminoorganosilane.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The starting cyanoorganosilane reactant herein is preferably one possessing the general formula
R 1 3 Si R 2 CN
in which case the product primary aminoorganosilane will conform to the general formula
R 1 3 Si R 2 CH 2 NH 2
wherein each R 1 group is independently selected from the group consisting of alkyl and alkoxy radical of from 1 to about 10 carbon atoms, and R 2 is a divalent hydrocarbon radical of from 1 to about 20 carbon atoms.
The R 1 radical can be, for example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, dodecyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenyl and phenoxy. R 1 is preferably selected from the group consisting of methyl, methoxy, ethyl and ethoxy.
The divalent radical R 2 can be, for example, a divalent radical of an alkane, cycloalkane, or an aromatic or aralkane compound. Thus, divalent radical R 2 can be, for example, a linear or branched alkylene group such as methylene, ethylene, 1,2-propylene, 1,3-propylene, 2-methyl-1,3-propylene, 3-methyl-1,3-propylene, 3,3-dimethyl-1,3-propylene, ethylidene or isopropylidene, a cycloalkylene group such as cyclohexylene or cycloheptylene, an arylene group such as phenylene, tolylene, xylylene or naphthylene, or the divalent group —C 6 H 4 —R 3 — in which R 3 is 10 methylene, ethylene, ptopylene, etc.
Examples of cyanoorganosilanes which can be hydrogenated by the process of this invention include 2-cyanoethyltrimethysilane, 2-cyanoethyldimethylmethoxysilane, 2-cyanoethylmetbyldimethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyldimethylsilane, 2yanoethyldimethoxylsilane, 2-cyanoethyltriethoxysilane, 2-cyanoethyldimethylethoxysilane, 2-cyanoethylphenymethylsilane, 2-cyanoethylphenylmethoxysilane, 3-cyanomethyltriethoxysilane, 3cyanopropyltrtethylsilane, 3-cyanopropylmethyldimethylsilane and 3-cyanopropylmethyldimethoxysilane.
The reaction of the starting cyanoorganosilane with hydrogen in the presence of sponge cobalt catalyst to provide the desired primary aminoorganosilane in accordance with this invention can be carried out in known and conventional high pressure reactors. The reactor can be, for example, a fixed bed, stirred-bed or fluidized-bed type reactor. The process can be run as a batch process or as a continuous process. A stirred-bed reactor is preferred. The reaction tends to be rapid and is generally determined by the amount of catalyst, the pressure of the reactor, reaction temperature and related factors as appreciated by those skilled in the art. In general, residence times of from about 0.2 hours to about 5.0 hours provide acceptable results When the process is run as a batch process, it is generally preferred to use residence times of from about 0.5 to about 3.0 hours accompanied by the addition of hydrogen as it is consumed by the reaction.
It is preferred that the process herein be carried out in the presence of a molar excess of hydrogen, preferably two or more moles of hydrogen per mole of the selected cyanoorganosilane starting reactant. In general, the greater the amount of hydrogen present, the faster the reaction. Therefore, in a preferred mode of operating the process, hydrogen is added in excess at a concentration sufficient to maintain the pressure within the reactor within the range of from about 200 psig to about 2000 psig, and more preferably within the range of from about 500 psig to about 1000 psig, since these pressures permit the use of standard high pressure reactors.
The present process can conventionally be conducted at a temperature within the range of from about 50EC to about 250EC, and preferably at from about 100EC to about 200EC.
The sponge cobalt catalyst employed in the process of this invention can conveniently be selected from among any of several kinds that are commercially available, e.g., Raney7 cobalt, type 2724, from W. R. Grace and Co-0138P from Englehard Corp. If desired and for particular applications, the sponge cobalt can be combined with one or more other catalytically active components, e.g., one or more metals of Group 6B and/or 8B of the Periodic Table of the Elements such as chromium, nickel and/or iron. These metals can be combined with the sponge cobalt catalyst employing any known or conventional process such as doping.
The amount of sponge cobalt catalyst employed in the process of this invention, can vary widely provided, of course, that a catalytically effective amount of the catalyst is present. Useful amounts of sponge-cobalt catalyst can range from about 0.05 to about 20 weight percent, and preferably from about 0.5 to about 1 weight percent, based on the weight of the cyanoorganosilane reactant.
It is convenient to add the sponge cobalt catalyst to the reactor as a slurry, e.g., in a quantity of the intended product primary aminoorganosilane. While the starting cyanoorganosilane could also be utilized for this purpose, it is preferable not to do so since on standing, there may be a tendency of the cyano functionality to result in some poisoning of the catalyst.
The presence of liquid water and/or water vapor is to be substantially avoided as water tends to result in polymerization of some product primary aminoorganosilane to a polysiloxane. It is therefore advantageous to purge the reactor, once sealed, with an inert gas such as nitrogen to substantially remove any water that may be present.
The process of this invention can, if desired, be conducted in the presence of an organic solvent as the use of an organic solvent may increase the rate and/or yield of the process without, however, significantly affecting its selectivity for the desired primary aminoorganosilane. The organic solvent can be a polar or non-polar solvent with a polar solvent, for example, an alkanol such as methanol, ethanol, propanol or isopropanol, being preferred. When using an alkanol solvent, it is preferred that the allanol correspond to any alkoxy group(s) R 1 that may be present in the starting cyanoorganosilane reactant in order to minimize or avoid transesterification. Thus, where the starting cyanoorganosilane contains one or more methoxy groups (e.g., as in the case of the reactants 2-cyanoethyldimethylnethoxysilane, 2-cyanoethylmethyldimethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyl-dimethoxysilane, 2-cyanoethylphenylmethoxysilane and 3-cyanopropylmethyldimethoxysilane), the alkanol solvent of choice would be methanol. When the process is conducted as a batch process, it is preferred that the solvent be present at from about 5 to about 50 weight percent, and preferably from about 10 to about 20 weight percent, of the total reaction mixture. When the process is conducted as a continuous process and a solvent is utilized, the starting cyanoorganosilane reactant can be diluted in the solvent with the cyanoorganosilane comprising from about 50 to about 95 weight percent, and preferably from about 80 to about 90 weight percent, of the liquid feed to the reactor.
It is advantageous to conduct the process of this invention in the presence of a substantially anhydrous base, e.g., an alkali metal alkoxide such as lithium methoxide, lithium ethoxide, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, anhydrous ammonia, their combinations, and the like, to suppress or inhibit the production of secondary aminoorganosilane. Of these bases, the alkali metal alkoxides are preferred. In general, the amount of base added can range from about 0.01 to about I weight percent, and preferably from about 0.05 to about 0.1 weight percent, based on the weight of the sponge cobalt catalyst. When using an alkoxide for the aforestated purpose, a solvent, e.g., the parent alkanol of the alkoxide, can conveniently be used as a vehicle for incorporating the alkali metal alkoxide in the reaction medium. Thus, e.g., lithium methoxide can be added as a solution in methanol, sodium ethoxide as a solution in ethanol, etc. When at least one R 1 group in the starting cyanoorganosilane reactant is an alkoxy group, in order to minimnize or avoid transesterification, it is preferable to use an alkali metal alkoxide corresponding to the alkoxy group and, as solvent for the alkoxide, the corresponding alkanol. Thus, e.g., when at least one R 1 group is a methoxy group, the preferred alkoxide would be a methanol solution of an alkali metal methoxide such as lithium methoxide, sodium methoxide or potassium methoxide.
As previously stated, it is also a particular aspect of this invention to prepare a primary aminoorganosilane by the catalyzed reaction of a cyanoorganosilane with hydrogen under substantially anhydrous conditions in the presence of any suitable catalyst therefor, e.g., sponge cobalt catalyst as previously described or the supported cobalt catalyst of U.S. Pat. No. 5,117,024, and in the presence of the aforesaid alkali metal alkoxide to inhibit or suppress the formation of secondary aminoorganosilane. Optionally, this reaction can additionally employ a different substantially anhydrous base such as anhydrous ammonia to contribute to the suppression of secondary amine formation.
The product primary aminoorganosilane can be recovered by any known or conventional procedure for separating liquid-solid mixtures and mixtures of liquids, for example, filtration andlor distillation.
Primary aminoorganosilanes that can be produced by the present process include, for example, 3-aminopropyltrimethylsilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrirnethoxysilane, 3-aminopropyldimethylsilane, 3-aminopropyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylphenylmethylsilane, 3-aminopropylphenylmethoxysilane, 2-aminoethyltrietioxysilane, 4-aminobutyltrinethylsilane, 4-aminobutyldimethysilane and 4-aminobutylmethyldimethoxysilane.
The following examples are illustrative of the process of this invention for obtaining primary aminoorganosilanes.
EXAMPLE 1
In a 2 liter autoclave containing a magnadrive stirrer, cooling coil, and sample tube for sampling, was added 1000 g of distilled cyanoethyltrimethoxysilane. A slurry of 7.1 g of cobalt catalyst (W. R. Grace, Raney® cobalt, type 2724) in 10 mls of 3-aminopropyltrimethoxysilane (Crompton Corp./OSi Specialities, Silquesto A-1110 Silane), was combined with 0.6 mis of 25% sodium methoxide in methanol solution (Aldrich Chemical Co.,) and allowed to stir for one hour prior to addition to the reactor. Upon addition of the catalyst slurry, the reactor was sealed, purged with nitrogen and then twice pressurized with 200 psig hydrogen and vented to atmospheric pressure. The reactor was then pressurized to 500 psi with hydrogen and heated to 145EC with agitation. The reaction was allowed to continue for five hours, or until hydrogen uptake appeared to have stopped, before cooling to room temperature, venting, and discharging the reactor contents. Samples were taken periodically during the reaction with the progress of the reaction being shown in Table I as follows:
TABLE I
Secondary
Primary
Amine
Uneluted
Time (hrs)
Nitrile (wt %)
Amine (wt %)
(wt %)
Heavies (wt %)
1
73.7
22.6
0.41
0.49
2
46.0
49.9
0.83
0.5
3
23.7
72.1
1.48
0.5
4
8.5
85.5
1.9
0.2
5
1.47
88.8
1.1
5.9
Nitrile = cyanoethyltrimethoxysilane.
Primary amine = 3 aminopropyltrimethoxysilane.
Secondary amine = Bis-[3-(trimethoxysilyl)propyl]amine.
EXAMPLE 2
In a 2 liter autoclave containing a magnadrive stirrer, cooling coil, and sample tube for sampling, was added 1000 g of distilled cyanoethyltrimethoxysilane. A slurry of 2.5 g of sponge cobalt catalyst (W.R. Grace, Raney® cobalt, type 2724) in 10 mls of 3-aminopropyltrimetboxysilane (Crompton Corp./OSi Specialties, Silquest® A-1110 Silane), and 0.5 mls of a 1 M lithium methoxide in methanol solution (Aldrich Chemical Co.) were combined and allowed to stir for one hour prior to addition to the reactor. The reactor was sealed, purged with nitrogen and then twice pressurized with 200 psig hydrogen and vented to atmospheric pressure. The reactor was then pressurized to 500 psi with hydrogen and heated to 145EC with agitation. The reaction was allowed to continue for three hours, or until hydrogen uptake appeared to have stopped, before cooling to room temperature, venting, and discharging the reactor contents. Samples were taken periodically during the reaction with the progress of the reaction being shown in Table II as follows:
TABLE II
Nitrile
Primary
Secondary
Uneluted
Time (hrs)
(wt %)
Amine (wt %)
Amine (wt %)
Heavies (wt %)
0.5
92.0
5.77
0
0
1
77.7
16.9
3.44
0
1.5
58.6
31.6
6.98
0
2
33.3
54.8
8.5
0.7
2.5
7.9
79.0
9.98
0.3
3
1.9
86.8
10.17
0
Nitrile = cyanoethyltrimethoxysilane.
Primary amine = 3-aminopropyltrimethoxysilane.
Secondary amine = Bis-[3-trimethoxysilyl)propyl]amine.
EXAMPLE 3
In a 1 liter Parr autoclave containing a magnadrive stirrer, cooling coil, and sample tube for sampling, was added 500 g of distilled cyanoethyltrimethoxysilane and a slurry of 1.5 g of sponge cobalt catalyst (W. R. Grace, Raney® cobalt, type 2724) in 10 mils of 3-aminopropyltrirnethoxysilane (Crompton Corp./OSi Specialities, Silquest® A-1110 Silane). The reactor was sealed, purged with nitrogen and then twice pressurized with 200 psig hydrogen and vented to atmospheric pressure. The reactor was then pressurized to 500 psi with hydrogen and heated to 160EC with agitation. The reaction was allowed to continue for three hours, or until hydrogen uptake appeared to have stopped, before cooling to room temperature, venting, and discharging the reactor contents. Samples were taken periodically during the reaction with the progress of the reaction being shown in Table III as follows:
TABLE III
Nitrile
Primary
Secondary
Uneluted
Time (hrs)
(wt %)
Amine (wt %)
Amine (wt %)
Heavies (wt %)
0.5
89.8
5.78
1.2
0
1
72.056
16.25
5.8
2.9
1.5
56.1
26.25
9.5
4.5
2
34.4
43.5
13.7
5.6
Nitrile = cyanoethyltrimethoxysilane.
Primary amine = 3-aminopropyltrimethoxysilane.
Secondary amine = Bis-[3-(trimethoxysilyl)propyl]amine.
EXAMPLE 4
In a 2 liter autoclave containing a magnadrive stirrer, cooling coil, and sample tube for sampling, was added 1106 g of cyanoethyltrimethoxysilane, and a slurry of 6.0 g of sponge cobalt catalyst (W. R. Grace, Raney® cobalt, type 2724) in 10 mls of 3-aminopropyltrimethoxysilane (Crompton Corp./OSi Specialties, Silquest A-1110 Silane). The reactor was sealed, purged with nitrogen and then twice pressurized with 200 psig hydrogen and vented to atmospheric pressure. The reactor was then pressurized to 500 psi with hydrogen and heated to 150EC with agitation. The reaction was allowed to continue for three hours, or until hydrogen uptake appeared to have stopped, before cooling to room temperature, venting, and discharging the reactor contents. Samples were taken periodically during the reaction with the progress of the reaction being shown in Table IV as follows:
TABLE IV
Nitrile
Primary
Secondary
Uneluted
Time (hrs)
(wt %)
Amine (wt %)
Amine (wt %)
heavies (wt %)
0.5
59.461
31.77
2.38
3.4
1
1.804
82.14
7.38
6.3
1.5
1.506
82.15
10.5
4.17
Nitrile = cyanoethyltrimethoxysilane.
Primary Amine = 3-aminopropyltrimethoxysilane.
Secondary amine = Bis-[3-(trimethoxysilyl)propyl]amine.
EXAMPLE 5
In a 2 liter autoclave containing a magnadrive stirrer, cooling coil, and sample tube for sampling, was added 1000 g of distilled cyanoethyltrimethoxysilane and a slurry of 3.1 g of unpromoted sponge cobalt catalyst (W. R. Grace, Raney® cobalt, type 2724) in 10 mls of 3-aminopropyltrimethoxysilane (Crompton Corp./OSi Specialities, Silquest® A-1110 Silane) with agitation. The reactor was sealed, purged with nitrogen and then twice pressurized with 200 psig hydrogen and vented to atmospheric pressure. To the reactor was then added 30.4 g of anhydrous ammonia, and then pressurized to 500 psi with hydrogen. The reactor was then heated to 154EC and the stirrer speed increased to 1000 rpm. The reaction was allowed to continue for three hours, or until hydrogen uptake appeared to have stopped, before cooling to room temperature, venting, and discharging the reactor contents. Samples were taken periodically during the reaction with the progress of the reaction being shown in Table V as follows:
TABLE V
Nitrile
Primary
Secondary
Uneluted
Time (hrs)
(wt%)
Amine (wt %)
Amine (wt %)
Heavies (wt %)
0.5
88.0
10.5
0.33
0
1
71.0
25.8
1.6
0
2
32.75
62.0
2.2
1.0
3
6.1
89.8
1.9
0.5
Nitrile = cyanoethyltrimethoxysilane.
Primary amine = 3-aminopropyltrimethoxysilane.
Secondary amine = Bis-[3-(trimethoxysilyl)propyl]amine.
EXAMPLE 6
In a 2 liter autoclave containing a magnadrive stirrer, cooling coil, and sample tube for sampling was added 989 g of distilled cyanoethyltrimethoxysilane. A slurry of 6.5 g of sponge cobalt catalyst (W. R. Grace, Raney® cobalt, type 2724) in 10 mils of 3-aminopropyltrimethoxysilane (Crompton Corp./OSi Specialities, Silquest® A-1110 Silane) was combined with 0.5 ml of a 25% sodium methoxide in methanol solution (Aldrich Chemical Co.) and allowed to stir for one hour prior to addition to the reactor. The reactor was sealed, purged with nitrogen and then twice pressurized with 200 psig hydrogen and vented to atmospheric pressure. To the reactor was then added 42.3 g of anhydrous ammonia, and then pressurized to 500 psi with hydrogen. The reactor was subsequently heated to 160EC and the stirrer speed increased to 1000 rpm. The reaction was allowed to continue for three hours, or until hydrogen uptake appeared to have stopped, before cooling to room temperature, venting, and discharging the reactor contents. Samples were taken periodically during the reaction with the progress of the reaction being shown in Table VI as follows:
TABLE VI
Nitrile
Primary
Secondary
Uneluted
Time (hrs)
(wt%)
Amine (wt %)
Amine (wt %)
Heavies (wt %)
0.5
86.98
18.047
0
0
1
22.3
77
0
0
1.5
2.45
94
1
0
Nitrile = cyanoethyltrimethoxysilane.
Primary amine = 3-aminopropyltrimethoxysilane.
Secondary amine = Bis-[3-(trimethoxysilyl)propyl]amine.
EXAMPLE 7
In a 2 liter autoclave containing a magnadrive stirrer, cooling coil, and sample tube for sampling, was added 1022 g of distilled cyanoethyltrimethoxysilane. A slurry of 2 g of sponge cobalt catalyst (Engelhard Corp.,) in 10 mls of 3-aminopropyltrimethoxysilane (Crompton Corp./OSi Specialities, Silquest® A-1110 Silane) was added to the reactor. The reactor was sealed, purged with nitrogen, and then twice pressurized with 200 psig hydrogen and vented to atmospheric pressure. To the sealed reactor was then added 29.3 g of anhydrous ammonia, and then pressurized to 500 psi with hydrogen. The reactor was then heated to 160EC and the stirrer speed increased to 100 rpm. The reaction was allowed to continue for three hours, or until hydrogen uptake appeared to have stopped, before cooling to room temperature, venting, and discharging the reactor contents. Samples were taken periodically during the reaction with the progress of the reaction being shown in Table VII as follows:
TABLE VII
Nitrile
Primary
Secondary
Uneluted
Time (hrs)
(wt%)
Amine (wt %)
Amine (wt %)
Heavies (wt %)
0.5
96.6
2
0
0
1
84.7
10.6
2.2
0
1.5
68.7
21.95
2.2
0
2
52.431
33.6
1.1
0
3
7.77
74.2
10.2
0
Nitrile = cyanoethyltrimethoxysilane.
Primary amine = 3-aminopropyltrimethoxysilane.
Secondary amine = Bis-[3-(trimethoxysilyl)propyl]amine.
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A process is provided for preparing a primary aniinoorganosilane in which a cyanoorganosilane is reacted with hydrogen under hydrogenation conditions and in the substantial absence of water in the presence of a catalytically effective amount of sponge cobalt to produce the primary aminoorganosilane.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of application Ser. No. 309,829, filed Oct. 8, 1981, abandoned.
BACKGROUND
Throughout the last five years there has been a considerable interest growing among chemists, physicists, and electrical engineers in the development of electrically-conductive organic polymers for use in a variety of applications. Potential applications include lightweight electrical conductors, microwave shields, anti-static devices, photocopying processes, and photovoltaic devices. There are several advantages in using organic polymers versus classical inorganic materials for these applications: organic polymers are by nature lightweight and easily processable, and they offer lower materials costs. For purposes hereof, the term "electrically-conductive organic polymers" refers to polymers whose conductive properties are derived from the conduction band structure of the polymer itself, rather than through the addition or impregnation of a conductor into a polymer substrate. Accordingly, conductive polymeric systems composed of a conductive material (such as powdered graphite or copper fibers) imbedded in an insulating organic polymer matrix or substrate is not considered a conducting polymer within the meaning of the present invention.
To the best of our knowledge, the first example of a highly conductive organic polymer film was demonstrated by researchers at the University of Pennsylvania and reported by Shirakawa et al., Chem. Commun., 1977, p. 578. Their results with chemically doped polyacetylene films greatly stimulated research in this field.
The electrical conductivities of most organic polymers in their virgin state tend to be low; typical values range from 10 -5 to 10 -14 (Ω-cm) -1 . If compared to the conductivities of classical inorganic materials, such as copper (10 6 (Ω-cm) -1 ), silicon (10 -5 (Ω-cm) -1 ), or quartz (10 -18 (Ω-cm) -1 ), most organic polymers would be termed insulators or poor semiconductors. In fact, organic polymers are widely used as electrically-insulating materials in the electronics industry.
A consideration of the band theory as developed for classical inorganic materials is often helpful in describing in very simple terms the insulating nature of a multitude of organic polymers, such as polytetrafluoroethylene (Teflon), polyethylene, polystyrene, and like materials. The low conductivities exhibited by most polymers can be envisioned as resulting from the presence of filled valence electron bands with large energy separations between the valence or highest occupied molecular orbital (HOMO) and conduction or lowest unoccupied molecular orbital (LUMO) bands in these materials. The HOMO-LUMO energy gaps in polyethylene and similar polymers are generally greater than about 3 eV. Classical inorganic materials with valence-conduction band gaps of this magnitude exhibit electrically insulating behavior.
However, presently there are a number of different highly conductive (conductivities around 10° (Ω-cm) -1 ) organic polymers that have been well documented in the open literature. The earliest recognized and most extensively studied of these is polyacetylene, (CH) x , doped with electron-accepting or donating reagents. Work has been done in this area by Shirakawa et al.; Chiang et al., Phys. Rev. Lett., 1977, 39, 1098; Park et al., J. Chem. Phys., 1980, 73, 946; and Chiang et al., Ber. Bunsenges. Phys. Chem., 1979, 83, 407. Shacklett et al., Synthetic Metals, 1979, 1, 307 has worked with doped poly-p-phenylene and others have investigated poly-p-phenylenesulfide, poly-p-phenylenevinylene, polypyrrole and poly-thienylene. A common feature of all these polymers is a molecular structure possessing some degree of π-electron conjugation along the polymer chain. For poly-p-phenylenesulfide, it is postulated that empty sulfur d-orbitals participate in π-conjugation with the phenylene π-system. Although the exact mechanism of charge transport in these doped polymers is still under great debate, it is generally recognized that some degree of π-conjugation in the polymers is a prerequisite to high conductivity.
The polymers mentioned above all exhibit low electrical conductivities (e.g., 10 -9 (Ω-cm) -1 for cis-polyacetylene) before they are chemically treated or "doped" with appropriate electron-accepting or donating reagents. For purposes hereof, the term "doped" in this art refers to the formation of charge transfer complexes between suitable organic polymers and appropriate electron-accepting or electron-donating reagents. This usage of the term is to be distinguished from the usage associated with the semiconductor art which pertains to the positional substitutions of certain atoms for other atoms, as in "doped" inorganic semiconductors. Reaction of suitable organic polymers with electron-accepting reagents results in transfer of electron density from the π-orbitals of the polymers to the acceptor. Similarly, reaction with an electron donor causes addition of electron density to the π-system of the polymers from the donor. For purposes hereof, a "doped polymer" is therefore a polymer which has undergone changes in its π-system electron density through the formation of charge-transfer complexes by reaction of the polymer with suitable electron-acceptor or electron-donor reagents. Such partial oxidation or reduction of polymers upon doping with appropriate reagents is believed to be responsible for the greatly enhanced electrical conductivities displayed by these polymer systems.
Shirakawa et al. and Park et al. have disclosed that a variety of Lewis acids and bases are effective dopants for enhancing the conductivity of polyacetylene. Oxidants such as iodine, bromine, and AsF 5 have been employed, and they indicate that the dopants remain in the polymer matrix after charge transfer as, for example, I n - or AsF 6 - anions. It is also known in the art that polyacetylene can also be reduced with Lewis base alkali metal alloys or sodium naphthalide in tetrahydrofuran; charge transfer results in the inclusion of cations (i.e., alkali metal cations) in the polymer matrix.
There has not been total agreement upon a description of the ways in which the polymer-dopant charge transfer complex manifests itself and influences the charge transport mechanisms in these conjugated polymer systems. For heavily-doped polyacetylene films with conductivity of about 10 2-3 (Ω-cm) -1 ), a band theory model seems adequate. In this model, the population of charge carriers in the valence and conduction bands of (CH) x has been altered sufficiently that individual strands of polyacetylene within a polymer film are described as metallic; however, the "metallic" strands are separated by thin regions of interstrand contact characterized by a potential barrier to charge transport. Along the strands, conduction is metallic; between strands, conduction occurs via a thermally-activated process.
For lightly-doped semiconducting (CH) x films with conductivities of about 10 -6 (Ω-cm) -1 , band theory is inadequate in explaining all the charge transport phenomena. Instead, a mechanism involving the formation of charged solitons--or rather localized charged domain walls, akin to organic radicals--has been proposed. In this mechanism, charge transport would occur via thermally-activated hopping along the polymer chain of the domain walls.
Of these conjugated polymer systems, only poly-p-phenylenesulfide (PPS) exhibits favorable fabrication properties as well as favorable thermal and atmospheric stability; PPS can be heat molded. However, PPS doped with AsF 5 is much less stable to the atmosphere and more brittle than virgin PPS. To date, only AsF 5 has been reported as a suitable dopant for PPS. With certain of these polymer systems (PPS, poly-p-phenylene, poly-p-phenylenevinylene) it appears that I 2 and Br 2 are not strong enough oxidants to effect conductivity enhancements. Fabrication difficulties also exist with polypyrrole. Films of this polymer can only be obtained in situ as the monomer is polymerized. Once polymerized, polypyrrole cannot be further processed by solution or melt methods. Polythienylene is quite stable in air and can be doped with I 2 , but it exists as an intractable powder.
Although doped polyacetylene exhibits the highest conductivity as well as the broadest range of accessible conductivities (as a function of dopant concentration) of an organic polymer currently known, polyacetylene does not exhibit environmental stability or desirable fabricating properties. More specifically, the major limitations in the practical applications of polyacetylene as an organic conductor are the extreme insolubility of (CH) x in solvents other than concentrated H 2 SO 4 , and the chemical instability of (CH) x and its conductive derivatives in the ambient atmosphere and at elevated temperatures. Fabricating films or coatings of (CH) x , after the acetylene has been polymerized, is nearly impossible due to the insolubility of (CH) x and its inability to be molded by heat-pressing techniques. Consequently, fabrication of (CH) x would be necessary in situ, as the acetylene is polymerized. Polyacetylene is also unstable with respect to air oxidation before doping and becomes even more unstable after doping. The chemical degradation of the conductive (CH) x in air or at elevated temperatures is accompanied by a decrease in the electrical conductivity of these materials. Hence, long-term stability of the electrical properties in these systems is difficult to achieve.
Carr et al. in U.S. Pat. No. 4,160,760 disclose a method for interacting Prussian blue with polyacrylonitrile to produce a polymer with enhanced color fastness and electrical properties. While the primary focus of the Carr et al. reference appears to be obtaining a polymer which exhibits a homogeneous color, Carr et al. note that "enhanced . . . conductivity" may also occur. No reason for this speculation and no conductivity measurements or tests were reported, however. It should also be noted that Carr et al. deals exclusively with uncondensed polyacrylonitrile.
For potential applications of conductive organic polymers, it is desirable to develop polymeric systems exhibiting favorable fabrication, solubility, environmental and stability characteristics in addition to electronic structures conducive to the formation of conductive charge transfer complexes with electron acceptors.
It is an object of the present invention to develop a polymer system which exhibits conductivity in the range of semiconductors (from about 10 -10 to about 10 2 (Ω-cm) -1 ). It is a further object of this invention to develop a conductive polymer possessing semiconductor properties as well as favorable environmental properties. It is another object of this invention to develop a conductive polymer having favorable environmental properties which can be readily fabricated and processed. It is another object of this invention to develop a conductive polymer system possessing favorable stability and solubility characteristics. It is a further object of this invention to develop a method for fabricating such a polymer system.
SUMMARY OF THE INVENTION
In general, the objects of this invention are achieved by a composition comprising a doped solid resinous acrylonitrile polymer wherein said polymer is selected from the group consisting of at least one condensed polyacrylonitrile and dehydrohalogenated polyalphahaloacrylonitrile and said polymer is doped with at least one reagent capable of forming charge transfer complexes with said acrylonitrile polymer selected from the group consisting of electron donors and electron acceptors.
The composition of this invention exhibits conductivities in the range of semiconductors and advantageous environmental qualities. Thin films can be readily fabricated and processed with compositions of the present invention which remain quite stable and can be easily handled.
For purposes hereof, it is to be understood that condensation of a polymer in accord with the present invention can be effected in two ways. First, in the simplest case, the condensation process comprises condensing or conjugating a plurality of pendant cyano-groups in a polyacrylonitrile polymer to form a conjugated carbon-nitrogen "ladder" polymer which possesses linear, substantially uncrosslinked chains of fused aliphatic rings. A simple example of such a condensation of polyacrylonitrile has been represented by Mark, "Polymeric Conductors and Semiconductors," Israel Journal of Chemistry, 10, 1972, 407, 413, as ##STR1## wherein Δ represents the condensation or conjugation process. Second, in cases wherein the starting material is a polyalphahaloacrylonitrile, the term "condensation" is understood to include dehydrohalogenation of polyalphahaloacrylonitrile, which can be schematically represented as ##STR2## wherein R 2 is the halo substituent.
In a first aspect, the present invention comprises a resinous polymer of an acrylonitrile comprising a plurality of condensed pendant cyano-groups forming a conjugated carbon-nitrogen chain, and a plurality of charge-transfer complexes formed between said polymer and a suitable doping reagent capable of either donating or accepting an electron.
In another aspect, the present invention comprises a solid resinous polymer of a dehydrohalogenated polyalphahaloacrylonitrile comprising a carbon-carbon conjugated backbone and a plurality of charge-transfer complexes formed between said polymer and a suitable doping reagent capable of either donating or accepting an electron.
In the simplest embodiment of the present invention, the starting material prior to condensation and doping is unsubstituted polyacrylonitrile (PAN) which can be represented as ##STR3##
In another embodiment, substituted derivatives of PAN, such as polyalphahaloacrylonitrile (preferably chloro or bromo) and polymethacrylonitrile, can be condensed and doped within the meaning of the present invention to yield materials which display increased electrical conductivities relative to those of the uncondensed and undoped polymers.
From these starting materials, polymers possessing enhanced electrical properties can be made by the process comprising doping a condensed solid resinous acrylonitrile polymer with a dopant capable of forming charge-transfer complexes with said condensed polymer at a temperature above about ambient but below the decomposition temperature of said polymer (for example, about 300° C.).
The essential step in the process of this invention involves contacting the condensed polymer with at least one electron donor or electron acceptor doping reagent capable of forming charge transfer complexes with the polymer. As the formation of charge-transfer complexes with electron acceptors and donors effectively oxidizes or reduces the polymer, suitable reagents in accord with the present invention include conventional oxidants and reductants, such as Lewis acids and Lewis bases, respectively. Among these, Lewis acids such as iodine, bromine and AsF 5 , and Lewis bases, such as alkali metal alloys and sodium naphthalide in tetrahydrofuran are preferred. For oxidants, it is believed that the dopants remain in the polymer matrix after charge transfer as, for example, I n - or AsF 6 - anions. For reductants, charge-transfer results in the inclusion of cations, for example, alkali metal cations, in the polymer matrix.
While it has been suggested that condensation of an acrylonitrile polymer alone may result in an increase in conductivity, we have found that such enhancement is very slight. In addition, Carr et al. has separately noted that halogen treatment of uncondensed polyacrylonitrile may enhance the electrical properties of the polymer. There is no appreciation in Carr et al., however, that halogen treatment of condensed polyacrylonitrile polymers results in compositions of this invention. A key feature of the present invention is the surprising and novel discovery that the combination of condensation and doping results in dramatic increases in the conductivity of acrylonitrile polymers of this invention substantially greater than that which can be attributed to the combined individual effects of condensation and doping.
Generally, the condensation of the polymer backbone is induced thermally and, in most cases, is accompanied by an intense coloration of the polymer films. The heat-treated films are then contacted with a suitable dopant, preferably halogen vapors at ambient or elevated temperatures, for varying lengths of time. The electrical properties of the films are a function of the doping parameters (temperature and length of exposure) and can be optimized by routine experimentation.
DETAILED DESCRIPTION
There are two essential aspects of the chemical modification process to attain increased conductivities in both substituted and unsubstituted acrylonitrile polymers. The first is condensation, or the formation of a conjugated carbon-carbon or carbon-nitrogen backbone in at least a portion of the polymer; the second is the treatment of the conjugated system with electron acceptors, (preferably iodine or bromine) or electron donors (preferably sodium naphthalide) to form an electrically conductive material.
For simplicity and clarity, the ensuing general discussion will refer to unsubstituted polyacrylonitrile (PAN), although it should be understood that, except where noted, the general features discussed below apply equally well to polymers formed from substituted derivatives of acrylonitrile.
The PAN starting material can be either obtained commercially in powder form from any one of a variety of commercial suppliers of PAN, or the polymer can be made simply by bulk polymerizing the acrylonitrile monomer using an initiator such as 2,2'-azo bis (isobutyronitrile). The powder is then purified by washing with hexane or toluene.
It should be understood that the steps of fabrication (e.g., processing into a film) condensation and doping can be performed in any order. Care need only be taken to ensure that fabrication or processing after doping and condensation does not result in degradation of the condensed chains of the polymer. Moreover, condensation and doping can, for example, be accomplished simultaneously with the fabrication step. For simplicity, however, the discussion herein will address doping and condensation after a film has been made.
To form a film, a viscous solution of the polymer is prepared in a polar solvent such as dimethylformamide (DMF). Films of the acrylonitrile polymers are then solvent-cast onto glass slides and the solvent is allowed to evaporate. To effect condensation, the clear, colorless PAN films are heated to about 200° C., yielding translucent deep reddish-brown films of condensed polyacrylonitrile (ΔPAN). Very flexible films are obtained in this manner. Alternatively, powdered PAN is heated at about 200° C. under pressure; translucent, reddish-brown ΔPAN films are obtained with greater thicknesses than those prepared via solution casting. Condensation can be performed under a variety of atmospheres: air, nitrogen, and vacuum have proven to be suitable.
As noted previously, suitable dopants in accord with the present invention can be either electron acceptors or electron donors capable of forming charge-transfer complexes with the polymers. If electron acceptors are used, it is believed that electron density is removed from the outer π-orbitals of the polymer constituents and transferred to the outer orbitals of the acceptors. It should be noted that such charge-transfer phenomena involve a migration of electron density which is both critical to effect conductivity enhancement and distinct from covalent bond formation.
Suitable electron-acceptor dopants comprise conventional oxidants, such as Lewis acids. Suitable Lewis acids for use in accord with the present invention include bromine, iodine, chlorine, IBr, ICl, AsF 5 , HBr, BF 3 , BCl 3 , SO 2 , SO 3 , and transition metal complexes. Lewis acids such as bromine or iodine are generally preferred due to the fact that they are normally in a liquid or gaseous state and are thereby easier to handle. Suitable electron-donor dopants comprise conventional reductants such as Lewis bases, including Na, K, Ba, Li, Ca, Mg and Al.
It appears, however, that both electron-acceptor and electron-donor dopants are capable of achieving roughly the same degree of conductivity enhancement. Accordingly, the choice of dopant in any particular application may be dictated by availability or ease of handling as opposed to any intrinsic advantage. It should also be noted that electron-donor dopants may be expected to cause smaller band gaps than electron-acceptor dopants.
The doping process itself is preferably done in gas phase. Two tungsten electrodes for resistance measurements are first attached to the sample film with either graphite or silver paint. The sample is placed in a vacuum chamber and evacuated to about 10 -6 torr. A valve is then opened to allow the free expansion of the dopant vapor into the region of the sample. Resistance measurements are then taken as the doping takes place until the dopant vapor has reached equilibrium; at this point no further uptake of dopant by the sample is expected and the maximum increase in conductivity is attained.
Specific preferred operating conditions under which the doping is carried out can be affected by the character and dimensions of the film. If only surface conductivity is desired, the dopant need only be absorbed at the surface of the film. Current paths that are through the film (i.e., front face to back face) are expected to require more extensive doping to facilitate distribution of the dopant into the interior of the film.
Substituted derivatives of an acrylonitrile polymer are also contemplated as precursors of the conductive polymers of the present invention. In general, polymers of uncondensed derivatives of an acrylonitrile polymer will have recurring acrylonitrile units with the structure ##STR4## wherein R 1 , R 2 and R 3 are independently selected from the group consisting of hydrogen, alkyl of from 1 to 6 carbon atoms, aryl, alkoxy, cyano, amino and halo. Thus, polyalphahaloacrylonitriles are examples of substituted derivatives of acrylonitrile polymers useful in this invention. Examples of such substituted derivatives include polyalphachloroacrylonitrile (PACN) wherein R 1 =Cl and R 2 =H, and polymethacylonitrile wherein R 1 =CH 3 and R 2 =H. In accord with the present invention, formation of the condensed form of a polyalphahaloacrylonitrile, such as polyalphachloroacrylonitrile (ΔPACN), by dehydrohalogenation yields a carbon-carbon conjugated polymer with recurring units of ##STR5## whereas polymerization of the nitrile substituents of polymethacrylonitrile (PMAN) results in carbon-nitrogen conjugated polymer, i.e. condensed polymethacrylonitrile (ΔPMAN), with recurring units having the structure ##STR6##
The formation of the condensed or conjugated systems (ΔPACN and ΔPMAN) from the unmodified polymers by thermal degradation has been described by Grassie et al., J. Polym. Sci., Part C, 1967, 591-599, and Nakamura et al., J. Appl. Polym. Sci., 1972, 16, 1817-1825, and is expressly incorporated herein by reference.
Analogous to unsubstituted polymers of acrylonitrile, condensation of polyalphahaloacrylonitriles is generally induced thermally and is accompanied by an intense coloration of the polymer. Heating colorless films of polyalphachloroacrylonitrile at about 100° C. to promote dehydrochlorination results in dark shiny-purple ΔPACN films. Deep red-orange films of ΔPMAN result from the condensation of the nitrile groups in PMAN at about 190° C.
As is known in the art, the rate at which thermal degradation of PMAN occurs is dependent upon the polymerization initiator used and, thus, upon the functional group impurities introduced into the polymer by the initiators. For comparison purposes, two methods found in the literature were employed for polymerizing methacrylonitrile. The first entailed the polymerization of bulk methacrylonitrile utilizing a free radical catalyst such as azobisisobutyronitrile (AIBN) under inert atmosphere. The polymerization was carried out at ambient rather than elevated temperature to avoid premature thermal degradation, which would decrease the solubility of the polymer in solvents such as dimethylformamide (DMF). Unreacted monomer was removed via vacuum distillation. The polymer was obtained as a waxy, colorless solid.
In the second approach, methacrylonitrile was polymerized at -78° C. in toluene solution with n-butyllithium (BuLi) as the initiator. The polymer was filtered from the solution as a finely divided, light yellow powder.
More detailed features of the present invention may be discerned by reference to the following specific examples.
EXAMPLE I
A thin film of polyacrylonitrile (PAN) was prepared by solution casting from a dimethylformamide (DMF) solution. The polymer was air-dried at ambient or room temperature (about 25° C.) to minimize condensation of the PAN. Tungsten wire leads were then attached to the film with conductive graphite paint. Two probe resistance measurements were taken through the wire leads using a Keithley 616 digital electrometer. The conductivity (σ) was then calculated.
σ(PAN)=2.8×10.sup.-13 (Ωcm).sup.-1
The film was then treated with bromine vapor at a pressure corresponding to the equilibrium pressure at about 25° C. and the conductivity determined.
σ(PAN-Br.sub.2)=5.1×10.sup.-13 (Ω-cm).sup.-1
Thus, bromination of uncondensed PAN results in a slight increase in conductivity (about double) but still results in a material best classified as an insulator.
EXAMPLE II
Two samples of condensed polyacrylonitrile (ΔPAN) were prepared (one by heating a solvent cast film, one by pressure treatment) by heating at about 200° C. for over 3 hours and the conductivity of both samples of undoped ΔPAN was determined.
σ(ΔPAN)<10.sup.-10 (Ω-cm).sup.-1
Thus, it appears that condensation alone accounts for an increase in conductivity of approximately three orders of magnitude. Such conductivity would place ΔPAN as a marginal semiconductor.
EXAMPLE III
"Brominated" ΔPAN was prepared by exposing ΔPAN to bromine gas at a pressure corresponding to the equilibrium pressure at ambient temperature. Equilibrium was attained after 10 minutes. The conductivity of the resulting material was determined.
σ(ΔPAN-Br.sub.2)=10.sup.-2 (Ω-cm).sup.-1
Thermoelectric power measurements demonstrated that the ΔPAN-Br 2 was a p-type semiconductor. Bromination of additional samples demonstrated that the electrical conductivity of ΔPAN-Br 2 can be varied over 8 orders of magnitude by variation of the Br 2 vapor pressure.
EXAMPLE IV
"Iodinated" ΔPAN was prepared by exposing ΔPAN to the equilibrium vapor pressure of iodine at ambient. After 30 minutes, equilibrium was reached and the conductivity determined.
σ(ΔPAN-I.sub.2)=10.sup.-3 (Ω-cm).sup.-1
Thermoelectric power measurements demonstrated that the ΔPAN-I 2 was a p-type semiconductor.
EXAMPLE V
A ΔPAN sample was placed in a solution of sodium, naphthalene and tetrahydrofuran for 16 hours with no evidence of an increase in conductivity. A ΔPAN-Br 2 sample was then prepared as in Example III. When Br vapor was pumped away, the conductivity of the sample reverted to less than 10 -10 (Ω-cm) -1 . The sample was then placed in a solution of sodium, naphthalene and tetrahydrofuran for 30 minutes and the conductivity of the resulting ΔPAN-Na polymer was determined.
σ(ΔPAN-Na)=10.sup.-3 (Ω-cm).sup.-1
Thermoelectric power measurements demonstrated that the ΔPAN-Na was an n-type semiconductor.
EXAMPLE VI
ΔPAN-Br 2 was prepared as in Example III. A device comprising a layer of ΔPAN-Br 2 sandwiched between aluminum and gold electrodes showed diode characteristics which would be characteristic of a Schottky-type barrier between the aluminum and the ΔPAN-Br 2 .
EXAMPLE VII
In a nitrogen atmosphere, films of PMAN prepared by both methods described above were cast from DMF solution, dried at ambient temperature, and thermally degraded at about 190° C. for 24 hours. The resulting ΔPMAN films were translucent, deep red, and rather brittle. Above 220° C., depolymerization of PMAN to the monomer occurs. Deep red films of ΔPMAN can also be prepared by heating the yellow PMAN powder at 190° C. under pressure for 30 minutes. The films of AIBN- and BuLi-initiated ΔPMAN were exposed to the equilibrium vapor pressure of I 2 for 1-5 days at ambient and elevated temperatures and in ambient and dry nitrogen atmospheres. The various conditions for the ΔPMAN iodinations, together with the respective electrical conductivities exhibited by the samples initially after iodination, are summarized in Table 1.
TABLE 1______________________________________ Length of Temp. of Atmosphere Conduc-Polymer Iodination Iodination During tivityInitiator (days) (°C.) Iodination σ(Ω-cm).sup.-1______________________________________AIBN (untreated ΔPMAN) 10.sup.-12AIBN 1 ambient ambient 10.sup.-10AIBN 1 90° C. ambient 2 × 10.sup.-4AIBN 1 110° C. dry N.sub.2 1 × 10.sup.-5AIBN 2 110° C. ambient 2 × 10.sup.-7AIBN 1 110° C. dry N.sub.2 2 × 10.sup.-6AIBN 2 110° C. dry N.sub.2 5 × 10.sup.-6AIBN 3 110° C. dry N.sub.2 2 × 10.sup.-6AIBN 4 110° C. dry N.sub.2 2 × 10.sup.-6AIBN 5 110° C. dry N.sub.2 1 × 10.sup.-4BuLi 1 110° C. dry N.sub.2 2 × 10.sup.-5BuLi 1 90° C. dry N.sub.2 1 × 10.sup.-6______________________________________
Treatment of Various ΔPMAN Samples with I 2 Vapor
When iodination of ΔPMAN was performed at ambient temperature, little iodine was incorporated into the films, and no color change in the films was observed. An increase of two orders of magnitude in electrical conductivity from 10 -12 to 10 -10 (Ω-cm) -1 was observed upon iodination of ΔPMAN at ambient temperature. In contrast, exposure of ΔPAN to iodine vapor at ambient (Example IV) resulted in a much greater increase in conductivity (7 orders of magnitude from 10 -10 to 10 -3 (Ω-cm) -1 ).
Iodination of ΔPMAN at elevated temperatures (90°-110° C.) in ambient or dry nitrogen atmosphere resulted in greater conductivity increases and in greater iodine incorporation into the films relative to the samples treated at ambient temperature. These iodinated films were opaque and quite dark in color. However, a firm correlation between length of iodination and resulting conductivity is not apparent from the data. It should be noted that the highest conductivity observed for an iodinated ΔPMAN sample (10 -4 (Ω-cm) -1 ) is still lower than that reported for iodinated ΔPAN. Whether the lower conductivity for iodinated ΔPAN is due to a lower degree of C-N conjugation in ΔPMAN vs. ΔPAN is not certain. Substituted acetylene polymers (such as polyphenylacetylenes) also exhibit much lower conductivities than unsubstituted polyacetylene when halogenated. Steric effects, due to substituent groups, influence the electronic structure of acetylene polymers. Similar effects may also be present in PMAN and ΔPMAN.
After treatment with I 2 at 110° C., ΔPMAN films were found to be unstable with respect to halogen loss and electrical conductivity when maintained in an iodine-deficient atmosphere--even at ambient temperature. The opaque, deeply colored films eventually became translucent and red over a period of 1-2 weeks. The electrical conductivities of such films decreased throughout this time period. Hence, the iodine stability in ΔPMAN is not greater than that in ΔPAN.
EXAMPLE VIII
ΔPMAN films prepared as in Example VII were exposed to the equilibrium vapor pressure of Br 2 at ambient. The ΔPMAN films began to decompose, became lighter in color and somewhat pliable with no observed increase in conductivity.
EXAMPLE IX
A crystal of n-type cadmium sulfide coated on one face with PMAN was thermally degraded and then iodinated. The formation of a typical p-n rectifying junction between ΔPMAN-I 2 and the n-CdS crystal was verified when the current and voltage behavior of the combination were observed to exhibit diode-like characteristics.
It is significant to note that the conductivities of ΔPAN-Br 2 (Example III) and ΔPMAN-I 2 (Example VII) are neither predictable nor expected from the combined effects of condensation and bromination. In particular, bromination alone appears to account for only a doubling in the conductivity of PAN (Example I). Condensation alone results in ΔPAN having a conductivity about three orders of magnitude greater than PAN (Example II). Condensation followed by bromination results in an increase in conductivity of about 10 11 relative to PAN. Thus, successive condensation and bromination increases the conductivity of PAN by about 10 8 more than would be expected from their individual effects. Analogous observations also apply to ΔPMAN-I 2 .
EXAMPLE X
Polyalphachloroacrylonitrile (PACN) was made by polymerizing alphachloroacrylonitrile monomer using AIBN as an initiator. A colorless film of PACN was cast from DMF solution and dried at room temperature under nitrogen. ΔPACN was made by heating the film to effect dehydrochloronation. After 3 days of heating approximately 70% of theoretical HCl was lost from the ΔPACN film and the film became a deep, glossy purple color. The conductivity of undoped ΔPACN was determined
σ(ΔPACN)=10.sup.-12 (Ω-cm).sup.-1
The ΔPACN film was exposed to the equilibrium vapor pressure of Br 2 at ambient and the conductivity determined.
σ(ΔPACN-Br.sub.2)=10.sup.-6 (Ω-cm).sup.-1
The conductivity was observed to decrease if the sample was not maintained in a bromine saturated atmosphere.
EXAMPLE XI
A film of ΔPACN prepared as in Example X was exposed to the equilibrium vapor pressure of I 2 at ambient and the conductivity determined.
σ(ΔPACN-I.sub.2)=10.sup.-12 (Ω-cm).sup.-1
The same film was maintained in an iodine atmosphere for 2 days at ambient with no change in conductivity and no evidence of iodine uptake.
The ΔPACN was then exposed to the equilibrium vapor pressure of I 2 at 100° C. for two days with no change in conductivity or evidence of iodine uptake. The reason for the failure to dope ΔPACN with iodine is not yet understood.
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Disclosed is a composition comprising a doped solid resinous acrylonitrile polymer wherein said acrylonitrile polymer is selected from the group consisting of at least one condensed polyacrylonitrile and dehydrohalogenated polyalphahaloacrylonitrile and said polymer is doped with at least one reagent capable of forming charge-transfer complexes with said acrylonitrile polymer selected from the group consisting of Lewis acids and Lewis bases. Also disclosed are films of said polymer and a process for making said composition.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the priority of U.S. Provisional Appl. Ser. No. 61/630,345, filed Dec. 9, 2011, the entire disclosure of which is incorporated herein by reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH
[0002] This invention was made with Government support under Grant Nos. 2007-35203-18274 and 2011-67015-20025 from the USDA National Institute of Food and Agriculture (USDA-NIFA). The Government has certain rights in the invention.
FIELD OF THE INVENTION
[0003] The present invention relates to a composition and method of use for artificial insemination. More specifically, the invention relates to a sperm-stimulating additive to be employed in artificial insemination of farm animals and in vitro fertilization and embryo culture in human infertility clinics.
BACKGROUND OF THE INVENTION
[0004] Artificial insemination (AI) is a common technique in swine and cattle farming. Freshly ejaculated boar semen must be stored in extender solution for preservation at 15-18° C. or 4-5° C., and bull semen has to be extended prior to cryopreservation and storage in liquid nitrogen. Various types of extender solutions and compounds have been developed to reduce the metabolic activity of sperm and allow for extended preservation. However, new and improved culture media and/or sperm extenders are needed to improve artificial insemination in animals and in vitro fertilization and embryo culture in humans.
SUMMARY OF THE INVENTION
[0005] In one aspect, the invention provides a sperm preservation media comprising inorganic pyrophosphate (PPi). In one embodiment, the concentration of PPi is between about 1 μM and about 200 μM. In another embodiment, concentration of PPi is between about 1 μM and about 20 μM. In another embodiment, the concentration of PPi is about 10 μM. In still another embodiment, the preservation media is used to preserve sperm from a porcine.
[0006] In another aspect, the invention provides a media for sperm transfer comprising inorganic pyrophosphate (PPi). In one embodiment, the concentration of PPi is between about 1 μM and about 200 μM. In another embodiment, the concentration of PPi is between about 1 μM and about 20 μM.
[0007] Another aspect of the invention provides a media for in vitro fertilization (IVF) or artificial insemination (AI) comprising inorganic pyrophosphate (PPi). In one embodiment, the concentration of PPi is between about 1 μM and about 200 μM. In another embodiment, the concentration of PPi is between about 1 μM and about 20 μM.
[0008] In another aspect, the invention provides a semen sexing method, comprising: (a) separating a mixed sperm suspension in a first culture medium into a population of x-bearing or y-bearing sperm with the aid of an elutant medium; (b) preserving the x-bearing or y-bearing sperm in a second culture medium, wherein, inorganic pyrophosphate (PPi) is added to the first culture medium, the elutant medium or the second culture medium.
[0009] In still another aspect, the invention provides a method of sperm preservation comprising storing sperm in a media comprising inorganic pyrophosphate (PPi). In one embodiment, the concentration of PPi is between about 1 μM to about 200 μM. In other embodiments, the concentration of PPi is between about 1 μM to about 20 μM or the concentration of PPi is about 10 μM. In still another embodiment, the sperm is stored in the media comprising PPi for up to 10 days.
[0010] Another aspect of the invention provides a method of in vitro fertilization (IVF) comprising contacting an oocyte with sperm in the precence of inorganic pyrophosphate (PPi). In one embodiment, the concentration of PPi is between about 1 μM to about 200 μM. In another embodiment, the concentration of PPi is between about 1 μM to about 20 μM. In another embodiment, the sperm is stored in the precence of PPi.
[0011] In another aspect, the invention provides a method of culturing an embryo comprising culturing an embryo in a media comprising inorganic pyrophosphate.
[0012] In still another aspect, the invention provides a method of artificial insemination comprising providing sperm and inorganic pyrophosphate (PPi) to the reproductive tract of a female. In an embodiment, the PPi is gradually released into the reproductive tract of the female.
[0013] Another aspect of the invention provides a method of maturing an oocyte in vitro comprising culturing the oocyte in a media comprising inorganic pyrophosphate.
BRIEF DESCRIPTION OF DRAWINGS
[0014] FIG. 1 : Shows measurement of pyrophosphate (PPi) content by fluorometric assay. (A) Fluorescence intensity of PPi standards (final conc. 0-200 μM PPi). (B) PPi assay with boar seminal plasma (SP), porcine oviductal fluids (pOVF), rabbit sera, mouse sera (final conc. 10 μg/ml), boar spermatozoa (1×10 6 spermatozoa/ml) and 10 mM H 2 O 2 working solution (negative control). The fluorescence intensities were measured at multiple time points to follow the reaction kinetics (Excitation 530 nm; emission 590 nm). Experiments were repeated three times. Values are expressed as the mean of fluorescence intensity.
[0015] FIG. 2 : Shows generation of PPi. PPi is produced by the hydrolysis of ATP into AMP in cells. Inorganic pyrophosphatase (PPA1) catalyzes the hydrolysis of PPi to form 2 orthophosphates (2Pi), resulting in energy release.
[0016] FIG. 3 : Shows detection of inorganic pyrophosphatase (PPA1) by western blotting. Boar seminal plasma (SP; 20 μg/ml), porcine oviductal fluid (pOVF; 100 μg/ml), and boar, bull, mouse, and human spermatozoa (all at 1×10 6 spermatozoa/ml) were extracted to perform the protein analysis. Equal protein loads were used. Distinct band at ˜32 kDa was detected by rabbit polyclonal anti-PPA1 antibody. The purified PPA1 (extreme right lane; 1 μg/ml; Sigma 11643) from S. cerevisiae was used as a control protein.
[0017] FIG. 4 : Shows localization of inorganic pyrophosphatase (PPA1; red) in spermatozoa by immunofluorescence. (A, B) Whole-mount immunofluorescence of boar spermatozoa. Most prominent labeling is observed in the sperm tail connecting piece and in the postacrosomal sheath of the sperm head. (C) Identical labeling was observed in spermatozoa attached to oocyte zona pellucida at 30 min after gamete mixing during IVF. (D) Negative control with anti-PPA1 antibody immunosaturated with full-length PPA1 protein. DNA was counterstained with DAPI (blue). Epifluorescence micrographs were overlapped with parfocal transmitted light photographs acquired with DIC optics.
[0018] FIG. 5 : Shows sperm viability and mitochondrial membrane potential during sperm storage with/without PPi. (A) Percentages of viable spermatozoa based SYBR14 (live sperm) and PI (dead sperm) labeling. (B) Percentages of spermatozoa with polarized (live), depolarizing (dying) and depolarized (dead) mitochondrial membranes. Experiments were repeated three times. Values are expressed as the mean percentages±SEM. Different superscripts a & b in each group of columns denote a significant difference at p<0.05.
[0019] FIG. 6 : Shows the effect of PPi on proteasomal enzymatic activities of stored boar spermatozoa. Fresh boar spermatozoa were stored in BTS with and without 10 μM PPi for 3 or 10 days (No treat/PPi+BTS). Proteasomal proteolytic and deubiquitinating activities were measured using specific fluorometric substrates Z-LLE-AMC (A), Z-LLVY-AMC (B), Z-LLL-AMC (C) and ubiquitin-AMC (D). In a separate treatment, PPi was added before measurement to spermatozoa preserved without PPi (Add PPi). As a negative control, 10 μM MG132 (a proteasomal inhibitor) was added to “No treat” and “PPi+BTS” spermatozoa on day 3. Experiments were repeated three times. Values are expressed as the mean of fluorescence intensity.
[0020] FIG. 7 : Shows the effect of PPi on total and polyspermic fertilization during porcine IVF. Values are expressed as the mean percentages±SEM. □ % monospermic and ▪ % polyspermic oocytes. Different superscripts a-c in each group of columns denote a significant difference at p<0.05. Numbers of inseminated ova are indicated in parentheses. (A) Porcine oocytes matured in vitro were inseminated with a standard concentration of 1×10 6 spermatozoa/ml, in the presence of ascending concentrations of PPi. Experiments were repeated five times. (B) The polyspermy rates, reflective of sperm fertilizing ability in vitro (same as panel A) dramatically increased in the presence of PPi. (C) Fertilization rates of porcine oocytes inseminated with different concentrations of spermatozoa in the presence/absence of 10 μM PPi. Experiments were repeated three times. (D) Fertilization rates of oocytes inseminated with boar spermatozoa preserved for 3 days in BTS with/without 10 μM PPi. Other porcine oocytes were inseminated (sperm conc. 5×10 5 spermatozoa/ml) with and without 10 μM PPi, with spermatozoa stored with and without PPi. Experiments were repeated three times. (E) Effect of extrinsic PPA1 enzyme on porcine IVF. Oocytes were inseminated with different concentrations of purified PPA1 protein. Experiments were repeated twice. (F) Porcine oocytes were inseminated in the presence of rabbit polyclonal anti-PPA1 antibody or non-immune rabbit serum (a control of PPA1 antibody). Experiments were repeated twice.
[0021] FIG. 8 : (A) Shows the effect of PPi on sperm-zona binding. Porcine oocytes were inseminated (sperm conc. 5×10 5 spermatozoa/ml) with various concentrations of PPi for 30 min, fixed and stained with DNA stain DAPI. The numbers of spermatozoa bound per zona-pellucida (ZP) were counted under epifluorescence microscope. Values are expressed as the mean±SEM. Different superscripts a-c in each group of columns denote a significant difference at p<0.05. Numbers of inseminated ova are indicated in parentheses. (B) The percentage of acrosome-reacted spermatozoa of panel A (PNA-FITC stained). Values are expressed as the mean percentages±SEM. Different superscripts a & b in each group of columns denote a significant difference at p<0.05. (C) Effect of PPi supplementation on the viability of spermatozoa stored in commercial and custom made BTS extenders. Boar spermatozoa were preserved in BTS-IMV (IMV technologies, France) or BTS-HM (homemade) with and without 10 μM PPi for 7 days at room temperature. Sperm motilities were evaluated by observation under light microscopy at 37.5° C. Higher sperm motility was observed in BTS-IMV with PPi on day 6 than in any other group. Experiments were repeated twice. Different superscripts a, b in each group of columns denote a significant difference at p<0.05. (D) Excessive concentrations of PPi were added into IVF medium. Fertilization rates decreased with high concentrations of PPi. Experiments were repeated twice. Values are expressed as the mean percentages±SEM. □ % monospermic and ▪ % polyspermic oocytes. Numbers of inseminated ova are indicated in parentheses. (E) Effect of PPi on fertilization with spermatozoa stored in commercial extender, BTS-IMV. Nearly 100% fertilization was achieved using spermatozoa preserved in BTS-IMV with 10 μM PPi (day 3). Experiments were repeated twice. Values are expressed as the mean percentages±SEM. □ % monospermic and ▪ % polyspermic oocytes. Numbers of inseminated ova are indicated in parentheses.
DETAILED DESCRIPTION OF THE INVENTION
[0022] The present invention provides novel media and methods for sperm preservation, embryo culture, in vitro fertilization (IVF), artificial insemination (AI). In particular, the present invention represents an advance in the art in that it reports and confirms that inorganic pyrophosphate (PPi) exists in spermatozoa, seminal plasma (SP) and oviductal fluids (OVF) of mammalian species, though the previous studies have shown that the concentration of cytosolic PPi is precisely regulated in mammalian cells (Baykov et al., Prog Mol Subcell Biol 23:127-150, 1999; Sivula et al., FEBS Lett 454:75-80, 1999). In one aspect of the invention, PPi might therefore be used as an energy source for sperm viability.
[0023] In one embodiment, the present invention provides a new and improved sperm preservation media, also referred to as sperm extender that can extend semen storage period and maintain sperm viability, and thus improve AI in animals. The invention also provides a new and improved culture media for embryo transfer in animals.
[0024] In another embodiment, invention provides a new and improved method of IVF and AI as well as embryo culture media in an animal and human clinic.
[0025] In still another aspect of the invention, a new and improved method for semen sexing employing PPi is described. The present semen sexing method comprises the step of adding a certain amount of PPi in the media during a semen sexing procedure to enhance the sperm longevity and viability. For instance, according to certain embodiments of the invention, the present semen sexing method may comprise the step of adding PPi in the starting sperm processing media (with both x-and y-bearing sperm; before the conventional separation/sorting step), in the eluting media, or in the sex-separated sperm media.
[0026] Traditionally, Beltsville thawing solution (BTS) is added to frozen-thawed sperm as a thawing solution, and is also used for liquid storage for 3-5 days (Johnson et al., Zuchthygiene 23:49-55, 1988). Liquid semen extended by BTS has typically been utilized for AI due to its simple composition and developments of transportation. However, the motility of sperm preserved in extender gradually decreases during storage from natural aging, loss of ATP and cAMP, as well as reduced calcium uptake (Johnson et al., Anim Reprod Sci 62 143-172, 2000). Extended semen preserved for 5 days after collection shows a reduction in farrowing rates of approximately 50% compared to semen preserved for 2 days after collection, which shows a reduction in farrowing rates of approximately 65-70% (Johnson et al., Anim Reprod Sci 62 143-172; Johnson et al., Zuchthygiene 23:49-55, 1988; Johnson and Rath, (Eds), Proc. 2 nd Int. Conf. Deep Freezing Boar Semen. Reprod. Domest. Anim., Suppl. 1, p. 402, 1991; Rath et al., (Eds) Proc. Int. Conf. Deep Freezing of Boar Semen. Reprod. Domest. Anim. Suppl. 1. p. 342, 1996; Johnson, Proc. 15 th Int. Pig Vet. Sci. Congress 1, 225-229, 1998). Recently, Yeste et al. ( Anim Reprod Sci 108:180-195, 2008) suggested that addition of prostaglandin F 2α (PGF 2α ) to sperm diluted in BTS maintained better sperm viability and motility after 6 days of cooling.
[0027] Inorganic pyrophosphate (PPi) is a potent, mineral-binding small molecule inhibitor of crystal nucleation and growth (Fleisch et al., Nature 212:901-903, 1966), and presents in the extracellular matrix of most tissues and body fluids including plasma (Fleisch et al., Am J Physiol 203:671-675, 1962; Russell et al., J Clin Invest 50:961-969, 1971). PPi metabolism has been observed in cultured hepatocytes and chondrocytes (Davidson et al., Biochem J 254:379-384, 1988; Johnson et al., 1999; Rosen et al., Arthritis Rheum 40:1275-1281, 1997; Rosenthal et al., Calcif Tissue Int 59:128-133, 1996; Rosenthal et al., J. Rheumatol 26:395-401, 1999; Ryan et al., Arthritis Rheum 42:555-560, 1999). The intracellular PPi is generated in the mitochondria, and intra- and extracellular PPi concentrations are regulated by mitochondrial energy metabolism (Davidson et al., Biochem J 254:379-384, 1988; Johnson et al., Arthritis Rheum 43:1560-1570, 2000). In prokaryotes, PPi provides “high energy” compound, and is able to substitute for ATP in glycolysis-related reactions under attenuated respiration (Chi et al., J Biol Chem 275:35677-35679, 2000). Moreover, PPi produces a mitochondrial membrane potential with PPA (Pereira-da-Silva et al., Arch Biochem Biophys 304:310-313, 1993), and ATP-derived PPi serves as a phosphate donor in protein phosphorylation in yeast mitochondria as well as in mammalian cells (da Silva et al., Biochem Biophys Res Commun 178:1359-1364, 1991; Terkeltaub et al, Am J Physiol Cell Physiol 281:C1-C11, 2001). Consequently, PPi may be used as an energy source for viability.
[0028] Cellular PPi is yielded by various biosynthetic processes, and hydrolyzed to two inorganic phosphates (Pi) by inorganic pyrophosphatase (PPA1). PPA1 is a ubiquitous metal-dependent enzyme providing a thermodynamic pull for many biosynthetic reactions, such as DNA, RNA, protein, polysaccharide synthesis and cell life (Chen et al. 1990, Lundin et al. 1991, Sonnewald 1992, Lahti 1983, Peller 1976). The PPA1 has been detected in bacteria (Chen et al. 1990) and yeast (Lundin et al. 1991), and the soluble PPA1 was identified and characterized in Mycoplasma suis , which belongs to hemotrophic bacteria that attach to the surface of host erythrocytes (Hoelzle et al.). However, the PPi has not been used in any media related to sperm preservation or AI or IVF procedures.
[0029] The present invention identifies the PPi pathway as an important component of mammalian sperm physiology. Referring to FIG. 2 , PPi (P 2 O 7 4− ) is formed by the hydrolysis of ATP into AMP in cells, then, hydrolyzed by inorganic pyrophosphatase (PPA1) into two molecules of inorganic orthophosphate (Pi). PPA1, an important enzyme for energy metabolism (Chen et al., J Bacteriol 172:5686-5689, 1990; Lundin et al., J Biol Chem 266:12168-12172, 1991), has been implicated in the regulation of metabolism, growth and development in plants (Sonnewald, Plant J 2:571-581, 1992), and even in the development and molting in the parasitic roundworm Ascaris (Islam et al., Infect Immun 73:1995-2004, 2005). During cell division of S. cerevisiae , PPA1 is essential for mitochondria genome replication (Lundin et al., Biochim Biophys Acta 1098; 217-223, 1992).
[0030] While PPA1 is detectable in the sperm tail connecting piece, harboring sperm centriole and anchoring flagellar outer dense fibers and microtubule doublets, the invention suggests that from these locations, the PPi-metabolizing pathway may convey energy for flagellar movement and for acrosomal function during sperm-zona penetration. In addition, the invention also suggests that the PPi pathway in the sperm head and flagellum may support protein phosphorylation during sperm capacitation that is observed both in vitro and in vivo, in the oviductal sperm reservoir.
[0031] The invention further describes the ability of mammalian spermatozoa to utilize PPi as an energy source during sperm transport and sperm-egg interactions, as the spermatozoa undergo capacitation, acrosome reaction and sperm-zona penetration. It is presently disclosed that PPi can be used as a stable, inexpensive energy source to improve sperm viability during semen storage and transfer for large animal biotechnology and to enhance sperm penetration and fertilization rates enhance for assisted reproductive therapy in mammalian species (including humans). The invention further provides the addition of PPi in the culture media, the sperm extender, the IVF media, or in media employed in sperm sexing to provide beneficial effects in sperm preservation and fertilization, such as increasing sperm longevity and viability during sperm preservations and transfers and maintaining and enhancing sperm viability, penetration and fertilization rates during fertilization procedures.
[0032] Media of the present invention may therefore comprise PPi, the concentration of which may vary depending on the animal species. In certain embodiments, media of the present invention may comprise about 1 to 200 μM of PPi. In another embodiment, media of the present invention may comprise about 1 to 20 μM. The present invention may be employed for various mammals, including farm animals, such as, boar and bull.
[0033] For IVF or AI, PPi may be directly added or gradually released into the media. If needed, PPi release can be exactly controlled/modulated during AI, especially when the PPi-containing slow release gel is employed as a part of AI catheter, to gradually release PPi into the female reproductive tract.
[0034] Unless otherwise defined, 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. All publications, patent application, patents, and other references mentioned herein are incorporated by reference in their entirety.
EXAMPLES
[0035] The following disclosed embodiments are merely representative of the invention which may be embodied in various forms. Thus, specific structural, functional, and procedural details disclosed in the following examples are not to be interpreted as limiting.
Example 1
Semen Collection and Processing
[0036] Semen was collected from proven fertile adult Duroc boars 15-22 months of age under the guidance of approved Animal Care and Use Committee (ACUC) protocols of the University of Missouri-Columbia (UM-C). The boars were placed on a routine collection schedule of one collection per week. The sperm-rich fraction of ejaculate was collected into an insulated vacuum bottle. Sperm-rich fractions of ejaculates with greater than 85% motile spermatozoa were used.
[0037] Semen volumes were determined with a graduated cylinder. Sperm concentrations were estimated by a hemocytometer (Fisher Scientific, Houston, Tex.). The percentage of motile spermatozoa was estimated at 38.5° C. by light microscopy at 250× magnification. Semen was slowly cooled to room temperature (20-23° C.) by 2 h after collection and diluted with Beltsville thawing solution (BTS; 3.71 g glucose, 0.60 g trisodium citrate, 1.25 g ethylenediamine tetraacetic acid, 1.25 g sodium bicarbonate, 0.75 g potassium chloride, 0.06 g penicillin G, and 0.10 g streptomycin in 100.0 ml distilled water) (Pursel and Johnson 1975) diluent to a final concentration of 35×10 6 spermatozoa/ml in 100 ml of BTS diluent. The diluted semen was stored in Styrofoam™ boxes at room temperature for 10 days. Unless otherwise noted, all chemicals used in this study were purchased from Sigma Chemical Co. (St. Louis, Mo.).
Example 2
Collection and In vitro Maturation (IVM) of Porcine Oocyte
[0038] Ovaries were collected from prepubertal gilts at a local slaughterhouse and transported to the laboratory in a warm box (25-30° C.). Cumulus oocyte complexes (COCs) were aspirated from antral follicles (3-6 mm in diameter), washed three times in HEPES-buffered Tyrode lactate (TL-HEPES-PVA) medium containing 0.01% (w/v) polyvinyl alcohol (PVA), and then washed three times with maturation medium (Abeydeera et al., Biol Reprod 58:1316-1320, 1998). Each time, a total of 50 COCs were transferred to a 4-well multidish (Nunc, Roskilde, Denmark) containing 500 μl of maturation medium that had been covered with mineral oil and equilibrated at 38.5° C. with 5% CO 2 in the air. The medium used for oocyte maturation was tissue culture medium (TCM) 199 (Gibco, Grand Island, N.Y.) supplemented with 0.1% PVA, 3.05 mM D-glucose, 0.91 mM sodium pyruvate, 0.57 mM cysteine, 0.5 μg/ml LH (L5269, Sigma), 0.5 μg/ml FSH (F2293, Sigma), 10 ng/ml epidermal growth factor (E4127, Sigma), 10% porcine follicular fluid, 75 μg/ml penicillin G, and 50 μg/ml streptomycin. After 22 h of culture, the oocytes were washed twice and cultured in TCM199 without LH and FSH for 22 h at 38.5° C., 5% CO 2 .
Example 3
In vitro Fertilization (IVF) and Culture of Porcine Oocyte
[0039] After oocyte maturation, cumulus cells were removed with 0.1% hyaluronidase in TL-HEPES-PVA medium and washed three times with TL-HEPES-PVA medium and Tris-buffered (mTBM) medium (Abeydeera et al., Biol Reprod 58:1316-1320, 1998) containing 0.2% BSA (A7888, Sigma), respectively. Thereafter, 25-30 oocytes were placed into each of four 50 μl drops of the mTBM medium, which had been covered with mineral oil in a 35 mm polystyrene culture dish. The dishes were allowed to equilibrate in the incubator for 30 min until spermatozoa were added for fertilization. One ml of liquid semen preserved in BTS diluent was washed twice in PBS containing 0.1% PVA (PBS-PVA) at 800×g for 5 min. At the end of the washing procedure, the spermatozoa were resuspended in mTBM medium. After appropriate dilution, 50 μl of this sperm suspension was added to 50 μl of the medium that contained oocytes to give a final sperm concentrations of 1-10×10 5 spermatozoa/ml. Different concentrations of inorganic pyrophosphate (PPi; S6422, Sigma) were added to fertilization drops (final concentrations; 0-20 μM) at the time of sperm addition. Oocytes were co-incubated with spermatozoa for 6 h at 38.5° C., 5% CO 2 . At 6 h after IVF, oocytes were transferred into 100 μl NCSU23 containing 0.4% BSA (A6003, Sigma) for further culture during 16-20 h.
Example 4
Immunofluorescence and Evaluation of Fertilization Rates
[0040] Spermatozoa/oocytes were fixed in 2% formaldehyde for 40 min at room temperature, washed, permeabilized in PBS with 0.1% Triton-X-100 (PBS-TX), and blocked for 25 min in PBS-TX containing 5% normal goat serum. Spermatozoa/oocytes were incubated with rabbit polyclonal anti-pyrophosphatase 1 (PPA1) antibody (1:200 dilution; #ab96099, Abcam, San Francisco, Calif.) or rabbit polyclonal anti-ANKH antibody (1:200 dilution; #SAB1102581, Sigma) for 40 min, then incubated with goat-anti-rabbit (GAR)-IgG-TRITC (1/80 dilution; Zymed Inc., San Francisco, Calif.). For the evaluation of fertilization, oocytes/zygotes were fixed with 2% formaldehyde for 40 min at room temperature, washed three times with PBS, permeabilized with PBS-TX for 40 min at room temperature, and stained with 2.5 μg/ml DAPI (Molecular Probes, Eugene, Oreg.) for 40 min. Oocytes with two or more pronuclei and at least one sperm tail in the ooplasm were recorded as fertilized. In order to count the number of spermatozoa bound to zona pellucida or acrosome reacted spermatozoa, oocyte were fixed and stained with DAPI and acrosome-binding lectin PNA-FITC (Molecular Probes) after IVF 30 min (5×10 5 spermatozoa/ml). Image acquisition was performed on a Nikon Eclipse 800 microscope (Nikon Instruments Inc., Melville, N.Y.) with Cool Snap camera (Roper Scientific, Tucson, Ariz.) and MetaMorph software (Universal Imaging Corp., Downington, Pa.).
[0041] As shown in FIG. 4 , immunofluorescence detected a prominent labeling of PPA1 in the sperm tail connecting piece and in the postacrosomal sheath of boar spermatozoa. Identical labeling was found in spermatozoa attached to oocyte zona pellucida at 30 min of in vitro fertilization, while negative control with anti-PPA1 antibody immunosaturated with full length recombinant PPA1 protein showed no such fluorescence, and neither did labeling of non-permeabilized spermatozoa.
Example 5
Western Blotting and Immunofluorescence
[0042] For western blotting, extracts of 1×10 6 spermatozoa/ml were loaded per lane. Spermatozoa were washed in PBS and boiled with loading buffer (50 mM Tris [pH 6.8], 150 mM NaCl, 2% SDS, 20% glycerol, 5% β-mercaptoethanol, 0.02% bromophenol blue). Gel electrophoresis was performed on 4-20% gradient gels (PAGEr® Precast gels, Lonza Rockland Inc., Rockland, Me.), followed by transfer to PVDF membranes (Millipore) using an Owl wet transfer system (Fisher Scientific) at a constant 50 V for 4 h. The membranes were sequentially incubated with 10% non-fat milk for 1 h, then with anti-PPA1 or anti-ANKH antibodies (1:2,000 dilution) overnight. The membranes were then incubated with an HRP-conjugated goat anti-rabbit IgG (GAR-IgG-HRP; 1:10,000 dilution) for 1 h. The membranes were reacted with chemiluminiscent substrate (SuperSignal, Pierce, Rockford, Ill.) and visualized by exposing to Kodak BioMax Light film (Kodak, Rochester, N.Y.).
[0043] PPA1 was detected in mammalian seminal plasma, oviductal fluid and spermatozoa. As shown in FIG. 3 , a protein band corresponding to the calculated mass of PPA1 (32 kDa) was detected in boar seminal plasma, in porcine oviductal fluid, and in boar, bull, mouse and human spermatozoa by Western blotting with rabbit polyclonal anti-PPA1 antibody. Minor bands of higher (˜51 and 75 kDa) or lower mass (˜13 kDa in boar and ˜18 kDa in bull) were observed in each sperm sample, likely corresponding to posttranslational protein modification and degradation products of PPA1. The purified PPA1 from baker's yeast ( S. cerevisiae ), used as a positive control protein, also showed additional bands at 32 and 13 kDa.
Example 6
Pyrophosphate Assay
[0044] The measurement of pyrophosphate (PPi) was performed using PiPer™ Pyrophosphate Assay Kit (Cat. No. P22062, Molecular Probes), following manufacturer's protocol. The samples were prepared using 1× reaction buffer (Kit) with boar seminal plasma (SP), porcine oviductal fluids (OVF), rabbit sera, mouse sera (final conc. 10 μg/ml), boar spermatozoa (1×10 6 spermatozoa/ml) and 10 mM H 2 O 2 working solution (a negative control). The PPi standard was prepared by diluting the 50 mM PPi standard solution (final conc. 0-200 μM PPi). The working solution of 100 μM Amplex® Red reagent contains 0.02 U/ml inorganic pyrophosphatase (PPA1), 4 U/ml maltose phosphorylase, 0.4 mM maltose, 2 U/ml glucose oxidase and 0.4 U/ml HRP. In this reaction, PPA1 hydrolyzes PPi into two inorganic phosphates (Pi). In the presence of Pi, maltose phosphorylase converts maltose to glucose 1-phosphate and glucose. Glucose oxidase then converts glucose to gluconolactone and H 2 O 2 . In the presence of horseradish peroxidase (HRP), the H 2 O 2 reacts with the Amplex®Red reagent (10-acetyl-3,7-dihyroxyphenoxazine) to generate resorufin, which is detected by fluorescence. Fifty μl samples were loaded into black 96-well (Coster-Corning, Corning, N.Y.), and then 50 μl working solutions were added into sample, respectively. The 96-well was incubated at 37.5° C. for 30 min, and fluorescence was measured at multiple time points to follow the kinetics of the reaction. Fluorescence intensity was measured by Thermo Fluoroskan Ascent (ThermoFisher Scientific) using 530 nm excitation and 590 nm emission wavelengths.
[0045] Results for measurement of the content of PPi in boar SP, pOVF and boar spermatozoa by a fluorometric assay are shown in FIGS. 1A and 1B . Different concentrations of PPi were measured as standards (0-200 μM PPi), and the fluorescence intensities increased progressively with increasing concentrations of PPi ( FIG. 1A ). The fluorescence intensities also increased in pOVF, SP, spermatozoa, mouse sera and rabbit sera. As shown in FIG. 1B , the boar spermatozoa, mouse sera, and rabbit sera showed higher fluorescence intensities than SP or pOVF at 40 min of acquisition (98.2-101.1 vs. 83.8 & 85.5). However, the intensities of pOVF, mouse sera and rabbit sera decreased gradually. Only the SP and spermatozoa showed continuous increase of fluorescence intensity during measurement (fluorescence intensities: 111.5 & 117.7 at 60 min, p<0.05). A negative control, 10 mM H 2 O 2 , showed a decreasing pattern, most likely due to bleaching of fluorescence.
Example 7
Flow Cytometric Analysis of Sperm Viability and Mitochondrial Membrane Potential
[0046] Boar spermatozoa were washed twice with PBS-PVA, and sperm concentration was adjusted to 1×10 6 spermatozoa/ml in PBS-PVA. The sperm viability was assessed by LIVE/DEAD® Sperm Viability Kit (L-7011, Molecular Probes) which contains DNA dyes SYBR14 and propidium iodide (PI), following a manufacturer's protocol. Sperm samples (198 μl) were loaded onto a 96-well plate. SYBR14 (1 μl; final conc. 100 nM) and PI (1 μl; final conc. 12 μM) were added to sperm samples and incubated for 10 min at 37.5° C. in darkness. Flow cytometric analysis was performed using a Guava EasyCyte™ Plus flow cytometer (Guava Technologies, IMV Technologies, L'Aigle, France). For each sample, 5,000 events were analyzed by the Guava ExpressPro Assay program, using standard manufacturer settings. For assessment of sperm mitopotential, boar spermatozoa were stained with JC-1 (Cat. No. 4500-0250, MitoPotential Kit, IMV), and measured using manufacturer settings. For negative controls, DMSO or no staining solution was added to sperm samples.
[0047] Following an industry practice for boar semen storage, fresh boar semen was diluted in BTS extender and stored at room temperature (15-17° C.) for 10 days. The base extender is designed for short term storage (3-5 days); however, the storage period was prolonged up to 10 days to compare sperm viability and mitochondrial membrane potential between storage days 3 and 10 in the presence/absence of 10 μM PPi. As described above, sperm viability was assessed by flow cytometry using a SYBR14/PI viability kit and mitopotential was measured with JC-1 dye. Supplementation with PPi altered the histograms and scatter diagrams of fluorescence produced by the above probes a vehicle control, DMSO produced no fluorescence.
[0048] FIGS. 5A and 5B compare the sperm viabilities and mitochondrial membrane potentials during sperm storage with and without PPi. As shown in FIG. 5A , the percentage of live spermatozoa was higher on day 3 than on day 10 (p<0.05), but there was no significant difference between control spermatozoa and those supplemented with 10 μM PPi. Contrary to viability, PPi supplementation augmented the content of metabolically active spermatozoa with polarized mitochondrial membranes on day 3 ( FIG. 5B ). Similar tendency was observed in spermatozoa preserved with 10 μM PPi for 10 days ( FIG. 5B ).
Example 8
Measurement of Proteasomal-Proteolytic Activity
[0049] The proteasomal-proteolytic and deubiquitinating activities, which are essential for fertilization, were assayed using specific fluorometric substrates Z-LLL-AMC, Z-LLVY-AMC, Z-LLE-AMC and ubiquitin-AMCs in spermatozoa stored for 3 and 10 days, with or without PPi. Alternatively, 10 μM PPi+BTS was added to semen preserved without PPi at the time of assay (“Add PPi” treatment). As a negative control, 10 μM MG132 (a proteasomal inhibitor) was added to sperm samples before assay.
[0050] Spermatozoa preserved in BTS with and without 10 μM PPi were loaded into a 96-well black plate (final sperm conc. 1×10 6 spermatozoa/ml), and incubated at 37.5° C. with Z-LLE-AMC (a specific substrate for 20S chymotrypsin-like peptidyl-glutamylpeptide hydrolyzing [PGPH] activity not sensitive to MG132; final conc. 100 μM; Enzo Life Sciences, Plymouth, Pa.), Z-LLVY-AMC (a specific substrate for 20S proteasome and other chymotrypsin-like proteases, as well as calpains; final conc. 100 μM; Enzo), Z-LLL-AMC (a specific substrate for 20S chymotrypsin-like activity sensitive to proteasomal inhibitor MG132; final conc. 100 μM; BostonBiochem, Cambridge, Mass.) or ubiquitin-AMC (specific substrate for ubiquitin-C-terminal hydrolase activity; final conc. 1 μM; Enzo) for 1 h. Fluorogenic proteasomal core substrates are composed of a small peptide (LLL/LLE/LLVY) coupled to a fluorescent probe, aminomethylcoumarin (AMC). The intact AMC-coupled substrate does not emit fluorescence. In the presence of appropriate 20S core activity, the AMC molecule is cleaved off and becomes fluorescent. This emitted fluorescence was measured every 10 min for a period of 1 h, yielding a curve of relative fluorescence (no units). Fluorescence intensity was measured by Thermo Fluoroskan Ascent (Thermo Scientific), using a 380 nm excitation and 460 nm emission.
[0051] FIGS. 6A to 6D show the effects of PPi on proteasomal enzymatic activities of stored boar spermatozoa. As shown in FIG. 6A , higher chymotrypsin-like PGPH activity (Z-LLE-AMC substrate) was measured in Add PPi treatment on day 3 (relative fluorescence of 392.1; no units) and PPi+BTS on day 10 (relative fluorescence of 388), compared to other treatments (363.1-386.1; p<0.05). As shown in FIG. 6B , chymotrypsin-like proteasomal core activity (Z-LLVY-AMC substrate) gradually increased during measurement in all groups, and the PPi+BTS and Add PPi treatments showed higher fluorescence intensities with this substrate, compared to controls (110.8-121.5 vs. 85.7; p<0.05). The highest fluorescence intensity was observed in Add PPi at 10 min, but the intensity decreased progressively during measurement, and chymotrypsin-like activity showed no differences between treatments ( FIG. 6C ). On the contrary, a higher deubiquitinating activity (ubiquitin-AMC) was observed in PPi+BTS treatment on day 10, compared to other treatments (relative fluorescence of 138.9 vs. 98.4-122.7; FIG. 6D ). As anticipated, low chymotrypsin-like activity was detected in spermatozoa treated with proteasomal inhibitor MG132. Overall, supplementation with PPi increased the proteasomal-proteolytic and deubiquitinating activities in spermatozoa and showed beneficial effects during sperm preservation.
Example 9
PPi Enhances Sperm-Zona Penetration during Fertilization and Fertilizing Ability Following Extended Storage
[0052] FIGS. 7A to 7F and FIGS. 8A to 8E illustrate the effects of PPi on total and polyspermic fertilization during porcine IVF ( FIGS. 7A to 7F ), and the effects of PPi on sperm-zona binding ( FIGS. 8A to 8E ). Porcine oocytes were fertilized in the presence of PPi at different concentrations ( FIG. 7A ). The rates of total and polyspermic fertilization increased significantly and progressively (up to 10 μM PPi) with increasing concentrations of PPi (p<0.05). The highest polyspermy was observed after addition of 10 μM PPi (84.9% polyspermy; FIG. 7B ). The mean number of spermatozoa bound to ZP decreased slightly, but not significantly with increasing concentrations of PPi ( FIG. 8A ). However, the percentage of acrosome-reacted spermatozoa was significantly higher in the presence of 20 μM PPi than 0-15 μM PPi (p<0.05, FIG. 8B ). Since a reduction of an insemination dose is desirable in AI settings, porcine oocytes were also inseminated with reduced sperm concentrations with and without 10 μM PPi. Consistently, the percentage of total and polyspermic fertilization was augmented by PPi at 1, 2, and 5×10 5 spermatozoa/ml; the increase induced by PPi was statistically significant at 5×10 5 spermatozoa/ml concentration ( FIG. 7C ). To determine if sperm storage in PPi-supplemented BTS extender has a beneficial effect on sperm fertilizing ability, freshly ejaculated boar spermatozoa were stored in BTS with or without 10 μM PPi for 3-4 days, and used for IVF in the presence or absence of 10 μM PPi. The fertilization rates were higher, and the polyspermy was highest of all treatments with addition of PPi during IVF, in the absence of PPi in TBM ( FIG. 7D ; second column). However, the highest combined (mono+polyspermic) fertilization rate was observed with spermatozoa preserved with 10 μM PPi in BTS when used for IVF without PPi addition ( FIG. 7D ; third column), or with PPi in IVF medium ( FIG. 7D ; fourth column). Altogether, PPi showed statistically significant (p<0.05), beneficial effects on sperm preservation and sperm fertilizing ability.
[0053] Control experiments were conducted to deplete sperm PPi with extrinsic inorganic pyrophosphatase in the form of purified PPA1. To incapacitate sperm-borne PPA1, porcine oocytes were fertilized in the presence of anti-PPA 1 antibody. The specificity of both reagents was established by western blotting (see FIG. 3 ). Both PPA and anti-PPA1 antibody decreased the fertilization rate in a dose-dependent manner ( FIGS. 7E & F). No significant differences in fertilization rates were observed when the anti-PPA1 antibody was replaced with normal serum during fertilization ( FIG. 7F ).
[0054] To assess possible variation between sperm storage media, boar sperm batches were preserved in commercial BTS (BTS-IMV, IMV Technologies, L'Aigle, France) or homemade BTS (BTS-HM) (Pursel et al., J Anim Sci 40:99-102, 1975) in the presence of 10 μM PPi for 7 days. Higher sperm motility was found in BTS-IMV+10 μM PPi on day 6 than in all other groups ( FIG. 8C ). Excess PPi added into IVF medium (100-500 μM PPi) decreased fertilization rates in a dose-dependent manner ( FIG. 8D ). In a separate trial, boar spermatozoa were stored in BTS-IMV with 10 μM PPi for 3 days, and used for IVF. Near 100% fertilization was observed with spermatozoa preserved with 10 μM PPi, compared to below 70% fertilization without PPi in BTS-IMV ( FIG. 8E ).
Example 10
Statistical Analysis
[0055] Analyses of variance (ANOVA) were carried out using the SAS package in a completely randomized design. Duncan's multiple range test was used to compare values of individual treatment when the F-value was significant (p<0.05).
[0056] While the invention has been described in connection with specific embodiments thereof, it will be understood that the inventive device is capable of further modifications. This patent application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains and as may be applied to the essential features herein before set forth.
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The present invention provides a new and improved sperm stimulating additive comprising a certain amount of inorganic pyrophosphate (PPi). Addition of PPi in the media for human/animal in vitro fertilization (IVF) improves fertilization rate; addition of PPi in the semen extender for farm animal artificial insemination (AI) may improve pregnancy rates; furthermore, mamalian oocytes matured in vitro in a medium including PPi attain improved fertilization and developmental potential, while embryos cultured in medium supplemented with PPi have improved development to blastocyst.
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RELATED APPLICATION
[0001] This application claims the benefit of and priority to U.S. Provisional Patent Application No. 62/022,289, filed Jul. 9, 2014, the entire disclosure of which is hereby incorporated herein by reference.
TECHNICAL FIELD
[0002] In various embodiments, the present invention relates to the structure and operation of memory cells, and more particularly to memory cells being used to store more than one binary bit per memory cell.
BACKGROUND
[0003] Conventional high-capacity memory devices have been enabled by the fabrication of highly dense arrays of conductors and other memory components. In the case of memory devices, higher-capacity storage requires finer conductors and spacing between the conductors, which is typically enabled via photolithographic techniques. As the demand for higher capacity in memory devices increases, however, the need to form even finer features arises.
[0004] In an effort to reduce the cost and increase the capacity of memory devices, techniques for storing more than one binary bit in a single memory cell have been developed. The multiple bits are stored as intermediate levels within the cell. In the case of a flash memory cell, a range of voltages may be stored to represent the multiple bit states. In the case of a phase-change memory, a range of resistances may be stored to represent the multiple bit states. Similarly, capacitive memories can store a range of capacitance values. Most types of memory cell may be adapted to store multiple memory states by storing intermediate levels as appropriate for the particular storage cell technology, as known to those of skill in the art. However, one of the problems with multi-bit memory cells is that the range of levels corresponding to the various states may suffer from spreading and ultimately of overlapping levels, which can result in data loss.
[0005] In view of the foregoing, there is a need for a memory cell capable of storing two or more discrete bits of data but that enjoys the stability of a single-bit memory cell. Embodiments of the present invention fill this need by stacking two physical memory elements in a single cross-point array bit location, where each of the two stacked elements is set or reset to store information, thereby avoiding the condition where an intermediate level could drift to an adjacent state. Further embodiments allow for intermediate levels to be stored for even more bits stored at a given memory cell location.
SUMMARY
[0006] Embodiments of the present invention enable the construction of a memory element capable of storing two or more bits of information. Embodiments also enable the construction of a memory element that includes two or more elements, one of which may optionally be a threshold switch, and one or more of which may store one or more bit of information). Thus, embodiments of the present invention include any two terminal storage element formed in series with a switch element in a cross-point array, such as a diode or a threshold switch. Various embodiments of the invention also take advantage of the ability of a resistance-change material (e.g., a phase-change material) to be altered electrically to cause heating to change the element's resistance and store one of a plurality of states. Suitable phase-change materials include chalcogenides, in which the programmed resistivity may be one of two resistance values and, in the case of more than one bit per cell storage cells, in which the programmed resistivity may be one of three or more resistance values. One such chalcogenide is germanium-antimony-tellurium material (GST).
[0007] In accordance with various embodiments of the present invention, two or more memory elements are constructed in series (i.e., within a particular memory cell at a memory cell location, e.g., within an array of memory cells). Each memory element in the series of memory elements typically has a maximum current level (which may translate into a temperature due to resistive heating of the cell caused by the current) above which the state of that memory element is undefined and a minimum current (lower than the maximum current) below which the state of that memory element is fixed. When the current is above the greatest maximum current of all of the memory elements in the series of memory elements, the states of all of the memory elements in the series of memory elements are undefined (or “reset”). When the current is below the lowest minimum current of any of the memory elements in the series of memory elements, the states of all of the memory elements in the series of memory elements are fixed (or “set”). Between the maximum current and minimum current of any given memory element (i.e., the programming current range for that given memory element), the state of that memory element is changing and, in particular, when the current transitions from a current that is greater than the maximum current to a current that is less than the minimum current for a given memory element, the state of that memory element is being written; the resulting state of that memory element following that transition is a function of the specific characteristics of the current transition itself. Generally speaking, the programming current ranges of all of the memory elements in the series of memory elements are non-overlapping (a slight overlap is allowable). As a result, if the current is initially raised above the greatest maximum current of all of the memory elements in the series of memory elements (thereby putting all of the memory elements in an undefined state) and the current then is lowered to a current that is below the lowest minimum current of any of the memory elements in the series of memory elements, each of the memory elements in the series of memory elements will be written as the current transitions through the programming current range for that particular memory element. The specific characteristics of the current (e.g., ramp rate) as it transitions through the programming current range of each particular memory element determine the state of each individual memory element, respectively. For example, phase change material memory elements (e.g., chalcogenide alloys) will typically be written into different states for different rates of change of the current while passing through the programming current range; a very fast transition (such as an abrupt transition occurring in a few nanoseconds or less) will result in the corresponding memory element taking on an amorphous state having a high resistance whereas a slower transition (such as a transition taking 500 to 1000 nanoseconds and having a nearly constant rate of current change) will result in the corresponding memory element taking on a more crystalline state having a significantly lower resistance.
[0008] In an aspect, embodiments of the invention feature a method of programming a memory cell comprising (i) a first storage element comprising a first programmable material having a first melting point, and (ii) in series with the first storage element, a second storage element comprising a second programmable material having a second melting point less than the first melting point. Any or all of first, second, third, or fourth current pulses may be applied to the memory cell. The first current pulse may be applied to the memory cell to reset both the first and second storage elements. The first current pulse includes or consists essentially of (i) a first maximum current for heating the first and second storage elements above the first melting point, and (ii) a first trailing edge portion decreasing from the first maximum current sufficiently rapidly to quench each of the first and second programmable materials in a first bit state. The second current pulse may be applied to the memory cell to set both the first and second storage elements. The second current pulse includes or consists essentially of (i) a second maximum current for heating the first and second storage elements above the first melting point, and (ii) a second trailing edge portion decreasing from the second maximum current sufficiently slowly to anneal each of the first and second programmable materials in a second bit state different from the first bit state. The third current pulse may be applied to the memory cell to set the first storage element and reset the second storage element. The third current pulse includes or consists essentially of (i) a third maximum current for heating the first and second storage elements above the first melting point, (ii) a third trailing edge portion decreasing from the third maximum current to a first intermediate current sufficiently slowly to anneal the first programmable material in the second bit state, the second programmable material remaining substantially melted thereduring, and (iii) a fourth trailing edge portion decreasing from the first intermediate current sufficiently rapidly to quench the second programmable material in the first bit state. The fourth current pulse may be applied to the memory cell to reset the first storage element and set the second storage element. The fourth current pulse includes or consists essentially of (i) a fourth maximum current for heating the first and second storage elements above the first melting point, (ii) a fifth trailing edge portion decreasing from the fourth maximum current to a second intermediate current sufficiently rapidly to quench the first programmable material in the first bit state, the second programmable material remaining substantially melted thereduring, and (iii) a sixth trailing edge portion decreasing from the second intermediate current sufficiently slowly to anneal the second programmable material in the second bit state.
[0009] Embodiments of the invention may include one or more of the following in any of a variety of different combinations. The first bit state may correspond to a substantially amorphous microstructure. The second bit state may correspond to a substantially crystalline microstructure. Each of the first and second programmable materials may include or consist essentially of a chalcogenide material. The first and second programmable materials may include or consist essentially of the same material, and the geometries (e.g., cross-sectional areas) of the first and second storage elements may be different, such that the same current across both elements results in a different temperature in each element. The first and second programmable materials may include or consist essentially of different materials, and the geometries of the first and second storage elements may be substantially the same.
[0010] In another aspect, embodiments of the invention feature a memory cell including or consisting essentially of (i) a first storage element including or consisting essentially of a first programmable material having a first melting point, and (ii) in series with the first storage element, a second storage element including or consisting essentially of a second programmable material having a second melting point less than the first melting point. The memory cell is programmable via application of any or all of first, second, third, or fourth current pulses. The first current pulse may be applied to the memory cell to reset both the first and second storage elements. The first current pulse includes or consists essentially of (i) a first maximum current for heating the first and second storage elements above the first melting point, and (ii) a first trailing edge portion decreasing from the first maximum current sufficiently rapidly to quench each of the first and second programmable materials in a first bit state. The second current pulse may be applied to the memory cell to set both the first and second storage elements. The second current pulse includes or consists essentially of (i) a second maximum current for heating the first and second storage elements above the first melting point, and (ii) a second trailing edge portion decreasing from the second maximum current sufficiently slowly to anneal each of the first and second programmable materials in a second bit state different from the first bit state. The third current pulse may be applied to the memory cell to set the first storage element and reset the second storage element. The third current pulse includes or consists essentially of (i) a third maximum current for heating the first and second storage elements above the first melting point, (ii) a third trailing edge portion decreasing from the third maximum current to a first intermediate current sufficiently slowly to anneal the first programmable material in the second bit state, the second programmable material remaining substantially melted thereduring, and (iii) a fourth trailing edge portion decreasing from the first intermediate current sufficiently rapidly to quench the second programmable material in the first bit state. The fourth current pulse may be applied to the memory cell to reset the first storage element and set the second storage element. The fourth current pulse includes or consists essentially of (i) a fourth maximum current for heating the first and second storage elements above the first melting point, (ii) a fifth trailing edge portion decreasing from the fourth maximum current to a second intermediate current sufficiently rapidly to quench the first programmable material in the first bit state, the second programmable material remaining substantially melted thereduring, and (iii) a sixth trailing edge portion decreasing from the second intermediate current sufficiently slowly to anneal the second programmable material in the second bit state.
[0011] Embodiments of the invention may include one or more of the following in any of a variety of different combinations. The first bit state may correspond to a substantially amorphous microstructure. The second bit state may correspond to a substantially crystalline microstructure. Each of the first and second programmable materials may include or consist essentially of a chalcogenide material. The first and second programmable materials may include or consist essentially of the same material, and the geometries (e.g., cross-sectional areas) of the first and second storage elements may be different, such that the same current across both elements results in a different temperature in each element. The first and second programmable materials may include or consist essentially of different materials, and the geometries of the first and second storage elements may be substantially the same. The first storage element may be disposed above the second storage element. A selection device for selecting the memory cell (e.g., a diode) may be disposed below the second storage element. A third storage element may be connected in series with the first and second storage elements (e.g., at the same memory-cell location). The third storage element may include or consist essentially of a third programmable material having a third melting point different from the first and/or second melting points.
[0012] The first, second, third, and fourth maximum currents may be the same, or any of them may be different from the others, as long as the current level is sufficient to reprogram both of the first and second storage elements (e.g., by melting the material thereof). The first and second intermediate currents may be the same, or they may be different from each other, as long as the current level is (a) sufficiently high that the second programmable material (and thus the second storage element) remains unprogrammed (e.g., melted), and (b) sufficiently low that the first programmable material (and thus the first storage element) remains programmed (e.g., unmelted) below the temperature, its state being defined by the speed at which the current (and thus, in various embodiments, the temperature) in the first storage element changed when decreasing to the temperature. As used herein, a temperature or current change (e.g., a trailing edge of a current pulse) that is “sufficiently rapid” to quench a programmable material into a first bit state is rapid enough to “lock in” the melted or amorphous microstructure of the material by not allowing the atoms of the material sufficient time to realign in a crystalline state. A temperature or current change (e.g., a trailing edge portion of a current pulse) that is “sufficiently slow” to anneal a programmable material into a second bit state is slow enough to allow such atomic realignment from a melted or amorphous state into a crystalline state. As known to those of skill in the art, the requisite speed of such current and/or temperature changes is dependent at least in part on, e.g., the geometry of the storage element and the melting point (and even other materials-specific properties) of a particular programmable material. Nevertheless, the rates of such current and/or temperature changes may be determined without undue experimentation by, for example, a series of controlled current and/or temperature applications to a particular storage element followed by measurements of the resulting electrical resistance exhibited by the programmable material upon cooling. Materials characterization (e.g., x-ray diffraction analysis) may even be performed to determine the degree of crystallinity of a programmable material after such a current/temperature cycle.
[0013] These and other objects, along with advantages and features of the present invention herein disclosed, will become more apparent through reference to the following description, the accompanying drawings, and the claims. Furthermore, it is to be understood that the features of the various embodiments described herein are not mutually exclusive and may exist in various combinations and permutations. As used herein, the terms “approximately” and “substantially” mean±10%, and in some embodiments, ±5%. The term “consists essentially of” means excluding other materials that contribute to function, unless otherwise defined herein. Nonetheless, such other materials may be present, collectively or individually, in trace amounts.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] In the drawings, like reference characters generally refer to the same parts throughout the different views. Also, the drawings are not necessarily to scale, emphasis instead generally being placed upon illustrating the principles of the invention. In the following description, various embodiments of the present invention are described with reference to the following drawings, in which:
[0015] FIG. 1 is a schematic cross-section of a dual-bit memory element in accordance with various embodiments of the invention;
[0016] FIG. 2 is a plot of current as a function of time for resetting both bits of a dual-bit memory element in accordance with various embodiments of the invention;
[0017] FIG. 3 is a plot of current as a function of time for setting both bits of a dual-bit memory element in accordance with various embodiments of the invention;
[0018] FIG. 4 is a plot of current as a function of time for setting the upper bit and resetting the lower bit of a dual-bit memory element in accordance with various embodiments of the invention;
[0019] FIG. 5 is a plot of current as a function of time for resetting the upper bit and setting the lower bit of a dual-bit memory element in accordance with various embodiments of the invention;
[0020] FIG. 6 is a schematic cross-section of a memory cell having a single memory element and a self-aligned bottom contact in accordance with various embodiments of the invention; and
[0021] FIG. 7 is a schematic cross-section of a three-element memory cell in accordance with various embodiments of the invention.
DETAILED DESCRIPTION
[0022] Different memory element materials (R-RAM, PRAM, memristors, etc.) may be set and reset using different levels of current or voltage, and, within a particular type of memory element material, different chemical compositions will typically require different levels of current or voltage for the set and reset operations. For example, a phase-change memory element made of a chalcogenide material such as GST-172 (i.e., a chalcogenide alloy of germanium, antimony and tellurium in approximately the ratio of 1 to 7 to 2, respectively) may require a current for setting and resetting that is five to ten times greater than that required to set and reset a different chalcogenide material such as GST-433 (i.e., a chalcogenide alloy of germanium, antimony and tellurium in approximately the ratio of 4 to 3 to 3, respectively). Embodiments of the present invention advantageously exploit such differences in operating current.
[0023] Embodiments of the present invention feature the stacking of two or more physical memory elements in a single cross-point array bit location, where each of the two stacked elements is independently set or reset to store information, thus avoiding the condition where an intermediate level might drift to an adjacent memory state. FIG. 1 depicts a memory cell 100 fabricated according to embodiments of the present invention, in which different materials are utilized in each physical memory element. In the exemplary embodiment of memory cell depicted in FIG. 1 , two phase-change memory elements 110 , 120 are used to build the cell. For example, memory element 110 may include or consist essentially of a first chalcogenide material (such as GST-172), and memory element 120 may include or consist essentially of a second chalcogenide material having a operating current and/or a composition different from that of the memory element 110 .
[0024] As shown in FIG. 1 , the memory cell 100 is constructed on a surface or substrate in which a cross-point array of diode select devices 130 in a field of an insulating material 140 (which may include or consist essentially of, e.g., an oxide such as silicon dioxide) has already been constructed. The diode select devices 130 prevent “current sneak paths,” as is well known to those skilled in the art of cross-point memory arrays. (Alternatively, a threshold switch such as an ovonic threshold switch (OTS) device may be incorporated with the stacked memory elements in lieu of a diode select device 130 .) As shown, the diode select devices 130 each have a top contact including or consisting essentially of a conductive material such as tungsten (W). Above the top contact, a layer of a dielectric 150 (such as an oxide (e.g., silicon dioxide) or a nitride (such as silicon nitride)) is deposited, and openings are etched such that there is one hole on top of every memory cell aligned to the diode 130 top contact. Some misalignment (as is depicted in FIG. 1 as the imperfect registration between the diode 130 top contact and the bottom contact of the memory elements thereabove) is permissible. In various embodiments of the invention, the openings in dielectric 150 are first filled with conductive material 160 (e.g., W) and then etched back so as to leave a small amount in the bottom of the hole to facilitate a good electrical to the top contact of the diode 130 , particularly when the hole is slightly misaligned to the diode 130 (as depicted in FIG. 1 ). This approach has the additional advantage when fabricating a cross-point array that the diodes in the cross-point array are identical to any diodes formed in the periphery, thereby potentially eliminating any photo mask used to differentiate between diodes in the periphery and diodes having a stacked memory element. In embodiments of the invention utilizing an OTS device, the diode is omitted but the conductive material remains.
[0025] Once the holes are filled with the bottom conductor 160 to create a good electrical contact with the diode 130 top contact, a layer of barrier and/or adhesion material 170 (such as Ti or TiN) may be deposited and etched back (as was done to form the bottom conductor 160 for a good electrical contact) to leave a small layer over the bottom conductor 160 . This deposition and etch back sequence is repeated to fill the hole with a bottom memory-cell material 175 (e.g., a first chalcogenide material such as GST-433), an intra-element barrier material 180 (such as TiN), a top memory-cell material 185 (e.g., a second chalcogenide material such as GST 172), and a top contact 190 (such as TiN). The top contact 190 may alternately be formed by deposition and finished with a CMP step instead of an etch. From this point, a top dielectric layer may be deposited and then metal wordlines 195 formed by, for example, a copper damascene process, may be fabricated to complete the memory array. The cell 100 depicted in FIG. 1 also includes optional narrowing spacers 197 in the centers of the memory elements 110 , 120 , and these spacers 197 may be formed as detailed in U.S. Pat. No. 8,766,227, issued on Jul. 1, 2014, the entire disclosure of which is incorporated by reference herein.
[0026] In accordance with embodiments of the present invention, separately programming the memory elements 110 , 120 is accomplished by taking advantage of the different currents required to melt or anneal the two memory elements due to the difference in melting temperatures of the two elements' materials 175 , 185 . For example, a memory element 110 having a 50 nm diameter and a narrowing to about 20 nm at the neck due to a narrowing spacer (as shown in FIG. 1 ) may require a pulse of current of at least 500 μA to 800 μA with a fast trailing edge for a reset operation. The fast trailing edge is generally required to quench the heating quickly enough to trap the material (e.g., a phase-change material such as a chalcogenide) in a higher resistance, amorphous state. Setting a memory element 110 including or consisting essentially of GST-172 may be accomplished by ramping the trailing edge over an interval of about 500 nanoseconds (ns). The slow switching off of the current results in a slow reduction of heat in the cell, which anneals the memory-cell material into a lower resistance, crystalline state. This set pulse trailing edge ramp may be truncated once the amplitude reaches 10% to 20% of the initial amplitude because at this point, the annealing will typically be mostly completed. On the other hand, a similarly sized memory element including or consisting essentially of GST-433 may require a pulse of current of 90 μA with a fast trailing edge for a reset operation or a slow trailing edge for a set operation.
[0027] Other materials and pore sizes may be used in embodiments of the present invention. In general, for two or more memory elements in series, a current will be passed through all of the cells to effect melting of all of the cells (by passing a current that is selected for the cell with the highest melting temperature—the “top cell”). Melting the top cell will melt all cells substantially simultaneously. As the current is reduced, the top cell will drop below its melting point and, as the current is further reduced, this cell will attain its crystallization point. In various embodiments, a second cell of these cells in series will have a melting point that is below the crystallization point of the top cell (however, some overlap of the temperature ranges is possible). When the current is reduced to the point of reaching the melting point of this second cell, the top cell will (mostly) be done changing state and its resistance will be set. These temperature points will typically be determined by the alloys of the cell materials employed; however, they may also be determined by the geometry of the cells (e.g., one cell might have a much narrower pore opening (i.e., diameter or other lateral dimension) than the other, resulting in a higher current density; this will enable two cells that are made of the same material to melt and crystallize at different temperatures with the narrower pore cell melting and crystallizing at lower currents than the cell with the wider pore). A combination of different alloys and varying pore sizes may also be utilized. Furthermore, a threshold switch device OTS may be incorporated with the stacked memory elements, thereby eliminating the need for a diode select device for blocking sneak current paths. FIG. 7 depicts an exemplary memory cell 700 incorporating a three-element stack in which the bottom element 710 is an OTS device but could, alternatively, be a third programmable memory cell material (e.g., a GST alloy), with or without a narrowing spacer. A bottom barrier 720 (e.g., TiN) may be disposed between the bottom element 710 and the bottom contact 160 .
[0028] Once the current is reduced to the point near or below the crystallization point of the top cell, that top cell is removed from the programming function. As such, the bottom cell may actually be two cells in series, whereby one of these two cells functions as the new top cell and the other as the new second cell. This may be repeated for as many cells (as determined by their combinations of different alloys and varying pore sizes) as may be found having mostly non-overlapping melting to crystallizing temperature ranges.
[0029] FIG. 2 depicts an exemplary current pulse 200 for resetting both bits of a dual-bit memory element according to embodiments of the present invention. The high amplitude (e.g., between 500 μA and 800 μA) results in a memory cell temperature sufficient to melt the material of both storage elements 110 , 120 , and the rapid cutoff quenches both bits into their amorphous states.
[0030] FIG. 3 depicts an exemplary current pulse 300 for setting both bits of a dual-bit memory element according to embodiments of the present invention. The high amplitude (e.g., between 500 μA and 800 μA) will melt the material of both storage elements 110 , 120 . The slow ramping trailing edge will cause the upper element 110 (which may include or consist essentially of, e.g., GST-172) to be annealed into its crystalline state as the amplitude ramps through the approximately 100 μA level, whereas the lower element 120 (which may include or consist essentially of, e.g., GST-433) will still be in its melted state. As the ramp continues downward through 90 μA and down to 0 μA, the lower element 120 will then also be annealed into its crystalline state.
[0031] FIG. 4 depicts an exemplary current pulse 400 for setting the upper bit 110 and resetting the lower bit 120 of a dual-bit memory element according to embodiments of the present invention. The high initial amplitude (e.g., between 500 μA and 800 μA) will melt both storage elements 110 , 120 . The slow ramping trailing edge will cause the upper element 110 (which may include or consist essentially of, e.g., GST-172) to be annealed into its crystalline state as the amplitude ramps through the approximately 100 μA level, whereas the lower element 120 (which may include or consist essentially of, e.g., GST-433) will still be in its melted state. However, from this point, the current is quickly quenched and this rapid cutoff will quench the bottom bit 120 into its amorphous state.
[0032] FIG. 5 depicts an exemplary current pulse 500 for resetting the upper bit 110 and setting the lower bit 120 of a dual-bit memory element according to embodiments of the present invention. The high initial amplitude (e.g., between 500 μA and 800 μA) will melt both storage elements 110 , 120 . The rapidly dropping trailing edge will cause the upper element 110 (which may include or consist essentially of, e.g., GST-172) to be trapped in its amorphous state (as the pulse drops quickly to 10% to 20% of the initial value) while the lower element 120 will still be in its melted state. However, from this point, as the ramp continues downward from 90 μA and down to 0 μA, the lower element 120 will then be annealed into its crystalline state.
[0033] Memory cells having been programmed with more than a single binary bit may exhibit a typical failure mode by taking on the level of an adjacent state. This may occur because the level being stored is not stored to exactly the correct value. This may result from temperature variations, voltage fluctuations, poor circuit design or many other causes while programming. This may also result after correctly programming a cell due to the physics of the storage element; for example, phase-change storage elements tend to drift towards becoming less crystalline over time (because the atomic structure of the phase-change material spontaneously evolves towards thermodynamic equilibrium, which is the state of maximum entropy). Charged floating gates such as those in flash memory cells, even if initially programmed correctly, will occasionally lose an electron from the floating gate and, consequently, may drift in the direction of the fully discharged state. One solution to this problem is to program fewer levels in a given storage element. For example, a single middle level may be added to a cell otherwise only having a set and a reset state. Such an approach combined with the techniques described herein would result in a memory cell having three bits of storage. The programming of a middle level may be accomplished by altering the point at which the trailing edge transitions from a slow ramp to a final fast quench. Referring to FIG. 4 , if the current were quickly reduced to about 100 μA from the point in the middle of the ramping portion, the upper element would be partially annealed (i.e., to an intermediate level) while the lower bit would still be in its melted state. The bottom bit may then be likewise placed into an intermediate state by quenching the current from near the middle of its current ramp (as depicted in FIG. 5 ).
[0034] Reading of the memory cell is accomplished by applying a low voltage (typically less than 0.4 volts) and reading the current through the cell to determine the combined series resistance of the two elements. For example, a lower element 120 made of GST-433 may have a set resistance in the vicinity of 40KΩ, whereas it could have a reset resistance of about 1MΩ. An upper element 110 made of GST-172 may have a set resistance in the vicinity of 200KΩ, whereas it may have a reset resistance of about 2MΩ (to insure this different range of resistances, either element's length through the neck of the cell's hourglass shaped spacer may be increased or reduced to achieve a discernable difference in resistance values between the two elements). In this example, a resistance of 3MΩ would correspond to both bits being reset, a resistance of 2.04MΩ would correspond to the lower bit 120 being set and the upper bit 110 being reset, a resistance of 1.2MΩ would correspond to the lower bit 120 being reset and the upper bit 110 being set, and a resistance of 240KΩ would correspond to both bits being set.
[0035] The memory elements shown herein in a stacked form within a hole or cup-like opening above the diode 130 whereby the hole is filled with barrier and/or adhesion material (such as Ti or TiN but which could be an alternate material such as TaN) which is deposited into the hole and then etched back (as was done to form the bottom conductor for a good electrical contact); this leaves a small layer of this barrier material in the bottom of the hole which is self-aligned in the structure. A memory element such as GST (but could be other materials or types of information storage elements) is then deposited into the hole above the barrier and/or adhesion material. The structure may include a spacer at the bottom of the hole, the hourglass spacer described above, or no spacer. FIG. 6 depicts a single layer memory cell element 600 in which barrier and/or adhesion material 610 (which may include or consist essentially of, e.g., TiN) has been deposited below the memory element 620 (which may include or consist essentially of a phase-change material such as GST). In practice, the barrier and/or adhesion material 610 may be deposited to fill the hole, and then this barrier and/or adhesion material 610 may be etched back using a timed etch in order to leave a desired amount of the barrier and/or adhesion material 610 in the bottom of the hole. Deposition techniques for filling a high aspect ratio hole are known to those skilled in the art as are etch techniques for selectively removing one material more quickly than another. As an example of an embodiment of the present invention, the surrounding insulating material 630 is SiO 2 and the barrier and/or adhesion material 610 to be put at the bottom of the hole is TiN with a titanium salicide (Self-aligned titanium silicide (TiSi x )) layer underneath the TiN. A thin layer of thin Ti (e.g., 6 nm deposited at 680° C.) is deposited first and may be done separately using PVD sputtering at room temp, then CVD TiN (e.g., 64 nm, 680 C, precursor is titanium chloride (TiCl 4 )) which is enough to fill the hole. The deposition temperature is high enough to form the Ti salicide layer. The purpose of this salicide is to provide current spreading on the diode 130 . This makes sure the current is spread across the entire diode surface to keep the current density at any one point from becoming too great as will be well understood by those skilled in the art. The TiN has a dual purpose of providing a chemical barrier between the salicide and GST while also being a thermally resistive metal that reduces heat loss to the silicide and silicon diode.
[0036] Following the deposition of the barrier and/or adhesion and/or conductive material 610 , a titanium nitride etchback is performed by inductively coupled plasma etching using a chlorine-containing etchant gas such as Cl 2 with high selectivity to silicon dioxide. The resulting shape is a very short cylinder of TiN in the bottom of the hole without requiring the use of photolithography. Following the etchback of the barrier and/or adhesion and/or conductive material 610 , the information storage material 620 (e.g., a chalcogenide alloy such as GST) is deposited and etched back, and following this deposition and etchback of the information storage material 620 , a top contact 630 (e.g., a barrier and/or adhesion and/or conductive material such as TiN) may be formed through deposition and, typically, finished with a CMP step (or could be an etchback step).
[0037] Memory devices incorporating embodiments of the present invention may be applied to memory devices and systems for storing digital text, digital books, digital music (such as MP3 players and cellular telephones), digital audio, digital photographs (wherein one or more digital still images may be stored including sequences of digital images), digital video (such as personal entertainment devices), digital cartography (wherein one or more digital maps may be stored, such as GPS devices), and any other digital or digitized information as well as any combinations thereof.
[0038] Devices incorporating embodiments of the present invention may be embedded or removable, and may be interchangeable among other devices that can access the data therein. Embodiments of the invention may be packaged in any variety of industry-standard form factor, including compact flash, secure digital, multimedia cards, PCMCIA cards, memory stick, any of a large variety of integrated circuit packages including ball-grid arrays, dual in-line packages (DIPs), SOICs, PLCCs, TQFPs, and the like, as well as in proprietary form factors and custom designed packages. These packages may contain just the memory chip, multiple memory chips, one or more memory chips along with other logic devices or other storage devices such as PLDs, PLA's, micro-controllers, microprocessors, controller chips or chip-sets or other custom or standard circuitry.
[0039] Systems incorporating memory devices comprising embodiments of the present invention have the advantages of high density, non-volatile memory. Such systems may provide long term storage as a solid state storage device instead of or in addition to rotating media storage (e.g., magnetic disks, read only or read/write optical disks, and the like) and/or network based storage. Such systems may be in the form of a desk-top computer system, a hand-held device (such as a tablet computer or a laptop computer), a communication device (such as a cell phone, a smart phone, a portable wirelessly networked device for music, video or other purposes, or the like), and/or any other system based device having data storage.
[0040] While it is a benefit of embodiments of the present invention to provide multiple bits per memory cell whereby each storage element holds a single bit, demands for ever higher storage capacity may result in embodiments of the present invention being operated with more than one bit per storage element. This may be enabled by utilizing a given bit element set to an intermediate level. For example, referring to the upper bit setting in FIG. 4 , the slow ramping trailing edge may be rapidly dropped half way through the ramp, causing the upper element 110 to be trapped in an intermediate resistance state. From this point, as the ramp may be slowly dropped downward from 90 μA and down to 0 μA (as depicted in FIG. 5 ) or rapidly quenched (as depicted in FIG. 4 ) to program the lower element 120 , which will then be annealed into its crystalline or amorphous state, respectively. A similar approach may also be used to program the lower element into an intermediate state.
[0041] The terms and expressions employed herein are used as terms and expressions of description and not of limitation, and there is no intention, in the use of such terms and expressions, of excluding any equivalents of the features shown and described or portions thereof. In addition, having described certain embodiments of the invention, it will be apparent to those of ordinary skill in the art that other embodiments incorporating the concepts disclosed herein may be used without departing from the spirit and scope of the invention. Accordingly, the described embodiments are to be considered in all respects as only illustrative and not restrictive.
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In various embodiments, a memory cell for storing two or more bits of information includes two series-connected memory storage elements composed of programmable materials having different melting points, enabling independent programming of the storage elements via different current pulses.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is a continuation of U.S. patent application Ser. No. 13/526,672, filed 19 Jun. 2012, (issuing as U.S. Pat. No. 8,408,302 on 2 Apr. 2013), which was a continuation of U.S. patent application Ser. No. 13/286,676, filed 1 Nov. 2011 (now U.S. Pat. No. 8,201,627, issued on 19 Jun. 2012), which was a continuation of U.S. patent application Ser. No. 12/413,636, filed 30 Mar. 2009 (now U.S. Pat. No. 8,047,290, issued on 1 Nov. 2011), which was a continuation of U.S. patent application Ser. No. 11/975,131, filed 16 Oct. 2007 (now U.S. Pat. No. 7,510,007, issued on 31 Mar. 2009), which was a continuation of U.S. patent application Ser. No. 11/334,083, filed 17 Jan. 2006 (now U.S. Pat. No. 7,281,582, issued 16 Oct. 2007), which was a continuation-in-part of U.S. patent application Ser. No. 10/658,092, filed 9 Sep. 2003 (now U.S. Pat. No. 7,007,753, issued 7 Mar. 2006), which was non-provisional of U.S. provisional patent application Ser. No. 60/409,177, filed 9 Sep. 2002, all of which are incorporated herein by reference and to which priority is hereby claimed.
[0002] This is a continuation of U.S. patent application Ser. No. 13/526,672, filed 19 Jun. 2012, (issuing as U.S. Pat. No. 8,408,302 on 2 Apr. 2013), which was a continuation of U.S. patent application Ser. No. 13/286,676, filed 1 Nov. 2011 (issuing as U.S. Pat. No. 8,201,627 on 19 Jun. 2012), which was a continuation of U.S. patent application Ser. No. 12/413,636, filed 30 Mar. 2009 (now U.S. Pat. No. 8,047,290, issued on 1 Nov. 2011), which was a continuation of U.S. patent application Ser. No. 11/975,131, filed 16 Oct. 2007 (now U.S. Pat. No. 7,510,007, issued on 31 Mar. 2009), which was a continuation of U.S. patent application Ser. No. 11/334,083, filed 17 Jan. 2006 (now U.S. Pat. No. 7,281,582, issued 16 Oct. 2007), which was non-provisional of U.S. provisional patent application Ser. No. 60/644,683, filed 19 Jan. 2005, all of which are incorporated herein by reference and to which priority is hereby claimed.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0003] Not applicable
REFERENCE TO A “MICROFICHE APPENDIX”
[0004] Not applicable
BACKGROUND
[0005] In top drive rigs, the use of a top drive unit, or top drive power unit is employed to rotate drill pipe, or well string in a well bore. Top drive rigs can include spaced guide rails and a drive frame movable along the guide rails and guiding the top drive power unit. The traveling block supports the drive frame through a hook and swivel, and the driving block is used to lower or raise the drive frame along the guide rails. For rotating the drill or well string, the top drive power unit includes a motor connected by gear means with a rotatable member both of which are supported by the drive frame.
[0006] During drilling operations, when it is desired to “trip” the drill pipe or well string into or out of the well bore, the drive frame can be lowered or raised. Additionally, during servicing operations, the drill string can be moved longitudinally into or out of the well bore.
[0007] The stem of the swivel communicates with the upper end of the rotatable member of the power unit in a manner well known to those skilled in the art for supplying fluid, such as a drilling fluid or mud, through the top drive unit and into the drill or work string. The swivel allows drilling fluid to pass through and be supplied to the drill or well string connected to the lower end of the rotatable member of the top drive power unit as the drill string is rotated and/or moved up and down.
[0008] Top drive rigs also can include elevators are secured to and suspended from the frame, the elevators being employed when it is desired to lower joints of drill string into the well bore, or remove such joints from the well bore.
[0009] At various times top drive operations, beyond drilling fluid, require various substances to be pumped downhole, such as cement, chemicals, epoxy resins, or the like. In many cases it is desirable to supply such substances at the same time as the top drive unit is rotating and/or moving the drill or well string up and/or down, but bypassing the top drive's power unit so that the substances do not damage/impair the unit. Additionally, it is desirable to supply such substances without interfering with and/or intermittently stopping longitudinal and/or rotational movement by the top drive unit of the drill or well string.
[0010] A need exists for a device facilitating insertion of various substances downhole through the drill or well string, bypassing the top drive unit, while at the same time allowing the top drive unit to rotate and/or move the drill or well string.
[0011] One example includes cementing a string of well bore casing. In some casing operations it is considered good practice to rotate the string of casing when it is being cemented in the wellbore. Such rotation is believed to facilitate better cement distribution and spread inside the annular space between the casing's exterior and interior of the well bore. In such operations the top drive unit can be used to both support and continuously rotate/intermittently reciprocate the string of casing while cement is pumped down the string's interior. During this time it is desirable to by-pass the top drive unit to avoid possible damage to any of its portions or components.
[0012] The following US patent is incorporated herein by reference: U.S. Pat. No. 4,722,389.
[0013] While certain novel features of this invention shown and described below are pointed out in the annexed claims, the invention is not intended to be limited to the details specified, since a person of ordinary skill in the relevant art will understand that various omissions, modifications, substitutions and changes in the forms and details of the device illustrated and in its operation may be made without departing in any way from the spirit of the present invention. No feature of the invention is critical or essential unless it is expressly stated as being “critical” or “essential.”
BRIEF SUMMARY
[0014] The apparatus of the present invention solves the problems confronted in the art in a simple and straightforward manner. The invention herein broadly relates to an assembly having a top drive arrangement for rotating and longitudinally moving a drill or well string. In one embodiment the present invention includes a swivel apparatus, the swivel generally comprising a mandrel and a sleeve, the swivel being especially useful for top drive rigs.
[0015] The sleeve can be rotatably and sealably connected to the mandrel. The swivel can be incorporated into a drill or well string and enabling string sections both above and below the sleeve to be rotated in relation to the sleeve. Additionally, the swivel provides a flow path between the exterior of the sleeve and interior of the mandrel while the drill string is being moved in a longitudinal direction (up or down) and/or being rotated/reciprocated. The interior of the mandrel can be fluidly connected to the longitudinal bore of casing or drill string thus providing a path from the sleeve to the interior of the casing/drill string.
[0016] In one embodiment an object of the present invention is to provide a method and apparatus for servicing a well wherein a swivel is connected to and below a top drive unit for conveying pumpable substances from an external supply through the swivel for discharge into the well string, but bypassing the top drive unit.
[0017] In another embodiment of the present invention is provided a method of conducting servicing operations in a well bore, such as cementing, comprising the steps of moving a top drive unit longitudinally and/or rotationally to provide longitudinal movement and/or rotation/reciprocation in the well bore of a well string suspended from the top drive unit, rotating the drill or well string and supplying a pumpable substance to the well bore in which the drill or well string is manipulated by introducing the pumpable substance at a point below the top drive power unit and into the well string.
[0018] In other embodiments of the present invention a swivel placed below the top drive unit can be used to perform jobs such as spotting pills, squeeze work, open formation integrity work, kill jobs, fishing tool operations with high pressure pumps, sub-sea stack testing, rotation of casing during side tracking, and gravel pack or frac jobs. In still other embodiments a top drive swivel can be used in a method of pumping loss circulation material (LCM) into a well to plug/seal areas of downhole fluid loss to the formation and in high speed milling jobs using cutting tools to address down hole obstructions. In other embodiments the top drive swivel can be used with free point indicators and shot string or cord to free stuck pipe where pumpable substances are pumped downhole at the same time the downhole string/pipe/free point indicator is being rotated and/or reciprocated. In still other embodiments the top drive swivel can be used for setting hook wall packers and washing sand.
[0019] In still other embodiments the top drive swivel can be used for pumping pumpable substances downhole when repairs/servicing is being done to the top drive unit and rotation of the downhole drill string is being accomplished by the rotary table. Such use for rotation and pumping can prevent sticking/seizing of the drill string downhole. In this application safety valves, such as TIW valves, can be placed above and below the top drive swivel to enable routing of fluid flow and to ensure well control.
[0020] In an alternative embodiment the unit can include double swivel portions. In another alternative embodiment unit can include an insertion tool for inserting a plug or ball into the unit.
[0021] The drawings constitute a part of this specification and include exemplary embodiments to the invention, which may be embodied in various forms.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0022] 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:
[0023] FIG. 1 is a schematic view showing a top drive rig with one embodiment of a top drive swivel incorporated in the drill string;
[0024] FIG. 2 is a schematic view of one embodiment of a top drive swivel;
[0025] FIG. 3 is a sectional view of a mandrel which can be incorporated in the top drive swivel of FIG. 2 ;
[0026] FIG. 4 is a sectional view of a sleeve which can be incorporated into the top drive swivel of FIG. 2 ;
[0027] FIG. 5 is a right hand side view of the sleeve of FIG. 4 ;
[0028] FIG. 6 is a sectional view of the top drive swivel of FIG. 2 ;
[0029] FIG. 6A is a sectional view of the packing unit shown in FIG. 6 ;
[0030] FIG. 6B is a top view of the packing injection ring shown in FIGS. 6 and 6A ;
[0031] FIG. 6C is a side view section of the packing injection ring shown in FIG. 6B ;
[0032] FIG. 7 is a top view of a clamp which can be incorporated into the top drive swivel of FIG. 2 ;
[0033] FIG. 8 is a side view of the clamp of FIG. 7 ;
[0034] FIG. 9 is a perspective view and partial sectional view of the top drive swivel shown in FIG. 2 ;
[0035] FIG. 10 is a schematic view of an alternative embodiment of a top drive swivel having double swivel portions;
[0036] FIG. 11 is a schematic view of an alternative embodiment of a top drive swivel having double swivel portions;
[0037] FIG. 12 is a schematic view of an alternative valve wherein the valve ball holds a plug or ball;
[0038] FIG. 13 shows a tool for inserting a ball into the top drive swivel or drill string;
DETAILED DESCRIPTION
[0039] Detailed descriptions of one or more preferred embodiments are provided herein. It is to be understood, however, that the present invention may be embodied in various forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but rather as a basis for the claims and as a representative basis for teaching one skilled in the art to employ the present invention in any appropriate system, structure or manner.
[0040] FIG. 1 is a schematic view showing a top drive rig 1 with one embodiment of a top drive swivel 30 incorporated into drill string 20 . FIG. 1 is shows a rig 1 having a top drive unit 10 . Rig 5 comprises supports 16 , 17 ; crown block 2 ; traveling block 4 ; and hook 5 . Draw works 11 uses cable 12 to move up and down traveling block 4 , top drive unit 10 , and drill string 20 . Traveling block 4 supports top drive unit 10 . Top drive unit 10 supports drill string 20 .
[0041] During drilling operations, top drive unit 10 can be used to rotate drill string 20 which enters wellbore 14 . Top drive unit 10 can ride along guide rails 15 as unit 10 is moved up and down. Guide rails 15 prevent top drive unit 10 itself from rotating as top drive unit 10 rotates drill string 20 . During drilling operations drilling fluid can be supplied downhole through drilling fluid line 8 and gooseneck 6 .
[0042] At various times top drive operations, beyond drilling fluid, require substances to be pumped downhole, such as cement, chemicals, epoxy resins, or the like. In many cases it is desirable to supply such substances at the same time as top drive unit 10 is rotating and/or moving drill or well string 20 up and/or down and bypassing top drive unit 10 so that the substances do not damage/impair top drive unit 10 . Additionally, it is desirable to supply such substances without interfering with and/or intermittently stopping longitudinal and/or rotational movements of drill or well string 20 being moved/rotated by top drive unit 10 . This can be accomplished by using top drive swivel 30 .
[0043] Top drive swivel 30 can be installed between top drive unit 10 and drill string 20 . One or more joints of drill pipe 18 can be placed between top drive unit 10 and swivel 30 . Additionally, a valve can be placed between top drive swivel 30 and top drive unit 10 . Pumpable substances can be pumped through hose 31 , swivel 30 , and into the interior of drill string 20 thereby bypassing top drive unit 10 . Top drive swivel 30 is preferably sized to be connected to drill string 20 such as 4½ inch IF API drill pipe or the size of the drill pipe to which swivel 30 is connected to. However, cross-over subs can also be used between top drive swivel 30 and connections to drill string 20 .
[0044] FIG. 2 is a schematic view of one embodiment of a top drive swivel 30 . Top drive swivel 30 can be comprised of mandrel 40 and sleeve 150 . Sleeve 150 is rotatably and sealably connected to mandrel 40 . Accordingly, when mandrel 40 is rotated, sleeve 150 can remain stationary to an observer insofar as rotation is concerned. As will be discussed later inlet 200 of sleeve 150 is and remains fluidly connected to a the central longitudinal passage 90 of mandrel 40 . Accordingly, while mandrel 40 is being rotated and/or moved up and down pumpable substances can enter inlet 200 and exit central longitudinal passage 90 at lower end 60 of mandrel 40 .
[0045] FIG. 3 is a sectional view of mandrel 40 which can be incorporated in the top drive swivel 30 . Mandrel 40 is comprised of upper end 50 and lower end 60 . Central longitudinal passage 90 extends from upper end 50 through lower end 60 . Lower end 60 can include a pin connection or any other conventional connection. Upper end 50 can include box connection 70 or any other conventional connection. Mandrel 40 can in effect become a part of drill string 20 . Sleeve 150 fits over mandrel 40 and becomes rotatably and sealably connected to mandrel 40 . Mandrel 40 can include shoulder 100 to supper sleeve 150 . Mandrel 40 can include one or more radial inlet ports 140 fluidly connecting central longitudinal passage 90 to recessed area 130 . Recessed area 130 preferably forms a circumferential recess along the perimeter of mandrel 40 and between packing support areas 131 , 132 . In such manner recessed area will remain fluidly connected with radial passage 190 and inlet 200 of sleeve 150 (see FIGS. 4 , 6 ).
[0046] To reduce friction between mandrel 40 and packing units 305 , 415 ( FIG. 6 ) and increase the life expectancy of packing units 305 , 415 , packing support areas 131 , 132 can be coated and/or sprayed welded with a materials of various compositions, such as hard chrome, nickel/chrome or nickel/aluminum (95 percent nickel and 5 percent aluminum) A material which can be used for coating by spray welding is the chrome alloy TAFA 95MX Ultrahard Wire (Armacor M) manufactured by TAFA Technologies, Inc., 146 Pembroke Road, Concord N.H. TAFA 95 MX is an alloy of the following composition: Chromium 30 percent; Boron 6 percent; Manganese 3 percent; Silicon 3 percent; and Iron balance. The TAFA 95 MX can be combined with a chrome steel. Another material which can be used for coating by spray welding is TAFA BONDARC WIRE-75B manufactured by TAFA Technologies, Inc. TAFA BONDARC WIRE-75B is an alloy containing the following elements: Nickel 94 percent; Aluminum 4.6 percent; Titanium 0.6 percent; Iron 0.4 percent; Manganese 0.3 percent; Cobalt 0.2 percent; Molybdenum 0.1 percent; Copper 0.1 percent; and Chromium 0.1 percent. Another material which can be used for coating by spray welding is the nickel chrome alloy TAFALOY NICKEL-CHROME-MOLY WIRE-71T manufactured by TAFA Technologies, Inc. TAFALOY NICKEL-CHROME-MOLY WIRE-71T is an alloy containing the following elements: Nickel 61.2 percent; Chromium 22 percent; Iron 3 percent; Molybdenum 9 percent; Tantalum 3 percent; and Cobalt 1 percent. Various combinations of the above alloys can also be used for the coating/spray welding. Packing support areas 131 , 132 can also be coated by a plating method, such as electroplating. The surface of support areas 131 , 132 can be ground/polished/finished to a desired finish to reduce friction and wear between support areas 131 , 132 and packing units 305 , 415 .
[0047] FIG. 4 is a sectional view of sleeve 150 which can be incorporated into top drive swivel 30 . FIG. 5 is a right hand sectional view of sleeve 150 taken along the lines 4 - 4 . Sleeve 150 can include central longitudinal passage 180 extending from upper end 160 through lower end 170 . Sleeve 150 can also include radial passage 190 and inlet 200 . Inlet 200 can be attached by welding or any other conventional type method of fastening such as a threaded connection. If welded the connection is preferably heat treated to remove residual stresses created by the welding procedure. Also shown is protruding section 155 along with upper and lower shoulders 156 , 157 . Lubrication port 210 can be included to provide lubrication for interior bearings. Packing ports 220 , 230 can also be included to provide the option of injecting packing material into the packing units 305 , 415 (see FIG. 6 ). A protective cover 240 can be placed around packing port 230 to protect packing injector 235 (see FIG. 6 ). Optionally, a second protective cover can be placed around packing port 220 , however, it is anticipated that protection will be provided by clamp 600 and inlet 200 . Sleeve 150 can include peripheral groove 205 for attachment of clamp 600 . Additionally, key way 206 can be provided for insertion of a key 700 . FIG. 5 illustrates how central longitudinal passage 180 is fluidly connected to inlet 200 through radial passage 190 . It is preferred that welding be performed using Preferred Industries Welding Procedure number T3, 1550REV-A 4140HT (285/311 bhn) RMT to 4140 HT (285/311 bhn(RMT) It is also preferred that welds be X-ray tested, magnetic particle tested, and stress relieved.
[0048] FIG. 6 is a sectional view of the assembled top drive swivel 30 of FIG. 2 . As can be seen sleeve 150 slides over mandrel 40 . Bearings 145 , 146 rotatably connect sleeve 150 to mandrel 40 . Bearings 145 , 146 are preferably thrust bearings although many conventionally available bearing will adequately function, including conical and ball bearings. Packing units 305 , 415 sealingly connect sleeve 150 to mandrel 40 . Inlet 200 of sleeve 150 is and remains fluidly connected to central longitudinal passage 90 of mandrel 40 . Accordingly, while mandrel 40 is being rotated and/or moved up and down pumpable substances can enter inlet 200 and exit central longitudinal passage 90 at lower end 60 of mandrel 40 . Recessed area 130 and protruding section 155 form a peripheral recess between mandrel 40 and sleeve 150 . The fluid pathway from inlet 200 to outlet at lower end 60 of central longitudinal passage 90 is as follows: entering inlet 200 (arrow 201 ); passing through radial passage 190 (arrow 202 ); passing through recessed area 130 (arrow 202 ); passing through one of the plurality of radial inlet ports 140 (arrow 202 ), passing through central longitudinal passage 90 (arrow 203 ); and exiting mandrel 40 via lower end 60 at pin connection 80 (arrows 204 , 205 ).
[0049] FIG. 6A shows a blown up schematic view of packing unit 305 . Packing unit 305 can comprise packing end 320 ; packing ring 330 , packing ring 340 , packing injection ring 350 , packing end 360 , packing ring 370 , packing ring 380 , packing ring 390 , packing ring 400 , and packing end 410 . Packing unit 305 sealing connects mandrel 40 and sleeve 150 . Packing unit 305 can be encased by packing retainer nut 310 and shoulder 156 of protruding section 155 . Packing retainer nut 310 can be a ring which threadably engages sleeve 150 at threaded area 316 . Packing retainer nut 310 and shoulder 156 squeeze packing unit 305 to obtain a good seal between mandrel 40 and sleeve 150 . Set screw 315 can be used to lock packing retainer nut 310 in place and prevent retainer nut 310 from loosening during operation. Set screw 315 can be threaded into bore 314 and lock into receiving area 317 on sleeve 150 . Packing unit 415 can be constructed substantially similar to packing unit 305 . The materials for packing unit 305 and packing unit 415 can be similar.
[0050] Packing end 320 is preferably a bronze female packing end. Packing ring 330 is preferably a “Vee” packing ring—Teflon such as that supplied by CDI part number 0500700-VS-720 Carbon Reflon (having 2 percent carbon). Packing ring 340 is preferably a “Vee” packing ring—Rubber such as that supplied by CDI part number 0500700-VS-850NBR Aramid. Packing injection ring 350 is described below in the discussion regarding FIGS. 6B and 6C . Packing end 360 preferably a bronze female packing end. Packing ring 370 is preferably a “Vee” packing ring—Teflon such as that supplied by CDI part number 0500700-VS-720 Carbon Reflon (having 2 percent carbon). Packing ring 380 is preferably a “Vee” packing ring—Rubber such as that supplied by CDI part number 0500700-VS-850NBR Aramid. Packing ring 390 is preferably a “Vee” packing ring—Teflon such as that supplied by CDI part number 0500700-VS-720 Carbon Reflon (having 2 percent carbon). Packing ring 400 is preferably a “Vee” packing ring—Rubber such as that supplied by CDI part number 0500700-VS-850NBR Aramid. Packing end 410 is preferably a bronze male packing ring. Various alternative materials for packing rings can be used such as standard chevron packing rings of standard packing materials. Bronze rings preferably meet or exceed an SAE 660 standard.
[0051] A packing injection option can be provided for top drive swivel 30 . Injection fitting 225 can be used to inject additional packing material such as teflon into packing unit 305 . Head 226 for injection fitting 225 can be removed and packing material can then be inserting into fitting 225 . Head 226 can then be screwed back into injection fitting 225 which would push packing material through fitting 225 and into packing port 220 . The material would then be pushed into packing ring 350 . Packing ring 350 can comprise radial port 352 and transverse port 351 . The material would proceed through radial port 352 and exit through transverse port 351 . The material would tend to push out and squeeze packing rings 340 , 330 , 320 and packing rings 360 , 370 , 380 , 390 , 400 tending to create a better seal between packing unit 305 with mandrel 40 and sleeve 150 . The interaction between injection fitting 235 and packing unit 415 can be substantially similar to the interaction between injection fitting 225 and packing unit 305 . A conventionally available material which can be used for packing injection fittings 225 , 235 is DESCO™ 625 Pak part number 6242-12 in the form of a 1 inch by ⅜ inch stick and distributed by Chemola Division of South Coast Products, Inc., Houston, Tex. In FIG. 6 , injection fitting 235 is shown ninety degrees out of phase and, is preferably located as shown in FIG. 9 .
[0052] Injection fittings 225 , 235 have a dual purpose: (a) provide an operator a visual indication whether there has been any leakage past either packing units 305 , 415 and (b) allow the operator to easily inject additional packing material and stop seal leakage without removing top drive swivel 30 from drill string 20 .
[0053] FIGS. 6B and 6C shows top and side views of packing injection ring 350 . Packing injection ring 350 includes a male end 355 at its top and a flat end 356 at its rear. Ring 350 includes peripheral groove 353 around its perimeter. Optionally, ring 350 can include interior groove along its interior. A plurality of transverse ports 351 , 351 ′, 351 ″, 351 ′, etc. extending from male end 355 to flat end 356 can be included and can be evenly spaced along the circumference of ring 350 . A plurality of radial ports 352 , 352 ′, 352 ″, 352 ′″, etc. can be included extending from peripheral groove 353 and respectively intersecting transverse ports 351 , 351 ′, 351 ″, 351 ′″, etc. Preferably, the radial ports can extend from peripheral groove 353 through interior groove 354 .
[0054] Retainer nut 800 can be used to maintain sleeve 150 on mandrel 40 . Retainer nut 800 can threadably engage mandrel 40 at threaded area 801 . Set screw 890 can be used to lock in place retainer nut 800 and prevent nut 800 from loosening during operation. Set screw 890 threadably engages retainer nut 800 through bore 900 and sets in one of a plurality of receiving portions 910 formed in mandrel 40 . Retaining nut 800 can also include grease injection fitting 880 for lubricating bearing 145 . Wiper ring 271 set in area 270 protects against dirt and other items from entering between the sleeve 150 and mandrel 40 . Grease ring 291 set in area 290 holds in lubricant for bearing 145 .
[0055] Bearing 146 can be lubricated through grease injection fitting 211 and lubrication port 210 . Bearing 145 can be lubricated through grease injection fitting 881 and lubrication port 880 .
[0056] FIG. 7 is a top view of clamp 600 which can be incorporated into top drive swivel 30 . FIG. 8 is a side view of clamp 600 . Clamp 600 comprises first portion 610 and second portion 620 . First and second portions 610 , 620 can be removably attached by fasteners 670 , 680 . Clamp 600 fits in groove 205 / 605 of sleeve 150 ( FIG. 6 ). Key 700 can be included in keyway 690 . A corresponding keyway 691 is included in sleeve 150 of top drive swivel 30 . Keyways 690 , 691 and key 700 prevent clamp 600 from rotating relative to sleeve 150 . A second key 720 can be installed in keyways 710 , 711 . Shackles 650 , 660 can be attached to clamp 600 to facilitate handing top drive swivel 30 when clamp 600 is attached. Torque arms 630 , 640 can be included to allow attachment of clamp 600 (and sleeve 150 ) to a stationary part of top drive rig 1 and prevent sleeve 150 from rotating while drill string 20 is being rotated by top drive 10 (and top drive swivel 30 is installed in drill string 20 ). Torque arms 630 , 640 are provided with holes for attaching restraining shackles. Restrained torque arms 630 , 640 prevent sleeve 150 from rotating while mandrel 40 is being spun. Otherwise, frictional forces between packing units 305 , 415 and packing support areas 131 , 135 of rotating mandrel 40 would tend to also rotate sleeve 150 . Clamp 600 is preferably fabricated from 4140 heat treated steel being machined to fit around sleeve 150 .
[0057] FIG. 9 is an overall perspective view (and partial sectional view) of top drive swivel 30 . Sleeve 150 is shown rotatably connected to mandrel 40 . Bearings 145 , 146 allow sleeve 150 to rotate in relation to mandrel 40 . Packing units 305 , 415 sealingly connect sleeve 150 to mandrel 40 . Retaining nut 800 retains sleeve 150 on mandrel 40 . Inlet 200 of sleeve 150 is fluidly connected to central longitudinal passage 90 of mandrel 40 . Accordingly, while mandrel 40 is being rotated and/or moved up and down pumpable substances can enter inlet 200 and exit central longitudinal passage 90 at lower end 60 of mandrel 40 . Recessed area 130 and protruding section 155 form a peripheral recess between mandrel 40 and sleeve 150 . The fluid pathway from inlet 200 to outlet at lower end 60 of central longitudinal passage 90 is as follows: entering inlet 200 ; passing through radial passage 190 ; passing through recessed area 130 ; passing through one of the plurality of radial inlet ports 40 ; passing through central longitudinal passage 90 ; and exiting mandrel 40 through central longitudinal passage 90 at lower end 60 and pin connection 80 . In FIG. 9 , injection fitting 225 is shown ninety degrees out of phase and, for protection, is preferably located between inlet 200 and clamp 600 .
[0058] Mandrel 40 takes substantially all of the structural load from drill string 20 . The overall length of mandrel 40 is preferably 52 and 5/16 inches. Mandrel 40 can be machined from a single continuous piece of heat treated steel bar stock. NC50 is preferably the API Tool Joint Designation for the box connection 70 and pin connection 80 . Such tool joint designation is equivalent to and interchangeable with 4½ inch IF (Internally Flush), 5 inch XH (Extra Hole) and 5½ inch DSL (Double Stream Line) connections. Additionally, it is preferred that the box connection 70 and pin connection 80 meet the requirements of API specifications 7 and 7G for new rotary shouldered tool joint connections having 6⅝ inch outer diameter and a 2¾ inch inner diameter. The Strength and Design Formulas of API 7G-Appendix A provides the following load carrying specification for mandrel 40 of top drive swivel 30 : (a) 1,477 kpounds tensile load at the minimum yield stress; (b) 62,000 foot-pounds torsion load at the minimum torsional yield stress; and (c) 37,200 foot-pounds recommended minimum make up torque. Mandrel 40 can be machined from 4340 heat treated bar stock.
[0059] Sleeve 150 is preferably fabricated from 4140 heat treated round mechanical tubing having the following properties: (120,000 psi minimum tensile strength, 100,000 psi minimum yield strength, and 285/311 Brinell Hardness Range). The external diameter of sleeve 150 is preferably about 11 inches. Sleeve 150 preferably resists high internal pressures of fluid passing through inlet 200 . Preferably top drive swivel 30 with sleeve 150 will withstand a hydrostatic pressure test of 12,500 psi. At this pressure the stress induced in sleeve 150 is preferably only about 24.8 percent of its material's yield strength. At a preferable working pressure of 7,500 psi, there is preferably a 6.7:1 structural safety factor for sleeve 150 .
[0060] To minimize flow restrictions through top drive swivel 30 , large open areas are preferred. Preferably each area of interest throughout top drive swivel 30 is larger than the inlet service port area 200 . Inlet 200 is preferably 3 inches having a flow area of 4.19 square inches. The flow area of the annular space between sleeve 150 and mandrel 40 is preferably 20.81 square inches. The flow area through the plurality of radial inlet ports 140 is preferably 7.36 square inches. The flow area through central longitudinal bore 90 is preferably 5.94 square inches.
[0061] FIG. 10 is a schematic view of an alternative embodiment of a top drive swivel 1000 having double swivel portions 1030 , 2030 and intermediate valve 1006 . Each swivel portion 1030 , 2030 can be constructed similar to top drive swivel 30 . Similar to top drive swivel 30 shown in FIG. 1 , top drive swivel 1000 can be connected to top drive unit 10 and drill string 20 . Valve 1006 can be a full opening ball valve. One or more additional valves can be included between swivel portions 1030 , 2030 .
[0062] Stabilizing bracket 1005 can be used to stabilize swivels 1030 and 2030 (and sleeves 1050 and 2050 ). Stabilizing bracket can include arm 1010 which can be connected rigidly, slidingly, or otherwise to rig 1 (shown in FIG. 1 ) or some other fixed member for constraining or restricting movement of sleeves 1050 and 2050 . A sliding connection of arm 1010 allows top drive unit 1 to move drill string 20 up and down at the same time top drive unit 1 rotates drill string 20 . A rigid connection would restrict up and down movement (but not rotation) of drill string 20 . Connecting stabilizing bracket 1010 to rig 1 is preferred to address the tendency of frictional forces (occurring between mandrels 1040 and 2040 and sleeves 1050 and 2050 ) causing sleeves 1050 and 2050 to rotate when mandrels 1040 and 2040 rotate.
[0063] Rotation of top drive unit 1 can cause rotation of swivel mandrel 1040 as shown by arrow 1001 . Rotation of swivel mandrel 1040 in the direction of arrow 1001 causes rotation of valve member 1006 as shown by arrow 1002 . Rotation of valve member 1006 in the direction of arrow 1002 causes rotation of swivel mandrel 2040 as shown by arrow 1003 . Rotation of swivel mandrel 2040 in the direction 1003 causes rotation of drill string 20 . Rotation of top drive unit in the opposite direction as that described above will cause rotation of mandrel 1040 , valve member 1006 , and mandrel in the opposite direction of arrows 1001 , 1002 , and 1003 .
[0064] Line 1300 can be used for fluids or other items which are to be pumped into either or both of swivels 1030 , 2030 . Line 1300 can comprise manifold 1009 , lines 1301 , 1302 along with valve members 1007 and 1008 . Valve members 1007 and 1008 can be any conventionally available valves such as ball or gate valves and can be manually or automatically operated. Valve member 1007 can control flow to/from swivel 1030 . Valve member 1008 can control flow to/from swivel 2030 . Valve member 1006 can control flow between mandrel 1040 and mandrel 2040 . Control valve 2000 can be included in line 1300 to control flow to/from line 1300 .
[0065] With valve 1006 closed (and valves 1007 , 1008 open) fluids can be pumped from top drive unit 10 , into swivel 2050 , into line 1301 , through open valve 1007 , through manifold 1009 , through open valve 1008 , into mandrel 2040 , through lower portion of mandrel 2041 , and into drill string 20 . Control valve 2000 is typically closed for this flow circuit. This flow circuit allows valve 1006 to be circumvented when valve 1006 is closed. During this time period mandrels 1040 , 2040 can be rotated by top drive 10 while sleeves 1050 , 2050 remain stationary.
[0066] A double swivel construction provides the flexibility of allowing an operator to divert the flow of fluids from line 1300 to swivel 1030 or to swivel 2030 (or to both swivel 1030 and swivel 2030 ) while drill string 20 is worked without having to break down drill string 20 or stop operations of top drive unit 10 . For example during cementing operations top drive swivel 1000 can be used to pump cement into drill string 20 which can then be used to cement casing in well bore 14 . With valve 1006 open (and valve 1008 closed) cement can be pumped from line 1300 , through open valve 2000 , through open valve 1007 , into line 1301 , into and into swivel 1050 and mandrel 1040 , through lower portion of mandrel 1041 , through open valve 1006 , into mandrel 2040 , through lower portion of mandrel 2040 , and into drill string 20 . If a plug or ball 2005 (shown in FIG. 11 ) had been placed above valve 1006 , then the pumped cement would be separated from downstream fluid by plug or ball 2005 . With valve 1008 open (and valve 1006 closed), cement can be pumped from line 1300 through open valve 2000 , through open valve 1008 , and into swivel 2050 and mandrel 2040 , through lower portion of mandrel 2041 , and into drill string 20 . With valves 1006 , 1007 , and 1008 , cement can be pumped from line 1300 through open valve 2000 and into both swivels 1030 , 2030 .
[0067] FIG. 11 is a schematic view of an alternative embodiment of a top drive swivel 1000 ′ having double swivel portions. In this embodiment, a valve 2001 is placed between top drive unit 10 and swivel 1000 ′. Valves 1007 , 1008 are placed immediately adjacent swivels 1030 , 2030 . Valve 2001 will prevent any fluid being pumped into swivels 1030 , 2030 from entering top drive unit 10 . Valve 2001 will also prevent any fluid from top drive unit 10 from entering top drive swivel 1000 ′. Shown in FIG. 11 is plug or ball 2005 which can be used to clean the inside of drill string 20 or to separate two sets of fluids being pumped into drill string 20 (e.g., drilling/completion fluid versus cement). Preferably plug or ball 2005 is a 5½ inch rubber ball for 4½ inch IF drill string 20 . Different sized balls can be used for different size drill or work strings 20 . Additionally conventionally available plugs can also be used.
[0068] In another alternative embodiment, valve 2001 can be placed above valve 1006 and between swivels 1050 , 2050 . Plug or ball 2005 can be placed between valves 2001 , 1006 . In this embodiment valves 2001 , 1006 hold plug or ball 2005 until it is to be dropped into drill string 20 . Plug or ball 2005 is dropped by opening valves 2001 , 1006 . Fluid being pumped through mandrel 1040 will force plug or ball 2005 to drop into drill string 20 .
[0069] FIG. 12 shows another embodiment where valve 1006 is a ball valve and plug or ball 2005 is inserted into the through bore 1006 B of valve ball 1006 A of valve 1006 . Valve 1006 is constructed such that through bore 1006 B can accommodate plug or ball 2005 when valve 1006 A is completely in the closed position. In the closed position valve ball 1006 A will trap plug or ball 2005 , but in the open position fluid pressure (schematically illustrated by arrow 1004 ) will force plug or ball 2005 out of valve 1006 and into drill string 20 .
[0070] FIG. 13 shows a tool 2010 for inserting plug or ball 2005 into position in top drive swivel 1000 or valve 1006 . Tool 2010 can comprise three sections: upper section 2011 , middle section 2013 , and lower section 2012 . Upper section 2011 can include a connection for pumping fluid. Upper section 2011 can be removably connected to middle section 2013 by a threaded section 2014 . Middle section 2013 can include an enlarged inner diameter section 2015 and a narrowing diameter section 2016 . Middle section 2013 can also include an o-ring seal 2014 . Lower section 2012 can include threaded section 2018 and an o-ring seal 2019 .
[0071] To insert plug or ball into valve 1006 of top drive swivel 1000 shown in FIG. 10 , lower section 2012 can be threaded into the upper portion of mandrel 1040 . Valve 1006 should be partially closed to prevent plug or ball 2005 from passing. Plug or ball 2005 is inserted into enlarged inner diameter section 2015 of tool 2010 . Upper section 2011 is threaded into enlarged diameter section. A pipe or hose is connected to upper section 2011 and pressurized fluid is pumped through upper section 2011 in the direction of arrow 2020 . The pressurized fluid will force plug or ball 2005 through narrowing section 2016 and out through lower section 2012 and into mandrel 1040 . Plug or ball 2005 will continue downward until stopped by valve 1006 . At this point fluid pressure is cut off and tool 2010 is removed. Valve 1006 is complete closed and top drive swivel 1000 is installed in drill string 20 . When plug or ball 2005 is to be dropped into drill string 20 , valve 1006 is opened and fluid is pumped through mandrel 1040 in the in the direction of arrow 2021 .
[0072] The following will illustrate various methods for using swivels 30 , 1000 .
Swivel Tool 30 and Swiveling Ball Drop Assembly 1000
[0073] There are many advantages that will lead to successful operations and a reduction in rig time when utilizing Swivel Tool 30 and Swiveling Ball Drop Manifold Assemblies 1000 .
[0074] Cement Plugs set in open hole or in casing can be better distributed along the cement column, especially in directionally drilled wells, as pipe 18 , 20 rotation can be applied while pumping the plugs in place. Swivel Tool 30 will perform efficiently, either in setting a Balanced Plug or using a Plug Catcher.
[0075] When displacing a hole 14 to a reduced mud weight where a high differential pressure may be encountered, the bit can be run to Total Depth and hole 14 displaced in a single step procedure, saving time as to staging in the hole 14 . The pipe 20 can be rotated while the hole 14 is being displaced, which will lead to less contamination of the interface between fluids being displaced and less debris remaining in the hole 14 .
[0076] When the Well 14 is perforated underbalance with a Tubing Conveyed Perforate assembly, the Manifold 1000 assembly can be utilized. A Wireline can be rigged up above the Manifold 1000 and a Correlation Log run, the Tubing Conveyed Perforate moved to be put on depth, lines rigged up and tested, Tubing Conveyed Perforate Packer set, By-Pass 1007 opened, the desired underbalance pumped, By-Pass 1007 closed and the Tubing Conveyed Perforate fired and flow back achieved, By-Pass 1007 opened and the influx reversed out. If the primary detonation of the Tubing Conveyed Perforate is a bar drop, the Full Opening Ball Valve 1006 would be ideal for this purpose.
[0077] The Swivel Manifold 1000 , with the 4½″ IF connections can easily be spaced out with in a stand of drill pipe and stored on the derrick before and after the operation of choice has been performed and easily applied to the Top Drive system 10 .
[0078] The outside torque applied to the Swivel Tool assemblies 1050 , 2050 is a minimum torque value when the pipe 18 , 20 is rotated, however, a Stiff-Arm 1010 assembly can be easily attached and utilized.
[0079] The Swiveling Ball Drop Manifold 1000 can be equipped with 3 inch Low Torque Valves 1007 , 1008 leading to less restriction when pumping fluid through at higher volumes, if desired.
Open Hole Cement Plug Swivel Tool 30 Only
[0080] (1) Pick up Ported Mule Shoe Sub that has been orange peeled in with a round tapered bottom with one-half inch circular port at the bottom of sub with added one-half inch circular ports staggered on side of sub. The round tapered bottom will help keep the Mule Shoe Sub from setting down in a possible ledge or other downhole obstruction.
[0081] (2) Pick up enough Cement Stingers to cover the height of intended cement plug and 100 feet. Scratchers and Centralizers are optional.
[0082] (3) Trip in hole 14 to casing shoe.
[0083] (4) In a strand of Drill Pipe, pick up the Swivel Tool 30 (with a TIW Valve in the open position on top of the Swivel Tool and a Low Torque Valve in the closed position connected to the side-entry port 200 of the Swivel Tool 30 which is called the pump in sub) and set back on derrick 1 . Rig up Cement Lines on rig 1 floor to be ready for connection to Swivel Tool 30 , once in the hole 14 to cement depth.
[0084] (5) Continue in hole 14 to cement depth.
[0085] (6) Rig up cement lines to Swivel Tool 30 .
[0086] (7) Circulate and condition mud. Rotate the Drill Pipe 18 , 20 while circulating.
[0087] (8) Off-Line operations can be performed while circulating. Cementer can prepare the Spacers and Cement Mix water. The Pre-Job Task Meeting can also be conducted and cement lines tested.
[0088] (9) After the desired circulation time has passed, keep Drill Pipe 18 , 20 rotating, close the TIW Valve above the Swivel Tool 30 , pressure up on top of the TIW to +−1000 pounds per square inch with the Top Drive 10 and open the Low Torque Valve to inlet 200 .
[0089] (10) Pump Spacer, Cement, Spacer and displace as per Cement Program with pipe 18 , 20 rotating at all times.
[0090] (11) After cement has been spotted, rig down cement line and store Swivel Tool 30 on derrick 1 .
[0091] (12) Pull Drill Pipe 20 out of hole above top of cement. Pump Wiper Ball 2005 to Clean the Drill Pipe 20 if desired.
[0092] (13) Pull out of hole 14 .
Cement Plug Swivel Tool 1000 /Ball Launch Manifold Plug Catcher
[0093] (1) Pick up Ported Mule Shoe Sub that has been orange peeled in with a round tapered bottom with one-half inch circular port at the bottom of sub with added one-half inch circular ports staggered on side of sub. The round tapered bottom will help keep the Mule Shoe Sub from setting down in a possible ledge.
[0094] (2) Pick up enough Cement Stingers to cover the height of intended cement plug and 100 feet. Scratchers and Centralizers are optional.
[0095] (3) Pick up Plug Catcher.
[0096] (4) Place Cement Stringers in hole to casing shoe.
[0097] (5) In a stand of Drill Pipe, pick up the Swivel Tool and Ball Launch Manifold Assembly 1000 with the Full Opening Ball Valve 1006 in the closed position with proper Wiper Ball or Dart 2005 loaded above the closed Ball Valve 1006 . Place the Low Torque Valve 1008 on the Lower Swivel Pump-in Sub 2030 in open position. Place the Low Torque Valve 1007 to the Upper Swivel Pump-In Sub 1030 in the closed position. Stand the Swivel Tool and Ball Launch Manifold Assembly 1000 on the derrick 1 . Rig up Cement Lines on rig 1 floor to be ready to be connected to the Ball Launch Manifold 1000 and also where the Drill Pipe 14 can be circulated with Rig Pumps and/or from the Cement Pump with necessary valves to isolate either set of pumps.
[0098] (6) Continue in hole 14 to cement depth.
[0099] (7) Rig up cement lines to the Swivel Manifold 1000 .
[0100] (8) Circulate and condition mud with rig pumps. Rotate the Drill Pipe 18 , 20 while circulating.
[0101] (9) Off-Line Operations can be performed while circulating. Cementer can prepare the Spacers and Cement Mix water. The Pre-Job Task Meeting can also be conducted and cement lines tested.
[0102] (10) After the desired circulation time has been completed, keep the Drill Pipe 18 , 20 rotating and isolate the Rig Pumps from the Cement Pump. Set the Cement Pump to pump thru the Lower Swivel Pump-In Sub 2030 . Maintain rotation of Drill Pipe 18 , 20 .
[0103] (11) Pump the first Spacer and Cement. When pumping the second Spacer, pump the calculated volume of the Cement Stinger. Shut down the Cement Pump, close the Low Torque Valve 1008 to the Lower Swivel Pump-In Sub 2030 and open the Low Torque Valve 1007 to the Upper Swivel Pump-In Sub 1030 . Open the Full Opening Ball Valve 1006 , releasing the Wiper Ball or Dart 2005 .
[0104] (12) Displace the Cement. When the Wiper Ball or Dart 2005 lands at the Plug Catcher shut down pumping.
[0105] (13) Store the Swivel Tool and Ball Launch Manifold Assembly 1000 back on the derrick 1 .
[0106] (14) Pull Drill Pipe 20 out of hole 14 , above top of cement.
[0107] (15) Rig up pump line and shear Plug catcher to the Circulation position.
[0108] (16) Pull out of hole 14 .
Well Clean Out High Differential Displacement Floater Completion Swivel Tool Only
[0109] (1) Pick up Bit plus Scraper and Brush assembly.
[0110] (2) Trip in hole 14 , with Bit half way from Mud Line and Float Collar, pick up second Scraper/Brush assembly.
[0111] (3) Continue to Trip in hole 14 , tag Float Collar.
[0112] (4) Pick up Swivel Tool 30 (but omitting right angle inlet 200 ). Rig up high pressure pump plus rig pumps to the Swivel Tool 30 . Test lines to desired pressure.
[0113] (5) Circulate bottoms up with existing Mud System with rig pumps, rotate drill pipe 20 while circulating.
[0114] (6) Isolate the rig Pumps and test Production Casing with the high pressure pump, if not already tested.
[0115] (7) Displace the Choke, Kill and Booster lines with Seawater.
[0116] (8) Start displacing the existing Mud System with Seawater by pumping down the Drill Pipe 20 with returns up the Annulus with the High Pressure Pump. Once the Seawater has rounded the Bit and the Differential Pressure declines to a safe working pressure, switch to the Rig Pumps and finish the Displacement. (Maintain pipe 20 rotation throughout the displacement to help in removing debris from around the Tool Joints).
[0117] (9) Pull out of hole 14 until the Scraper/Brush assembly is at the Mud Line (boosting the Riser with Seawater)
[0118] (10) Trip in hole 14 , space out Dual Actuated Ball Service Tool and Riser Brush to be one stand above the Dual Actuated Ball Service Tool and the Riser Brush to be at plus or minus 30 feet above the Riser Flex Joint with the Bit at the Float Collar boost riser while Trip in hole 14 ).
[0119] (11) Rotate pipe 20 and circulate bottoms up with seawater.
[0120] (12) Drop ball and open circulating ports in the Dual Actuated Ball Service Tool.
[0121] (13) Jet wash the Well Head and Blow Out Preventers.
[0122] (14) With the Dual Actuated Ball Service Tool above the Blow Out Preventers, function the Annular and the Pipe Rams to have annular blow out preventer attach to Tool.
[0123] (15) Jet wash the Blow Out Preventers. Pull out of hole 14 jet washing the Marine Riser. Put on the side (lay out) the Riser Brush and Dual Actuated Ball Service Tool.
[0124] (16) Trip in hole 14 to the Float Collar.
[0125] (17) Rotate pipe 20 and circulate bottoms up with seawater.
[0126] (18) Align Fail Safe Valves and Choke Manifold to take returns up the Choke and Kill Lines.
[0127] (19) Pump Spacer Trains down the drill pipe 20 with returns up the Riser. When the Spacer Trains are 75 barrels from the Blow Out Preventers, close the Annular and take returns up the Choke and Kill lines. Slow the pumps if necessary, but do not shut down until the Spacer Trains are circulated from the Hole 14 .
[0128] (20) Align The Choke Manifold and Pump Riser Spacer Trains down the Choke, Kill, and Booster lines. Boost Spacer Trains from the Riser at 22 barrels per minute minimum.
[0129] (21) Displace seawater from the Choke, Kill, and Booster Lines with Filtered Completion Fluid.
[0130] (22) Displace seawater from the Hole 14 with Filtered Completion Fluid. Circulate and filter until the National Turbidity Units are at the desired level.
[0131] (23) Pull out of hole 14 .
Well Clean Out High Differential Displacement Floater Completion
[0132] (1) Pick up Bit plus Scraper and Brush assembly.
[0133] (2) Trip in hole 14 , with Bit half way from Mud Line and Float Collar, pick up second Scraper/Brush assembly.
[0134] (3) Continue Trip in hole 14 , tag Float Collar.
[0135] (4) Pick up Swivel Tool/Manifold Assembly 1000 with Full Opening Ball Valve 1006 in the closed position. Rig up high pressure pump plus rig pumps to the Manifold Assembly 1000 . Close the lower Low-Torque Valve 1008 and the upper Low-Torque Valve 1007 . Test lines and open the lower Low Torque Valve 1008 .
[0136] (5) Circulate bottoms up with existing Mud System with rig pumps, rotate Drill Pipe 18 , 20 while circulating.
[0137] (6) Isolate the rig Pumps and test Production Casing with the high pressure pump, if not already tested.
[0138] (7) Displace the Choke, Kill, and Booster lines with Seawater.
[0139] (8) Start displacing the existing Mud System with Seawater with the High Pressure Pump. Once the Seawater has rounded the Bit and the Differential Pressure declines to a safe working pressure, switch to the Rig Pumps and finish the displacement. (Maintain Drill Pipe 18 , 20 rotation throughout displacement to help in removing debris from around Tool Joints).
[0140] (9) Pull out of hole 14 until the Scraper/Brush assembly is at the Mud Line (boosting the Riser with Seawater)
[0141] (10) Trip in hole 14 , space out Dual Actuated Ball Service Tool and Riser Brush to be one stand above the Dual Actuated Ball Service Tool and the Riser Brush to be at plus or minus 30 feet above the Riser Flex Joint with the Bit at the Float Collar (boost riser while Trip in hole 14 ).
[0142] (11) Rotate Drill Pipe 18 , 20 and circulate bottoms up with seawater.
[0143] (12) Drop ball 2005 and open circulating ports in the Dual Actuated Ball Service Tool.
[0144] (13) Jet wash the Well Head and Blow Out Preventers.
[0145] (14) With the Dual Actuated Ball Service Tool above the Blow Out Preventers, function the Annular and the Pipe Rams.
[0146] (15) Jet wash the Blow Out Preventers. Pull out of hole jet washing the Marine Riser. Lay down the Riser Brush and Dual Actuated Ball Service Tool.
[0147] (16) Trip in hole 14 to the Float Collar.
[0148] (17) Rotate pipe 18 , 20 and circulate bottoms up with seawater.
[0149] (18) Align Fail Safe Valves and Choke Manifold to take returns up the Choke and Kill lines.
[0150] (19) Pump Spacer Trains down the Drill Pipe 18 , 20 with returns up the Riser. When the Spacer Trains are 75 barrels from the Blow Out Preventers, close the Annular and take returns up the Choke and Kill Lines. Slow the pumps if necessary, but do not shut down until the Spacer Trains are circulated from the Hole 14 .
[0151] (20) Align The Choke Manifold and Pump Riser Spacer Trains down the Choke, Kill, and Booster Lines. Boost Spacer Trains from the Riser at a minimum of 22 barrels per minute.
[0152] (21) Displace seawater from the Choke, Kill, and Booster lines with Filtered Completion Fluid.
[0153] (22) Displace seawater from the Hole 14 with Filtered Completion Fluid. Circulate and filter until the National Turbidity Units are at the desired level.
[0154] (23) Pull out of hole 14 .
[0000] Tubing Conveyed Perforate Operations with Swivel Tool/Ball Drop Assembly 1000 Well Status: Well Bore has been Cleaned Up; Filtered Completion Fluid is in Place; No Block Squeeze Had to be Performed; Sump Packer has been Set on Depth with Wireline; Operations can be Performed with Omni or IRIS Valve
[0155] (1) Pick up the Tubing Conveyed Perforating Bottom Hole Assembly (pressure activation as primary detonation of Tubing Conveyed Perforate Guns) plus Snap-Latch assembly. Pick up the Omni or IRIS Valve to be in the Well Test Position. Pick up a Radio Active Sub one stand above the Tubing Conveyed Perforate assembly.
[0156] (2) Trip in Hole 14 with the Tubing Conveyed Perforate assembly, limit run in speed from slip to slip at two minutes per stand (94 foot stands). Drift each stand with maximum Outer diameter Drift. Monitor hole 14 on trip tank while Trip in hole 14 for proper fluid back for pipe displacement to confirm Omni/IRIS Valve is in proper position.
[0157] (3) With Snap-Latch one stand above the Sump Packer, obtain pick-up and slack-off weights.
[0158] (4) Sting into Sump Packer. Pick up the Work String to the neutral pipe weight and mark pipe at the Rotary. Snap out, should take 10,000 k to 20,000 k to snap out. (If any doubt of being in the Sump Packer, rig up Wireline and run Gamma-Ray and Collar Log for correct correlation).
[0159] (5) Pick up Swivel Tool/Ball Drop Assembly 1000 and space out as desired to put the Swivel tool 1000 at the desired distance above the Rotary with the Snap-Latch strung into the Sump packer.
[0160] (6) Rig up Choke Manifold on the Rig 1 Floor with lines from the Swivel Tool 1000 to the Manifold and lines from the High Pressure Pump to the Manifold. Rig up lines down stream of the Choke to take returns to the trip tank and to the Mud Pits.
[0161] (7) Sting into the Sump Packer and pick up to the neutral pre-recorded pipe weight. Set the Tubing Conveyed Perforate Packer by rotating the Work String the desired number of turns and slacking off the desired pipe weight onto Tubing Conveyed Perforate packer.
[0162] (8) Open the Upper Low Torque 1007 and Full Opening Ball Valve 1006 to the Work String 20 plus Choke Manifold Valves in the open position back to the Trip Tank. Close the Annular Blow Out Preventer and test the Tubing Conveyed Perforate Packer to the Annulus side to 1,000 pounds per square inch. Monitor for returns at the Trip Tank, no returns should be observed if the Tubing Conveyed Perforate Packer is holding.
[0163] (9) Cycle the Omni Valve to the Reverse Circulating position.
[0164] (10) Break circulation by pumping down the Work String 20 with returns up the Rig Choke or Kill line.
[0165] (11) Test the Pump Lines, Choke Manifold and Swivel Tool 1000 Valve to the desired pressure. Open the top Low Torque Valve 1007 and the Full Opening Ball Valve 1006 .
[0166] (12) Displace the Work String 20 with a lighter fluid, taking returns up the Rig Choke or Kill line until the desired under balance has been achieved.
[0167] (13) Cycle the Omni Valve to the Well Test Position.
[0168] (14) Pressure up the Annulus to 500 psi.
[0169] (15) Fire the Tubing Conveyed Perforate Guns by pressuring up on the Work String to the calculated detonation pressure. Bleed the pressure to 0.
[0170] (16) Monitor firing of the Guns (usually a 5 to 10 minute delay). Obtain Shut in Tubing Pressure. Calculate the difference between the estimated Bottom Hole 14 Pressure and the actual Bottom hole 14 pressure.
[0171] (17) Open the Well 14 thru the desired Positive Choke size and flow back the desired volume.
[0172] (18) Cycle the Omni Valve to the Reverse Circulating Position.
[0173] (19) Reverse out the Influx plus an additional Work String Volume.
[0174] (20) Bleed the pressure on the Annulus to 0.
[0175] (21) Open the Annular Blow Out Preventer.
[0176] (22) Start the Trip Tank Pump circulating on the Annulus. Open the By-Pass on the Tubing Conveyed Perforate Packer by picking up on the Work string. Monitor the fluid loss to the formation. If excessive losses are occurring, close the By-Pass.
[0177] (23) Pump and displace a Loss Circulation Pill of choice. Balance the Loss Circulation Pill by leaving Pill in the Work String above the Omni Valve and with Pill above the Omni Valve on the outside between the Omni and the casing.
[0178] (24) Open the By-Pass and monitor the Hole 14 on the Trip Tank. The Hole 14 should take the calculated volume of fluid from the Omni Valve to the bottom of the perforations and then become static.
[0179] (25) Close the By-Pass and Cycle the Omni Valve to the Well Test Position.
[0180] (26) Open the By-Pass and reverse out Influx that was trapped below the Omni Ball Valve.
[0181] (27) With the By-Pass in the open position, monitor the hole 14 on the Trip Tank while rigging down the Choke Manifold and pump lines.
[0182] (28) Rig down the Swivel Tool and Ball Drop assembly 1000 .
[0183] (29) Make a 5 stand short trip.
[0184] (30) Circulate bottoms up.
[0185] (31) Pull out of hole. Circulate at desired stages while Pull out of hole 14 as to monitor for possible trapped or swabbed Gas.
[0186] Note: If elected, the Choke Manifold that was rigged up on the Rig Floor can be eliminated and the Rig Choke Manifold could be used instead. The flow back could be flowed back to the Trip Tank and timed with the Super Choke adjusted to obtain the desired Barrel of Oil Per Day rate. This could be done to reduce additional expense and save Rig Time.
[0187] If a Bar Drop is elected to be the primary choice of the Tubing Conveyed Perforate detonation, a Pup Joint can be easily added between the Upper Swivel 1050 and the Top Drive 10 . The Full Opening Ball Valve 1006 would be closed and the Ball Valve Wrench taped. The Lower Low Torque Valve 1008 would then be used for circulation activities. Once all operations have been completed and the well is ready to be perforated, the Tape can be removed and the Bar can be dropped when intended. The tape is installed to the Ball Valve 1006 only as a safety factor so that the Bar will not be accidentally dropped prior to the contemplated drop.
[0188] The following is a list of reference numerals:
[0000]
LIST FOR REFERENCE NUMERALS
(Part No.)
(Description)
Reference Numeral
Description
1
rig
2
crown block
3
cable means
4
travelling block
5
hook
6
gooseneck
7
swivel
8
drilling fluid line
10
top drive unit
11
draw works
12
cable
13
rotary table
14
well bore
15
guide rail
16
support
17
support
18
drill pipe
19
drill string
20
drill string or work string
30
swivel
31
hose
40
swivel mandrel
50
upper end
60
lower end
70
box connection
80
pin connection
90
central longitudinal passage
100
shoulder
101
outer surface of shoulder
102
upper surface of shoulder
110
interior surface
120
external surface (mandrel)
130
recessed area
131
packing support area
132
packing support area
140
radial inlet ports (a plurality)
145
bearing (preferably combination 6.875
inch bearing cone, Timken Part number
67786, and 9.75 inch bearing cup bearing
cup, Timken part number 67720)
146
bearing (preferably combination 7 inch
bearing cone, Timken Part number 67791,
and 9.75 inch bearing cup bearing cup,
Timken part number 67720)
150
swivel sleeve
155
protruding section
156
shoulder
157
shoulder
158
packing support area
159
packing support area
160
upper end
170
lower end
180
central longitudinal passage
190
radial passage
200
inlet
201
arrow
202
arrow
203
arrow
204
arrow
205
peripheral groove
206
key way
210
lubrication port
211
grease injection fitting (preferably grease
zerk (¼ - 28 td. in. streight, mat.-monel
Alemite part number 1966-B)
220
packing port
225
injection fitting(preferably packing
injection fitting (10,000 psi) Vesta - PGI
Manufacturing part number PF10N4-10)
(alternatively Pressure Relief Tool for
packing injection fitting Vesta - PGI
Manufacturing part number PRT -PIF 12-20)
226
head
230
packing port
235
injection fitting (preferably packing
injection fitting (10,000 psi) Vesta - PGI
Manufacturing part number PF10N4-10)
(alternatively Pressure Relief Tool for
packing injection fitting Vesta - PGI
Manufacturing part number PRT -PIF 12-20)
240
cover
250
upper shoulder
260
lower shoulder
270
area for wiper ring
271
wiper ring (preferably Parker part number
959-65)
280
area for wiper ring
281
wiper ring (preferably Parker part number
959-65)
290
area for grease ring
291
grease ring (preferably Parker part number
2501000 Standard Polypak)
300
area for grease ring
301
grease ring (preferably Parker part number
2501000 Standard Polypak)
305
packing unit
310
packing retainer nut
314
bore for set screw
315
set screw for packing retainer nut
316
threaded area
317
set screw for receiving area
320
packing end
330
packing ring
340
packing ring
350
packing injection ring
351
transverse port
352
radial port
353
peripheral groove
354
interior groove
355
male end
356
flat end
360
packing end
370
packing ring
380
packing ring
390
packing ring
400
packing ring
410
packing end
415
packing unit
420
packing retainer nut
425
set screw for packing retainer nut
430
packing end
440
packing ring
450
packing ring
460
packing lubrication ring
470
packing end
480
packing ring
490
packing ring
500
packing ring
510
packing ring
520
packing end
600
clamp
605
groove
610
first portion
620
second portion
630
torque arm
640
torque arm
650
shackle
660
shackle
670
fastener
680
fastener
690
keyway
691
keyway
700
key
710
keyway
711
keyway
720
key
730
peripheral groove
800
retaining nut
801
threaded area
810
outer surface
820
inclined portion
830
bore
840
inner surface
850
threaded portion
860
upper surface
870
bottom surface
880
lubrication port
881
grease injection fitting (preferably grease
zerk (¼ - 28 td. in. streight, mat.-monel
Alemite part number 1966-B)
890
set screw
900
bore for set screw
910
receiving portion for set screw
1000
top drive swivel
1001
arrow
1002
arrow
1003
arrow
1005
stabilizing bracket
1006
intermediate valve
1006B
bore
1006A
valve ball
1007
valve member
1008
valve member
1009
manifold
1010
arm
1030
swivel portion
1040
mandrel
1041
lower portion of mandrel
1050
sleeve
1300
line
1301
line
1302
line
2000
valve member
2001
valve
2005
plug or ball
2010
tool
2011
upper section
2012
lower section
2013
middle section
2014
threaded section
2015
enlarged inner diameter section
2016
narrowing diameter section
2018
threaded section
2019
o-ring seal
2020
o-ring seal
2021
arrow
2030
swivel portion
2040
mandrel
2041
lower portion of mandrel
2050
sleeve
[0189] All measurements disclosed herein are at standard temperature and pressure, at sea level on Earth, unless indicated otherwise. All materials used or intended to be used in a human being are biocompatible, unless indicated otherwise.
[0190] It will be understood that each of the elements described above, or two or more together may also find a useful application in other types of methods differing from the type described above. Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention set forth in the appended claims. 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.
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A double swivel for use with a top drive power unit supported for connection with a well string in a well bore to selectively impart longitudinal and/or rotational movement to the well string, a feeder for supplying a pumpable substance such as cement and the like from an external supply source to the interior of the well string in the well bore without first discharging it through the top drive power unit including a mandrel extending through double sleeves which are sealably and rotatably supported thereon for relative rotation between the sleeves and mandrel. The mandrel and sleeves have flow passages for communicating the pumpable substance from an external source to discharge through the sleeve and mandrel and into the interior of the well string below the top drive power unit. The unit can include a packing injection system, clamp, and novel packing configuration. In an alternative embodiment the unit can include a plug or ball insertion tool.
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This application is a Continuation of application Ser. No. 08/592,399, now U.S. Pat. No. 5,792,786, filed Feb. 1, 1996 which is a 371 of PCT/AU94/00440 filed Aug. 2, 1993.
FIELD OF THE INVENTION
The present invention relates to therapeutic conjugates which comprise a therapeutic compound bound to one to three acyl groups derived from fatty acids and to methods involving the use of these compounds. In particular the present invention relates to nonsteroidal anti-inflammatory compounds bound to one to three acyl derivatives of fatty acids.
BACKGROUND OF THE INVENTION
Among the most commonly used therapeutic agents are the nonsteroidal anti-inflammatory drugs. These are typically broken into three major groups:
carboxylic acids,
pyrazoles, and
oxicams.
Of particular interest in the present invention are the nonsteroidal anti-inflammatory agents which include a carboxylic acid group such as salicylates. Of these nonsteroidal anti-inflammatory drugs the most commonly used compounds are acetylsalicylic acid (aspirin), ibuprofen and indomethacin.
The present inventors have now discovered that the nonsteroidal anti-inflammatory drugs and other therapeutic compounds can be linked to one to three fatty acids. These new compounds are believed to improve the transdermal delivery, transdermal uptake, half-life and/or other modes of delivery of these nonsteroidal anti-inflammatory and other therapeutic agents. Further, it is believed that these novel compounds will aid in the oral, internasal and intraocular delivery of the nonsteroidal anti-inflammatory drugs and other therapeutic agents.
SUMMARY OF THE INVENTION
Accordingly, in a first aspect the present invention consists in a compound of the following formula:
in which X is a therapeutic compound
Y is absent or is one or two amino acids or a peptide or spacer group
B is H or CH 2 O—R 3 ; and
R 1 , R 2 and R 3 are the same or different and are either hydrogen, methyl, ethyl, hydroxyl or an acyl group derived from a fatty acid (saturated or unsaturated) with the proviso that at least one of R 1 , R 2 and R 3 is an acyl group derived from a fatty acid.
In a second aspect the present invention consists in a compound of the following formula:
X—Y—NH—CH 2 —CH 2 O—R 4
in which X represents a therapeutic compound,
Y is absent or is one or two amino acids or a peptide or spacer group, and R 4 is an acyl group derived from a fatty acid.
In a third aspect the present invention consists in a method of prolonging the activity of a nonsteroidal anti-inflammatory compound comprising administering the compound in the form
in which X is the nonsteroidal anti-inflammatory compound
Y is absent or is one or two amino acids or a peptide or spacer group
B is H or CH 2 O—R 3 ; and
R 1 , R 2 and R 3 are the same or different and are either hydrogen, methyl, ethyl, hydroxyl or an acyl group derived from a fatty acid with the proviso that at least one of R 1 , R 2 and R 3 is an acyl group derived from a fatty acid.
In a fourth aspect the present invention consists in a method of prolonging the activity of a nonsteroidal anti-inflammatory compound comprising administering the compound in the form:
X—Y—NH—CH 2 —CH 2 O—R 4
in which X represents the nonsteroidal anti-inflammatory compound
Y is absent or is one or two amino acids or a peptide or spacer group, and R 4 is an acyl group derived from a fatty acid.
In a fifth aspect the present invention consists in a method of treating burns comprising administering a compound of the formula:
in which X is ibuprofen
Y is absent or is one or two amino acids or a peptide or spacer group
B is H or CH 2 O—R 3 ; and
R 1 , R 2 and R 3 are the same or different and are either hydrogen, methyl, ethyl, hydroxyl or an acyl group derived from a fatty acid with the proviso that at least one of R 1 , R 2 and R 3 is an acyl group derived from a fatty acid.
In a sixth aspect the present invention consists in a method of treating burns comprising administering a compound of the formula:
X—Y—NH—CH 2 —CH 2 O—R 4
in which X is ibuprofen
Y is absent or is one or two amino acids or a peptide or spacer group, and R 4 is an acyl group derived from a fatty acid.
As will be recognised by persons skilled in the art, the compound of the first aspect of the present invention consists of a therapeutic compound linked, optionally via an amino acid(s) to a tromethamine derivative to which is linked an acyl group derived from a fatty acid(s). Similarly, the compound of the second aspect can be recognised as a therapeutic agent linked, optionally via an amino acid(s) to an ethanolamine derivative to which is linked an acyl group derived from a fatty acid.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In preferred embodiments of the present invention the therapeutic compound is a nonsteroidal anti-inflammatory compound which preferably includes a carboxylic acid group.
The nonsteroidal anti-inflammatory compound may be selected from a wide range of such known compounds including salicylate, acetylsalicylate, salsalate, diflunisal, fendosal, indomethacin, acemetacin, cinmetacin, sulindac, tolmetin, zomepirac, diclofenac, isoxepac, ibuprofen, flurbiprofen, naproxen, ketoprofen, tenoprofen, benoxdprofen, indoprofen, pirprofen, carprofen, mefenamic acid, flufenamic acid, meclofenamate, niflumic acid, tolfenamic acid, flunixin and clonixin. It is, however, presently preferred that X is selected from the group consisting of acetylsalicylate, salicylate, indomethacin and ibuprofen.
Further examples of nonsteroidal anti-inflammatory compounds are provided in Weissman, Scientific American, January 1991, 58-64, the disclosure of which is incorporated herein by reference.
In yet a further preferred embodiment R 1 , R 2 and R 3 are either hydrogen or an acyl group derived from a fatty acid.
It will also be apparent to those skilled in this field that substitutions other than methyl, ethyl and hydroxyl are possible at R 1 , R 2 or R 3 . The prime requirement is that at least one of R 1 , R 2 or R 3 is an acyl group derived from a fatty acid.
In a further preferred embodiment of the first aspect of the present invention, each of R 1 , R 2 and R 3 are acyl groups derived from fatty acids, and more particularly, are each the same acyl group. It is presently preferred that the fatty acid has a carbon chain of 3 to 18 carbon atoms, more preferably 10 to 18 carbon atoms, and most preferably 16 carbon atoms. In the same manner it is preferred that R 4 is an acyl group derived from a fatty acid having a carbon chain of 3 to 18 carbon atoms, more preferably 10 to 18 carbon atoms, and most preferably 16 carbon atoms.
In a further preferred embodiment of the present invention Y is either absent or is alanine or glycine.
In a further preferred embodiment of the present invention the compound is selected from the group consisting of salicylate-Tris-tripalmitate, salicylate-Tris-dipalmitate, salicylate-Tris-monopalmitate, ibuprofen-alanine-Tris-tripalmitate, ibuprofen-alanine-Tris-dipalmitate, ibuprofen-alanine-Tris-monopalmitate, indomethacin-glycine-Tris-monopalmitate, indomethacin-glycine-Tris-dipalmitate indomethacin-glycine-Tris-tripalmitate, indomethacin-glycine-ethanolamine palmitate, and indomethacin-ethanolamine palmitate.
As stated above the compounds may optionally include a spacer group. Spacer groups useful in the present invention are well known and include:
1. Between a compound with a carboxyl group and the amino group of Tris
a) a spacer group with an amino group to the compound and a carboxyl group to the Tris such as amino acids and antibiotics
b) a spacer group with an amino group to the compound and a sulphonic acid group to the Tris such as 2-aminoethanesulphonic acid (taurine)
c) a spacer group with an amino group to the compound and an hydroxyl group to the Tris such as 2-aminoethanol (e.g. via a chloride or bromide intermediate)
d) a spacer group with an hydroxyl group to the compound and a carboxyl group to the Tris such as glycolic acid, lactic acid etc
e) a spacer group with an hydroxyl group to the compound and a sulphonic acid group to the Tris such as 2-hydroxyethanesulphonic acid (isethonic acid)
f) a spacer group with an hydroxyl group to the compound and a reactive halide group to the Tris such as 2-chloroethanol
g) other examples of potentially suitable spacer groups between a compound with a reactive carboxyl and the amino group of Tris include the compound families exemplified by p-hydroxybenzaldehyde, 2-chloroacetic acid, 1,2-dibromoethane and ethyleneoxide.
2. Between a compound with an hydroxyl group and the amino group of Tris
a) a spacer group with a carboxyl group to the compound and a carboxyl group to the Tris such as dicarboxylic acids via the anhydride e.g. succinic anhydride, maleic anhydride etc.
b) a spacer group with a carboxyl group to the compound and an aldehyde group to the Tris such as glyoxylic acid (in the presence of a reducing agent e.g. NaBH 4 ).
c) a spacer group with a carboxyl group to the compound and a halide group to the Tris such as chloroacetic acid
d) a spacer group with a carboxyl group to the compound and a N═C═O group to the Tris such as ethylisocyanatoacetate.
3. Between a compound with an amine group and the amino group of Tris
a) a spacer group with a carboxyl group to the compound and a carboxyl group to the Tris such as dicarboxylic acids via the anhydride e.g. succinic anhydride, maleic anhydride etc.
b) a spacer group with a carboxyl group to the compound and an aldehyde group to the Tris such as glyoxylic acid (in the presence of a reducing agent e.g. NaBH 4
c) a spacer group with a carboxyl group to the compound and a halide group to the Tris such as chloroacetic acid
d) other examples of potentially suitable spacer groups between a compound with an amide group and the amino group of Tris include the compound families exemplified by acrolein (in the presence of a reducing agent e.g. NaBH 4 ) and acrylic acid.
4. Between a compound with a thiol group and the amino group of Tris
Examples of potentially suitable spacer groups between a compound with a thiol group and the amino group of Tris include the compound families exemplified by choroacetic acid and acrolein (in the presence of a reducing agent e.g. NaBH 4 ).
In order that the nature of the present invention may be more clearly understood, preferred forms thereof will now be described with reference to the following examples and Figures.
Chemical Abbreviations used:
ATP1=Alanine-Tris-monopalmitate
ATP2=Alanine-Tris-dipalmitate
ATP3=Alanine-Tris-tripalmitate
CDCl 3 =Chloroform-d
DCC=Dicyclohexylcarbodiimide,
DCM=Dichloromethane,
DCU=Dicyclohexylurea
DIEA=Diisopropylethylamine,
DMAP=Dimethylaminopyridine,
DMF=Dimethylformamide,
DMSO-d 6 =Dimethylsulfoxide-d 6 ,
GTP1=Glycine-Tris-monopalmitate
GTP2=Glycine-Tris-dipalmitate
GTP3=Glycine-Tris-tripalmitate
HOSu=N-Hydroxysuccinimide,
Ibuprofen=α-Methyl-4-(2-methylpropyl)benzene acetic acid
Indomethacin=1-(4-Chlorobenzoyl)-5-methoxy-2-methyl-1H-indole-3-acetic acid
NSAID=Nonsteroidal anti-inflammatory drug
TFA=Trifluoroacetic acid,
THF=Tetrahydrofuran,
Tris=2-Amino-2-hydroxy-methyl-1,3 propanediol.
TSTU=(O-(N-Succinimidyl)-N,N,N′N′-tetramethyl uronium tetrafluoroborate,
Z=Benzyloxycarbonyl
MATERIALS AND METHODS
HIGH PERFORMANCE LIQUID CHROMATOGRAPHY (HPLC)
Analytical HPLC was carried out on Millipore Waters HPLC equipment (Waters Chromatography Division of Millipore, Milford, Mass.), comprising of a 6000A series solvent delivery system with an automated gradient controller and Model 746 Data Module. The separations were performed on a Novapak C18 reverse phase column (100×8 mm). Elution of non fatty acyl derivatives was carried out using a linear gradient from 24 to 80% acetonitrile with 0.1% TFA over 5 min at a flow rate of 2 ml/min (System A) (R t A ). Detection was at 260 nm using a Waters Lambda Max Spectrophotometer, Model 480.
The conjugates were analysed on a C18 column with a linear gradient from 40% water: 50% acetonitrile: 10% THF to 50% acetonitrile: 50% THF containing 0.1% TFA over 5 min at a flow rate of 2 ml/min (System B); (R t B ).
PREPARATIVE HPLC
Separations were carried out on a Millipore Waters DeltaPrep 4000 HPLC using PrepPak R C4 or C18 reverse phase columns (Prep Nova-Pak HR 40×100 mm) eluted with linear gradients using the same eluent buffer systems as for the analytical HPLC at flow rates of 20 ml/min.
NUCLEAR MAGNETIC RESONANCE (NMR)
NMR spectra were recorded with a 200 MHz Bruker spectrometer.
SYNTHESES
Two alternative methods were employed in the syntheses of palmitoyl derivatives of indomethacin and ibuprofen. In one, the active esters of the NSAID compounds were reacted with the freshly prepared, purified GTP1, GTP2, GTP3, or ATP1, ATP2 and ATP3, and in the other, the active esters were reacted with Ala-Tris or Gly-Tris, the products purified and then palmitoylated to give a mixture of mono, di, and tripalmitates. These were then separated and purified as described. Indomethacin-ethanolamide and indomethacin-glycine ethanolamide derivatives were synthesised via the active ester chemistry and palmitoylated.
Preparation of Gly-Tris
The title compound was obtained in quantitative yield by hydrogenation of a solution of Z-Gly-Tris in ethanol at 40 atm. pressure in a Parr hydrogenator in the presence of palladium on carbon (10%). The removal of the benzyloxycarbonyl group was monitored by HPLC (System A). The catalyst was removed by filtration and washed with ethanol. Evaporation of the solvent gave the title product in 95% purity as shown by 1 H NMR spectroscopy. Ala-Tris was prepared in an analogous manner. The preparation of Z-Gly-Tris and Z-Ala-Tris are described in Whittaker, R. G., Hayes, P. J., and Bender, V. J. (1993) Peptide Research 6, 125 and Australian Patent No. 649242.
Preparation of Indomethacin-Gly-Tris
To a stirred solution of indomethacin (1 g, 2.80 mmole) in DMF (50 ml), HOSu (484 mg, 4.2 mmole) was added. The solution was cooled to 0° C. and a solution of DCC (618 mg, 3 mmole) in DCM (5 ml) added. Stirring was continued at room temperature for 2 h to give the active ester in 92% yield (HPLC, System A, R t 8.38 min). DCU was removed by filtration and washed with DCM. The combined filtrates were added to a solution of Gly-Tris (1.70 g, 9 mmole) in DMF (10 ml) and stirring continued at room temperature for 4 h. The title compound was formed in 85% yield as determined by HPLC (System A). The solvents were removed under reduced pressure, and the residual oil extracted with ethyl acetate and dried (MgSO 4 ) to give the title compound as a yellow oil (0.91 g, 61% of the theoretical yield). HPLC (System A) gave a single peak, R t 5.35.
Preparation of Indomethacin-Gly-Tris Palmitates
To a solution of indomethacin-Gly-Tris (800 mg, 1.48 mmole) in DMF (20 ml), palmitic acid (570 mg, 2.22 mmole) in DCM (20 ml), DCC (310 mg, 1.5 mmole) and DMAP (20 mg) were added at 0° C. with stirring. The reaction was monitored by HPLC (System B). After 16 h under these conditions the indomethacin-Gly-Tris mono, di and tripalmitates were formed in a 66:30:4 ratio. The solvents were evaporated to dryness, the residue redissolved in DCM (100 ml) and washed with water, citric acid (10%), sodium hydrogen carbonate (5%) and water (100 ml each) and dried (MgSO 4 ). Mono, di and tripalmitates were separated by preparative HPLC on a C4 column (System B) to yield products which gave single peaks on analytical HPLC, Rt 7.49, 8.93 and 9.80. 1 H NMR of all three products indicated however, that some cleavage of the indomethacin molecule occurred during the reaction, most likely due to the effect of aqueous alkali, so an alternative method for these syntheses was employed.
Preparation of GTP1, GTP2 and GTP3
These compounds were obtained by hydrogenation of Z-Gly-Tris-mono, di, and tripalmitates at 40 atm. pressure in a Parr hydrogenator in the presence of palladium on carbon (10%) in ethanol. The removal of the benzyloxycarbonyl group was monitored by HPLC (System B). After removing the catalyst by filtration and evaporation of solvents GTP1, GTP2 and GTP3 were obtained in quantitative yields. The syntheses and purification of Z-GTP1, Z-GTP2, Z-GTP3 and the corresponding alanyl compounds are described in Whittaker, R. G., Hayes, P. J. and Bender, V. J., (1993), Peptide Research 6, 125-128, and Australian Patent No. 649249. The same source describes the synthesis of mono, di, and tri forms of myristate, laurate and caprate.
The following 1 H NMR data are shown as examples of purity:
1H NMR of GTP2
1 HNMR (CDCl 3 , δ, ppm): 0.87 (6H, t, Palmitate(CH 3 ), J=6.4 Hz), 1.19-1.42 (52H, m, CH 2 ), 1.60 (4H, m, Palmitate (βCH 2 ), 2.33 (4H, t, Palmitate (α-CH 2 ), J=7.2 Hz), 3.41 (1H, brs, OH), 3.70 (2H, q, Gly(CH 2 ), J=7 Hz), 3.80 (2H, s, Tris(CH 2 )), 4.17 (2H, d, Tris(CH 2 ), J=10.4 Hz), 4.31 (2H, d, Tris(CH 2 ), J=11.2 Hz), 7.92 (2H, brs, NH 2 ).
1H NMR of Z-GTP2
1 HNMR (CDCl 3 , δ, ppm): 0.89 (6H, t, Palmitate (CH 3 ), J=6.4 Hz), 1.19-1.42 (52H, m, CH 2 ), 1.61 (4H, m, Palmitate (βCH 2 )) 2.31 (4H, t, Palmitate (αCH 2 ), J=7.2 Hz), 3.8 (2H, d, Tris(CH 2 ), J=5.5 Hz), 3.82 (2H, d, Gly(CH 2 ), J=8 Hz), 4.21 (2H, d, Tris(CH 2 OCO), J=11.6 Hz), 4.39 (2H, d, Tris(CH 2 OCO), J=11.4 Hz), 5.14 (2H, s, Ar—CH 2 ), 5.31 (1H, t, Glyamide NH), J=5.4 Hz), 6.55 (1H, s, Tris(amide NH), 7.35 (5H, m, Ar (H)). production of Indomethacin-Gly-Tris-Dipalmitate.
To a solution of indomethacin (716 mg, 2 mmole) in dry DMF (15 ml) TSTU (Fluka, 85972), (1.20 g, 4 mmole) in DMF (10 ml) was added. The apparent pH of the solution was maintained at 8.3 with DIEA and the mixture stirred at room temperature. The formation of the active ester was monitored by reverse phase HPLC on a C18 column (System A). The reaction was complete in 1 h; Rt of indomethacin, 8.08 min; indomethacin-OSu, 8.38 min.
This solution was added dropwise to a solution of Gly-Tris-dipalmitate (GTP2, 640 mg, 1 mmole) in DCM (10 ml). The apparent pH was maintained at 8.3 with DIEA and the reaction monitored by HPLC on a C 18 column (System B) After the relative area counts indicated that the reaction had proceeded to 65-70% completion, the solution was evaporated to dryness under reduced pressure.
The title product was obtained in the form of a white solid after chromatography on Silica gel (Kieselgel S, 0.063-0.2 mm, for column chromatography, Riedel-de Haen A. G.) eluting with ethylacetate/hexane (1:9) to (6:4). The fractions were analysed by HPLC (System B). Fractions containing the pure product were combined, evaporated to dryness and lyophilised from tert. butanol.
A solution of a sample of the product in DCM (10 mg/ml) gave a single peak on HPLC, R B t 8.89 in higher than 95% purity as demonstrated by 1 H NMR.
1 HNMR (CDCl 3 , δ, ppm): 0.86 (6H, t, Palmitate CH 3 ), J=6.4 Hz), 1.02-1.39 (52H, m, CH 2 ), 1.59 (4H, m, Palmitate (βCH 2 ) 2.32 (4H, t, Palmitate (αCH 2 ), J=7.4 Hz), 2.39 (3H, s, CH 3 ) 3.69 (2H s, OCH 2 ) 3.77 (2H, t, Gly(CH 2 ), J=5.2 Hz), 3.82 (5H, s, Tris(CH 2 ), OCH 3 ), 4.19 (2H, d, Tris(CH 2 ), J=12.2 Hz), 4.37 (2H, d, Tris(CH 2 ), J=11.6 Hz), 6.23 (1H, t, Glyamide NH), J=5.4 Hz), 6.55 (1H, s, Tris(amide NH) 6.70 (1H, dd, Ar (CH), J=2.4, 8.8 Hz), 6.91 (1H, d, Ar (CH), J=9.1 Hz), 6.93 (1H, d, Ar (CH)J=2.4 HZ), 7.49 (2H, d, Ar (CH), J=8.5 Hz), 7.68 (2H, d, Ar (CH), J=8.8 Hz).
Production of Indomethacin-Gly-Tris-Tripalmitate
The title compound was prepared in a manner analogous to that described above for the dipalmitate derivative. Indomethacin (716 mg, 2 mmole), TSTU (1.2 g, 4 mmole) and Gly-Tris-tripalmitate (950 mg, 1 mmole) were reacted and monitored by HPLC (System B). The title compound was obtained after purification on silica gel to give the chromatographically pure compound with a R t 9.42 (System B).
Preparation of Indomethacin-Glycine
To a suspension of indomethacin (500 mg, 1.40 mmole) in acetonitrile (20 ml), HOSu (177 mg, 1.54 mmole) and DCC (317 mg, 1.54 mmole) were added and the solution stirred at room temperature for 2 h. A solution of glycine (178 mg, 2.38 mmole) and triethylamine (184 mg, 1.82 mmole) in water (10 ml) was added to the resulting indomethacin hydroxysuccinimide ester and stirred for 2 h, diluted with water (60 ml), acidified with 1M HCl and extracted with ethyl acetate (80 ml). After drying (MgSO 4 ) the solution was evaporated to dryness to give a yellow solid, which was recrystallised from ethylacetate/hexane to give the title product (406 mg, 70% theory) in 95% purity as determined by 1H NMR.
Preparation of Indomethacin-Glycine-Ethanolamide
To a solution of indomethacin-glycine (1.5 g, 3.62 mmole) in acetonitrile/DMF (60 ml, 5:1), HOSu (460 mg, 3.98 mmole) and DCC (820 mg, 3.98 mmole) were added and the solution stirred for 3 h until the reaction was complete. Ethanolamine (445 mg, 7.3 mmole) was added and stirring continued at room temperature for 1 h. Ethylacetate (300 ml) was added and the solution washed with 1M HCl (120 ml) water and with a saturated NaCl solution (120 ml each) and dried (MgSO 4 ). Evaporation of the solvent gave the crude title product, which on recrystallisation from ethylacetate/hexane afforded the title product (1.45 g, 88% of theory) as a yellow solid.
Preparation of Indomethacin-Glycine-Ethanolamide-Palmitate
To a suspension of indomethacin-glycine-ethanolamide (410 mg, 0.89 mmole) in DCM/DMF (25 ml, 9:1) palmitic acid (240 mg, 0.93 mmole) DMAP (10 mg) and DCC (192 mg, 0.93 mmole), were added and the solution stirred for 16 h. The solution was diluted with DCM (50ml) and washed with 1M HCl, water and saturated NaCl solution (50 ml each) and dried (MgSO 4 ). After the removal of the solvent, the residue was chromatographed on silica. Elution was with DCM/ethylacetate to afford the title product as a yellow solid. Final purification was by recrystallisation from ethanol (yield 510 mg, 82% of theory).
Preparation of Indomethacin-Ethanolamide
To a solution of indomethacin (1.0 g, 2.80 mmole) in acetonitrile (50 ml) HOSu (335 mg, 2.9 mmole) and DCC (605 mg, 2.9 mmole) were added and the solution stirred at room temp. for 1 h. Ethanolamine (340 mg, 5.5 mmole) was added and the solution stirred for a further 2 h. DCU was removed by filtration and washed with DCM. The combined filtrates and washes were evaporated and the residue redissolved in DCM (50 ml), washed with 1M HCl (30 ml) and water (30 ml) and dried (MgSO 4 ). Evaporation of the solvent afforded the title compound as a yellow solid (1.1 g, 98% of theory). Recrystallisation from ethyl acetate/hexane with a few drops of DCM afforded the pure product as a light yellow solid (750 mg, 67% theory).
1 HNMR (CDCl 3 , δ, ppm) 2.37 (3H, s, CH 3 ), 2.78 (1H brs, OH), 3.36 (2H, dt, CH 2 , J=5.5,5.5 Hz), 3.65 (4H, brs, CH 2 CO,CH 2 OH), 3.82 (3H, s, OCH 3 ), 6.16 (1H, brt, amide NH, J=5.5 Hz), 6.68 (1H, dd, Ar(CH), J2.4, 9.1 Hz), 6.87 (1H, d, Ar(CH), J=9.1 Hz), 6.90 (1H, d, Ar(CH), J=2.4 Hz), 7.46 (2H, d, Ar(CH), J=7.9 Hz), 7.64 (2H, d, Ar(CH), J=7.9 Hz).
Preparation of Indomethacin-Ethanolamide-Palmitate
To a solution of indomethacin-ethanolamide (600 mg, 1.50 mmole) in DCM (10 ml) palmitic acid (405 mg, 1.58 mmole), DMAP (10 mg) and DCC (320 mg, 1.55 mmole) were added. The solution was stirred at room temperature for 16 h and diluted with DCM (50ml), washed with 1M HCl (50 ml) and water (50 ml) and dried (MgSO 4 ). On evaporation of the solvent the crude product was obtained as a slightly oily solid, which was then purified by chromatography on silica. Elution was with DCM/ethyl acetate (9:1) to (8:2) to afford the title compound. Recrystallisation from ethyl acetate gave 610 mg, (66% of the theory) as a dense solid.
1 HNMR (CDCl 3 , δ, PPm) 0.86 (3H, t, Palmitate (CH 3 , J=6.4 Hz), 1.20-1.42 (26H, m), 1.46 (2H, m, Palmitate (βCH 2 )), 2.05 (2H, t, J=7.9 Hz), 2.38 (3H, s, CH 3 ) 3.45 (2H, dt, CONHCH 2 , J=5.5, 5.5 Hz), 3.63 (2H, s, CH 2 ) 3.80 (3H, s. OCH 3 ), 4.08 (2H, t, CH 2 —OCO J=5.5 Hz), 5.95 (1H, brt, amide NH, J=5.5 Hz), 6.67 (1H, dd, Ar(CH), J=2.4, 9.1 Hz), 6.84 (1H, d, Ar(CH), J=9.1 Hz), 6.85 (1H, d, Ar(CH), J=2.4 Hz), 7.47 (2H, d, Ar(CH), J=8.5 Hz), 7.70 (2H, d, Ar(CH), J=8.5 Hz).
SYNTHESES OF IBUPROFEN CONJUGATES
Preparation of Ibuprofen-Ala-Tris-Monopalmitate
Ibuprofen (206.3 mg, 1 mmole) in DMF (5 ml) was reacted with TSTU (377 mg, 1.25 mmole) which had been dissolved in DMF (5 ml) at pH 8.5 (DIEA). The formation of ibuprofen-OSu was monitored by HPLC (System A) and was found to be complete in 10 min, R t A 5.70. To this mixture a solution of ATP1 (536 mg, 1.25 mmole) in DCM (10 ml) was added and the pH maintained at 8.5 (DIEA). The formation of the title product was monitored by HPLC (System B). At the completion of the reaction the solvents were evaporated under reduced pressure. Preparative HPLC on a C4 column gave the chromatographically pure sample, R t B 7.83.
Ibuprofen-Ala-Tris-Dipalmitate
The title product was prepared in the manner as described above for the monopalmitate. Ibuprofen-OSu was reacted with ATP2 (835 mg 1.25 mmole) to give the chromatographically pure sample, R t B 9.17 min.
Ibuprofen-Ala-Tris-Tripalmitate
The title product was synthesised as above; ibuprofen-OSu was reacted with ATP3 (1.134 g, 1.25 mmole) to give the chromatographically pure sample, R t B 10.43.
Molecular weights of ibuprofen palmitates were determined by Mass Spectrometry to give clean peaks for 619.5, 858.0 and 1096.5, in good agreement with the calculated molecular weights. 1 H NMR studies of these preparations indicated, however, that the procedure resulted in a racemic mixture, so an alternative method was employed, which involved the separation of isomers by crystallisation of the ibuprofen-Ala-Tris compound.
Preparation of Ibuprofen-Ala-Tris
To a solution of ibuprofen (3 g, 14.5 mmole) in DCM (50 ml), HOSu (2.49 g, 21.6 mmole) and DIEA (1.25 ml, 7.25 mmole) were added and the solution cooled to 0° C. DCC (3 g, 14.5 mmole) dissolved in DCM (20 ml) was dropped into the reaction mixture. It was stirred at 0° C. for 2 h followed by continued stirring at room temperature for 12 h to obtain the activated ester (ibuprofen-OSu) in 95% yield by HPLC. The DCU precipitate was filtered off and Ala-Tris (2.77 g, 14.5 mmole) dissolved in DMF (10 ml) was added to the reaction mixture and stirring continued at room temperature for 4 h. The title compound was formed in 70% yield by HPLC. R t A: 5.43. The solvents were removed under reduced pressure and the oily residue dissolved in DCM and washed with citric acid (4%), sodium bicarbonate (5%) and water. The DCM was dried (MgSO 4 ) and evaporated to dryness, to obtain 5.4 g of an oily compound. The oily residue was a 50/50 racemized mixture which was identified by its 1 HNMR spectrum. The doublet peak of methyl proton of alanine and ibuprofen of the diasteroisomers shifted away about 6 Hz from each other.
1 HNMR of mixture (CDCl 3 , δ, ppm) : 0.89 (6H, d, Ibu (CH 3 ), J=6.4 Hz), 1.22, 1.25 (3H, 2d, Ala (BCH 3 ), J=5.2 Hz), 1.40, 1.43 (3H, 2d, Ibu (BCH 3 ), J=4.9 Hz), 1.86 (1H, m, Ibu (CH)), 2.46 (2H, d, Ibu (CH 2 ), J=7 Hz), 3.57 (1H, q, Ibu (αCH), J=7.9 Hz), 3.67 (6H, s, Tris (CH 2 ), 4.14 (3H, brs, Tris (OH)), 4.28 (1H, m, Ala (αCH), 5.99, 6.02 (1H, 2d, Ala amide NH), J=6.7 Hz, 7 Hz), 7.09 (1H, s, Tris-(amide NH), 7.16 (4H, m, Ar (H)).
The two different diasteroisomers were separated successfully by partial crystallisation of the racemate in DCM (1.6 g). Similar work has been also described by M. Bodanszky, “Principles of Peptide Synthesis”, volume 16, Springer-Verlag, Berlin 1984. 1 HNMR of the crystals and the oily residue confirmed the purity of the diasteroisomers.
1 HNMR of the crystal (CDCl 3 , δ, ppm) : 0.89 (6H, d, Ibu (CH 3 ), J=6.4 Hz), 1.3 (3H, d, Ala (βCH 3 ), J=7.6 Hz), 1.48 (3H, d, Ibu (CH 3 ), J=7.3 Hz), 1.86 (1H, m, Ibu (CH)), 2.46 (2H, d, Ibu (CH 2 ), J=7 Hz), 3.57 (1H, q, Ibu (αCH), J=7.9 Hz), 3.67 (6H, s, Tris (CH 2 )), 4.14 (3H, brs, Tris (OH)), 4.28 (1H, m, Ala (αCH), 6.02 (1H, d, Ala(amide NH, J=6.4 Hz), 7.09 (1H, s, Tris (amide NH)), 7.16 (4H, m, Ar (H)).
Ibuprofen-Ala-Tris-Palmitates
To a solution of ibuprofen-Ala-Tris (crystalline product, 1.2 g, 3 mmole) in a 50 % dry DCM/DMF solvent mixture (40 ml), palmitic acid (0.924 g, 3.6 mmole) and a catalytic amount of DMAP (20 mg) were added and the reaction mixture cooled to 0° C. DCC (0.77 g, 3.6 mmole) dissolved in DCM (20 ml) was dropped into the reaction mixture. It was stirred at 0° C. for 1 h and at room temperature for 20 h. The ratio of the mono, di, and tripalmitates of ibuprofen was 55%, 39% and 6% by HPLC (System B).
The solvent was evaporated to dryness and the residue was redissolved in DCM, the DCU filtered off and the filtrate washed with sodium bicarbonate (5%) and water. Preparative HPLC of this mixture on a C18 column yielded high purity compounds of monopalmitate (520 mg, Rt B :7.81 min), dipalmitate (720 mg, Rt B : 9.24 min), and tripalmitate (63 mg, Rt B :10.29 min) compounds (Total yield: 56%).
1 HNMR of the mono palmitate (CDCl 3 , δ, ppm) : 0.87 (3H, t, palmitate (CH 3 ), J=6.4 Hz) 0.89 (6H, d, Ibu (CH 3 ), J=6.4 Hz), 1.13-1.40 (26H, m, palmitate (CH 2 )), 1.49 (3H, d, Ibu (βCH 3 ), J=7 Hz), 1.58 (5H, m, Ala (βCH 3 ), palmitate (βCH 2 )), 1.86 (1H, m, Ibu (αCH)), 2.46 (2H, d, Ibu (CH 2 ), J=7 Hz), 3.56 (1H, q, Ibu (αCH), J=7 Hz), 3.64 (2H, t, Tris (CH 2 ), J=7.9 Hz), 3.74 (2H, t, Tris(CH 2 ), J=6.1 Hz), 3.82 (1H, t, Tris(OH), J=6.4 Hz), 3.99 (1H, t, Tris(OH), J=6.7 Hz), 4.26 (2H, s, Tris(CH 2 )), 4.27 (1H, m, Ala(αCH)), 5.77 (1H, d, Ala amide NH), J=6.7 Hz), 6.87(1H, s, Tris-NH), 7.16 (4H, m Ar(H)).
Preparation of Salicylate-Tris
Methyl salicylate (2.3g, 15.1 mmole) was reacted with Tris (14.8 g, 120.8 mmole) in DMF (182 ml) and water (121 ml) at pH 9.0 and 60° C. for 48 h. The formation of the title product (Rt 3.95) from methyl salicylate (Rt 7.66) was monitored by HPLC (System A) until the reaction stopped at 75% of completion. The mixture was then evaporated to dryness under reduced pressure and the sample dissolved in water. The pH was adjusted to 4.5 and the title product purified by preparative HPLC followed by ion exchange chromatography (Amberlite IR63 resin) to give the chromatographically pure salicylate-Tris (3.66, 65% of theoretical).
The salicylate-Tris is then ready for reaction with one to three fatty acids.
THE ANTI-INFLAMMATORY EFFECT OF MODIFIED NSAID'S AFTER ACUTE UVB INDUCED PHOTODAMAGE IN SKH-1 HAIRLESS MICE
Introduction
Chronic exposure of albino hairless mice (SKH-1) to sub-erythemal doses of ultraviolet (UV) light induces both visible and histological changes in the skin (Bissett et al., 1990). Acute exposure to UVB light induces sunburn erythema and oedema. Both these effects are transient and disappear within a few days (Reeve et al., 1994).
Kaidbey and Kurban, in 1976, and Snyder, 1975, both examined the extent to which topical indomethacin would suppress sunburn erythema in humans and guinea-pigs. In their experiments indomethacin was found to have a profound effect on erythema. The concentration which was found to be most effective was 2.5% indomethacin in a propylene glycol:ethanol:dimethylacetamide vehicle (19:19:2). The subjects received 3 MED's (median erythema doses) of UV light and indomethacin treatment at this concentration gave total protection.
Method Groups of 3 female mice were exposed to 3 MED of UVB on their dorsal surface and then were immediately painted (by smoothing the topical solution over the dorsal surface) with 60 μl or 100 μl of vehicle or vehicle containing increasing concentrations of NSAID's or NSAID fatty acid conjugates. The vehicle used was a variation of previously published vehicles and consisted of ethanol:DMSO at a 5:1 ratio. The test NSAID's and their conjugates were either applied after UVB irradiation to reduce the possibility of sun-screening effects (Day 0), or 1 to 5 days prior to UVB exposure. The oedema was then determined by measuring the skin fold thickness (SFT) of a folded mid-dorsal piece of skin using a hand-held micrometer. Measurements were taken at 0 hours, just prior to UVB exposure and at 24 hours post UVB exposure. A control group, painted with 60 or 100 μl of the vehicle, was used to determine the increase in skin oedema due to the inflammatory response. The time point of 24 hours was found to have maximal skin oedema. The pre UVB SFT measurement was subtracted from the 24 hour SFT measurement, to determine the Net Skin Fold Thickness increase (NSFT).
Results
Indomethacin protection against oedema
As a preliminary study the ability of indomethacin to protect against oedema in Skh-1 mouse was determined. Indomethacin over a concentration range from 0.1% to 2.5% was applied after the mice had been irradiated with UVB; non-irradiated controls were also run. Initially it was found that at concentrations of 2% and above, the indomethacin was lethal after 36 hours inducing typical gastrointestinal haemorrhage. This led to the setting of 1% indomethacin as the upper concentration in further experiments. Young mice were found to be even more susceptible to gastrointestinal damage and a limit of 0.75% indomethacin was set. NSFT measurements for this experiment are presented in FIG. 1 (▾ 24 hour indomethacin NSFT).
Mice that had not been exposed to UVB and painted with vehicle or vehicle plus indomethacin showed no sign of erythema or oedema indicating that neither the vehicle, the application method nor the indomethacin induced an inflammatory response. The mice that had been exposed to UVB and treated with indomethacin showed a decrease in erythema and oedema with increasing concentrations of indomethacin. Concentrations of 0.1% indomethacin had a mild anti-inflammatory effect, with maximal protection occurring with 1% indomethacin and above.
Indomethacin-Fatty acyl conjugates results
The indomethacin-fatty acyl conjugates were examined using an unexposed group of Skh-l female mice. It had been determined previously that the crude indomethacin-fatty acyl conjugates were not protective at concentrations below 1% (w/v based on the indomethacin content) (data not shown). The concentrations tested in the following experiments were 2% (w/v based on the indomethacin content) and were applied to the skin either after exposure to UVB or 5 days, 3 days and 1 day pre UVB exposure.
An aliquot of 100 μl of a 1% (w/u) solution of indomethacin in a 5:1 ethanol:DMSO vehicle was painted onto the dorsal surface of female hairless mice (Skh-1) at time intervals prior to their exposure to UVB, days −5 to −1 and after UVB exposure Day 0. Their NSFT was then calculated at 24 hours post exposure and presented in FIG. 2 (⋄ vehicle; ×1% indomethacin). A logarithmic fit of the data indicates that 1% indomethacin loses its protective effect on UVB induced oedema as the interval of application prior to exposure increases.
In FIG. 3 groups of Skh-1 mice were painted with 100 μl aliquots of crude 2% indomethacin-glycine-Tris-dipalmitate (30% purity contaminated with GTP2; free of uncoupled indomethacin) at the same time intervals prior to UVB exposure as for free indomethacin in FIG. 2 (⋄ vehicle; ×2% indomethacin-GTP2). A linear fit of the data indicates a different profile to that seen with unmodified indomethacin. Photoprotection against UVB induced oedema was most pronounced at 5 days prior to exposure with UVB, indicating that prolonged protection against UVB induced oedema was occurring.
Indomethacin was found to be approximately 50% protective 3 days prior to exposure with UVB, but this protection was not present 5 days prior to exposure, FIG. 2 . The Indo-GTP2 was found to be most protective 5 days prior to irradiation with UVB.
In FIG. 4 groups of 3 mice were painted with 2% solutions (indomethacin equivalent) of high purity indomethacin-glycine-Tris-dipalmitate (Indo-GTP2), indomethacin-glycine-Tris-tripalmitate (Indo-GTP3)., indomethacin ethanolamine monopalmitate (Indo-EP1) or indomethacin-glycine-ethanolamine-monopalmitate (Indo-GEP1) and tested for prolonged protective activity by painting 5 days prior to UVB exposure or for immediate activity by painting immediately after UVB exposure; 0 days. The controls were 0.75% indomethacin and vehicle (5:1 ethanol:DMSO). Indomethacin-GTP2 was found to have highest levels of prolonged and immediate activity. This confirmed the finding presented in FIG. 3 for the crude preparation.
Ibuprofen-alanine-Tris-fatty acyl conjugate results.
Experiment examining the anti-inflammatory effects of ibuprofen-fatty acyl conjugates have indicated that they are active in protecting against UVB induced oedema. FIG. 5 shows the 2% and 4% results for ibuprofen-fatty acid conjugates.
Groups of 3 mice were exposed to 3 MED of UVB and then painted with 4% (ibuprofen equivalent) solutions of ibuprofen-alanine-Tris-monopalmitate (Ibu-ATP1c), ibuprofen-alanine-Tris-dipalmitate (Ibu-ATP2c), ibuprofen-alanine-Tris-tripalmitate (Ibu-ATP3c, at 2%) or ibuprofen-alanine-Tris (Ibu-AT). The controls were 4% ibuprofen (Ibu) or Vehicle alone.
Immediate Activity Results.—highest to lowest 4% Ibu=4% Ibu-ATP>4% Ibu-ATP2>4% Ibu-AT=2% Ibu-ATP3 (c=crystalline Ibu-alanine-Tris form used in the synthesis.)
Ibuprofen-Tris Fatty Acyl Conjugate Effect on Burns
A subsequent finding with Ibuprofen-fatty acid conjugates was their surprising ability to reduce UVB burns and the results of a series of experiments with ibuprofen-alanine-Tris-monopalmitate are presented in Table 1.
TABLE 1
Effect of Ibuprofen and Ibuprofen-ATP1 on UVB
induced burns.
Groups of 3 mice were exposed to 3MED of UVB and then
painted with 100 μl aliquots of 2% ibuprofen-alanine-Tris-
monopalmitate (Ibu-ATP1). The mice were then compared with
2% Ibuprofen (Ibu cont) or vehicle (Vehicle) controls,
over an 8 day period and the results tabulated below. The
maximum UVB burn is denoted as 5 and the minimum burn 1.
If no burn was present a 0 is used.
Day 5
Day 6
Day 7
Day 8
Day 11
Expt 1
Vehicle
4,4,3
0,0,0
Ibu cont
4,3,2
0,0,0
Ibu ATP1
1,0,0
0,0,0
Expt 2
Vehicle
5,5,5
5,5,5
5,5,4
5,4,3
0,0,0
Ibu cont
5,4,4
5,5,4
4,4,4
3,3,3
0,0,0
Ibu ATP1
4,3,3
3,2,2
1,0,0
0,0,0
0,0,0
Expt 3
Vehicle
5,5,5
5,5,5
5,5,4
5,4,3
0,0,0
Ibu cont
5,5,5
5,5,5
5,5,4
4,4,3
0,0,0
Ibu ATP1
4,3,1
4,2,0
2,1,0
1,0,0
0,0,0
Individual scores are presented for each mouse ie a result indicated as 5,4,3 is interperated as the first mouse having a severe burn, the second mouse a moderate to severe burn and the third mouse a moderate burn.
The results from these experiments indicate that ibuprofen-alanine-Tris-monopalmitate (Ibu-ATP1) has a protective effect on UVB induced burns to a much greater extent than unmodified ibuprofen. This was seen as an initial reduction in burn response and then a faster resolution of the burn yielding a normal epidermis. This result appears to be independent of oedema reduction as 2% ibuprotein (either as the conjugate or as the free drug) have little effect on oedema at this concentration. In addition indomethacin levels that prevent oedema appear to have little or no effect on burn repair.
Conclusion
NSAID-fatty acid conjugates alter the bioavailability of indomethacin and ibuprofen when applied topically. This change in bioavailability is possibly due, to a slow-release property which allows prolonged protection against UVB induced oedema. Ibuprofen-fatty acyl conjugates give enhanced burn protection by speeding burn recovery after acute UVB exposure.
The present inventors have shown that the nonsteroidal anti-inflammatory compound component of the compounds of the present invention retain their activity in the conjugates and that this activity is sustained and prolonged. As it is has been suggested in the scientific literature that nonsteroidal anti-inflammatory compounds may have anti-tumour activity it is believed that the compounds of the present invention may also find application in this area.
It will be appreciated by persons skilled in the art that numerous variations and/or modifications may be made to the invention as shown in the specific embodiments without departing from the spirit or scope of the invention as broadly described. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive.
References
1. Bissett, D. L., Chatterjee, R. and Hannon, D. P., 1990 . Photodermatol Photoimmunol Photomed , Vol 7:pp153-158.
2. Reeve, V. E., Personal communication.
3. Kaidbey, K. H. and Kurban, A. K., 1976 . J. Invest. Dermatol . 1976, vol. p153-156.
4. Snyder, D. S. 1975 . J. Invest. Dermatol ., Vol 64, pp322-325.
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The present invention provides therapeutic conjugates which comprise a therapeutic compound bound to one to three acyl groups derived from fatty acids. The therapeutic compounds are preferably non-steroidal anti-infiammatory agents which include a carboxylic acid group. The compounds involve the use of tromethamine or ethanolamine derivative to link the acyl groups derived from fatty acids to the therapeutic compounds.
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FIELD OF THE INVENTION
The present invention relates to gum manufacturing methods and systems and more particularly relates to the forming and conditioning of gum products as a precursor to dividing the gum into individual slab, stick or pellet type units.
BACKGROUND OF THE INVENTION
The process of making and packaging gum products involves a significant amount of machinery. For example, a substantially automated system and method for making slab/stick type gums, is shown in U.S. Pat. No. 6,254,373 entitled Gum Processing and Packaging System, which is assigned to the predecessor of interest of the present assignee. As shown in the '373 patent, a process and apparatus for the continued production and processing and packaging of a final slab/stick type chewing gum is disclosed. The product is extruded as a continuous tape or ribbon and is eventually flattened into an approximate final cross-sectional size and shape and then inserted into a final gum sizing apparatus. Thereafter, the continuous strip of final chewing gum product is scored, cut into individual pieces and individually wrapped by a standard packaging machine. The present invention is directed towards improvements in the state of the art over such prior systems and equipment as shown in the '373 patent.
BRIEF SUMMARY OF THE INVENTION
The present invention is directed toward improvements in the conditioning of chewing gum product to attempt to reach the optimal temperature, viscosity, and moisture content for quality and processing reasons, particularly when rolling and/or scoring the chewing gum product in sheet form. Such uniformity better insures that the correct amount of gum is in each individual unit of gum and that the shape, size and consistency is substantially the same. Achieving such uniformity and high volume production with such automation are a significant advantage for cost and quality reasons.
A first patent aspect of the present invention is directed toward gum manufacturing machinery comprising a gum loafing machine have an inlet receiving finished gum product and a forming die providing an outlet proximate a knife that is adapted to generate loaves of finished gum product. A gum conditioner is arranged downstream of the gum loafing machine that has a conveyor running through an environmental enclosure with a temperature control. The conveyor is adapted to convey the loaves of finished gum through the environmental enclosure.
According to the above aspect, the conveyor of the gum conditioner may include at least three conveyors arranged in a stacked vertical configuration with two different operational modes. In a first operational mode, the second conveyor runs in a first direction conveying loaves in a serpentine path over substantially the entire length of the second and third conveyors. In a second operational mode, the second conveyor runs in a second direction opposite the first direction to convey loaves in a cascading path thereby substantially bypassing the length of the second and third conveyors. As such, the residence time of the conveyor can be greatly varied by utilizing more or less of the overall gum conditioning conveyor length as may be desired (speed controls and speed changes to the conveyors may be additionally employed).
Another different feature which may be employed with the first above aspect is that the gum loafing machine may be employed to prepare a generally uniform shape and thickness of the finished gum product to facilitate more uniform conditioning and avoid the otherwise non-uniform and irregularly shaped thicknesses that may be output, for example from a gum mixing extruder that forms the finished gum product. The size of the loaves may be optimized for conditioning as opposed to a form that is necessarily suitable for rolling operations. Further, after the finished gum product is loafed and conditioned within the gum conditioner, a second forming extruder may be employed having a die adapted to form a continuous ribbon from the individual loaves to facilitate further downstream rolling of the sheet by rollers that progressively reduce a thickness of the continuous gum ribbon for subsequent gum dividing operations. As such, conditioning may occur in one form, while rolling and scoring is accomplished in a different form.
Another aspect of the present invention is directed toward gum manufacturing machinery comprising a gum mixer (e.g. at least one of a mixing extruder and a batch mixer) that receives a plurality of gum ingredients and mixes the gum ingredients into a finished gum product. A first forming extruder is arranged downstream of the gum mixer and receives the finished gum and forces the finished gum through a first forming die to generate a substantially uniform output shapes sufficient for conditioning. A gum conditioner is arranged downstream of the first forming extruder and has a conveyor running through an environmental enclosure with a temperature control. The conveyor is adapted to convey the substantially uniform output through the environmental enclosure. Further, and after such conditioning, a second forming extruder is arranged downstream of the gum conditioner that has a second forming die. The second forming extruder forces the finished gum through the second forming die to form a continuous gum ribbon. Rollers are subsequently arranged downstream of the forming extruder to progressively reduce a thickness of a the continuous gum ribbon for subsequent gum diving operations.
A feature according to the above aspect is that a first forming extruder may provide a discontinuous output such as separate loaves to facilitate conditioning whereas the second forming extruder produces the ribbon to facilitate rolling operations.
A further aspect of the present invention is directed toward a method of manufacturing gum comprising of mixing a plurality of gum ingredients into a finished gum; forming the finished gum into a substantially uniform output shape; conditioning the formed finished gum in a controlled temperature environment for a residence time; forming a continuous gum ribbon; progressively reducing the thickness of the continuous gum ribbon; and dividing the gum ribbon into individual pieces of gum.
It is an advantage of this method and further feature that different gum batch recipes for different finished gum products may be run through the same gum line. For example, the method may further comprise running a first gum mixture at a first predetermined residence time for conditioning in a controlled temperature environment; and running a second gum mixture different than the first gum mixture using the same gum line as for the first gum mixture but at a second residence time different than the first residence time for the first gum mixture. This can be further facilitated by use of a conveyor having multiple vertically spaced conveyors with two different operational modes for generating a serpentine path and a cascading path as described previously. Significantly different conditioning residence times may therefore be employed for different gum batch recipes.
Other aspects, objectives and advantages of the invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings incorporated in and forming a part of the specification illustrate several aspects of the present invention and, together with the description, serve to explain the principles of the invention. In the drawings:
FIG. 1 is a schematic diagram of an embodiment of gum manufacturing machinery illustrating one operating mode with a cascading path of loaves through a gum conditioner in accordance with an embodiment of the present invention;
FIG. 1A shows a schematic diagram of an alternative embodiment for mixing gum that may be substituted for the mixing extruder shown in FIG. 1 ;
FIG. 2 is another schematic diagram of the embodiment shown in FIG. 1 but illustrated in a different operational mode with loaves spending a longer residence time with a serpentine path through the gum conditioner as illustrated; and
FIG. 3 is a flow diagram illustrating a process for handling and processing finished gum product in accordance with an embodiment of the present invention.
While the invention will be described in connection with certain preferred embodiments, there is no intent to limit it to those embodiments. On the contrary, the intent is to cover all alternatives, modifications and equivalents as included within the spirit and scope of the invention as defined by the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
Referring to the FIGS. 1-2 , gum manufacturing machinery generally indicated at 10 for handling and processing finished gum product 12 is illustrated with, methodology of running through such machinery diagramed in FIG. 3 .
The gum manufacturing machinery 10 generally includes a gum mixer which as illustrated in FIG. 1 may take the form of a gum mixing extruder 14 ; or alternatively as shown in FIG. 1A a batch mixer 16 . Each of these may be used to produce a finished gum product 12 . For example as illustrated in FIG. 1 , the gum mixing extruder 14 includes a plurality of gum ingredient inputs 20 along its length for receipt of gum base and other gum ingredients such as flavorings, sugars, sweeteners, fillers, various agents, and the like. These inputs 20 are arranged along the length of a single mixing screw 22 having different screw mixing elements for input and mixing at different stages during the mixing process. For example, gum mixing extruders or other gum mixers are disclosed for example in U.S. Provisional Patent Application Nos. 61/016,016; 61/036,626; and 61/045,764, which are assigned to the present assignee, the disclosures of which are hereby incorporated by reference in their entireties. The output from the gum mixing extruder 14 is a finished gum product 12 that is readily suitable for consumption and chewing as it includes the water soluble sweeteners and flavorings desired by the consumer as well as the underlying chewable gum base to facilitate chewing. As illustrated, the output from a gum mixing extruder 14 may be generally irregular or otherwise non-uniform in shape in that it often will be output in an uneven stream of material having a non-uniform thickness of material. The same can be said of the output of a batch mixer 16 in that it is generally irregularly shaped without a consistent thickness. Thus, by producing finished gum product 18 , it may generate a non-uniform output 24 as diagrammed in FIG. 3 .
Given that the temperature of the finished gum product is not yet suitable or optimal for rolling activities, and that the temperature may need to be cooled or otherwise adjusted to allow the material to set sufficiently, it can be appreciated that the non-uniform output 24 is not conducive to generating uniform conditioning of the finished gum product. As such, a feed conveyor 26 feeds the uneven output 12 into a loafing machine 28 (also referred to herein as a loafing extruder) that forms discrete loaves of finished gum product as in step 27 in FIG. 3 . The loafing machine 28 may include a forming extruder 30 that forces the finished gum product through a forming die, thereby forming a uniform extrusion 33 as in FIG. 3 , that is periodically cut off into separate loaves 34 with finished gum product loaves being indicated at 36 in FIGS. 1-2 . To facilitate the cutting operation 34 , a knife 32 is used that periodically moves laterally across the forming die to cut and slice off individual loaves 36 .
An output conveyor 38 picks up the loaves cut off from the forming extruder 30 and runs at a slightly faster pace so as to space the individual loaves 36 at regular intervals as they are output from the forming extruder 30 and cut off by knife 32 . The forming extruder 30 includes only a single input and does not provide for input or mixing of additional ingredients into the finished gum product at this stage. Instead the loafing machine 28 and forming extruder 30 is merely employed to generate a relatively uniform and consistent thickness of material to facilitate more even conditioning of the finished gum product downstream.
As illustrated, the individual loaves 36 generally take the shape of the extruding die at the output of the forming extruder 30 and may have separate loaves integrally connected by thin webs that may be produced by teeth on the extruding die as illustrated. The loaves may have a slight parallelogram shape or be of slight shape variations in width and length, but the thickness of the individual loaves 36 is preferably between about ½ and 2 inches thick (vertically) with the length and width being between about 6 inches and 18 inches. The length and width dimensions are not as critical or important as it is the minimum thickness in one dimension that controls heat transfer. Thus, the minimum thickness dimension is of importance as this determines the relative residence time necessary for achieving sufficiently uniform viscosity and temperature for forming a thin ribbon to facilitate subsequent rolling and scoring operations.
The output conveyor 38 feeds the individual loaves 36 into a gum conditioner 40 that conditions the loaves of finished gum product 42 . More specifically, the gum conditioner 40 adjusts or otherwise conforms the temperature of the finished gum product 12 and attempts to obtain a substantially uniform temperature throughout. The gum conditioner 40 is arranged downstream of the gum loafing machine 28 for receiving the output thereof and includes three vertically stacked conveyors including a top conveyor 44 , an intermediate conveyor 46 and a bottom conveyor 48 that are all substantially contained and run through an environmental enclosure 50 , such as a long enclosed tunnel. Each of the conveyers 44 , 46 , 48 is contained in the environmental enclosure 50 , such that the gum product carried thereon is subjected to the temperature and humidity controlled environment within the enclosure 50 .
The gum conditioner 40 includes a temperature control, a humidity control and a residence time control. The temperature and humidity control can set and/or adjust the temperature and humidity within the environmental enclosure such that it may be different than that of the room in which the machinery is contained. The residence time control is provided with a wide degree of residence time variability in part due to speed adjustment but also due to a unique aspect presented by the arrangement of three conveyors, 44 , 46 and 48 and the operational mode variance as illustrated when comparing FIGS. 1 and 2 . As a result, a residence time can be predetermined and set and/or adjusted based upon the gum batch recipe 52 as indicated in FIG. 3 .
Typically, and depending upon the finished gum product, the raw output of the gum mixing extruder 14 will generally produce a gum output having an average temperature between 40 and 50° C. Within the environmental enclosure 50 of the gum conditioner 40 a generally uniform temperature is controlled to move the finished gum temperature to a substantially consistent and desirable temperature. Specifically, the environmental enclosure 50 may include a controlled temperature between 40° C. and about 50° C.; and a humidity of between about 20 and about 40%. Typically the temperature and humidity will be set at predetermined set points within those ranges depending upon the gum recipe and batch that is being run through the gum line at any particular instant.
As for the residence time, the embodiment provides for a wide control possibility in residence time based on speed control and operational mode. In one embodiment, the residence time may be as fast as about two minutes and as slow as about 20 minutes to provide for a minimal residence time or a very long residence time depending upon the gum batch recipe to appropriately provide the gum in best condition for later processing, such as rolling and scoring into sheets. The conditioner preferably has a residence time control variance of at least 10 minutes during operation thereof that is at least about 1 minute and less than about 30 minutes.
As can be seen in comparing FIGS. 1 and 2 , the gum conditioner 40 has two different operational modes. As shown in FIG. 2 , a first operational mode is provided in which the loaves follow a serpentine path substantially over the entire length of the intermediate and bottom conveyors, 46 and 48 . By having to travel the entire length of the lower two conveyors, the residence time is increased by virtual of the distance over which the finished gum product loaves must travel. However, if such a long residence time is not desired or needed, the distance can be short circuited as shown in FIG. 1 where a second operational mode is provided in which the loaves substantially bypass the length of the second and third conveyors. In this operational mode, the intermediate conveyor 46 runs in an opposite direction as that shown in FIG. 2 to prevent the loaves from reversing direction and instead the loaves cascade over the conveyors with a cascading path, thereby to substantially bypassing the length of the second and third conveyors. As shown, the second intermediate conveyor 46 has a portion that overlaps the top conveyor 44 to receive loaves that vertically drop down from the top conveyor onto the intermediate conveyor and likewise the bottom conveyor 48 has ends that overlap both of the ends of the intermediate conveyor for receipt of loaves that drop down on either the front or back end of the intermediate conveyor depending upon which operational mode is employed.
Depending upon the gum recipe batch being run on the gum line, upon exiting the gum conditioner, the finished gum loaves may have a temperature of between about 40 and 50° C. However, residence time is important and formula dependent to develop crystal structure and/or otherwise set up the firmness of the gum product, even if little or no temperature change occurs. At this point, the loaves are also set up enough with a sufficiently uniform viscosity to facilitate further processing such as rolling and scoring.
Accordingly at this point, a further conveyor 54 feeds the finished gum product loaves (at step 56 in FIG. 3 ) into a second downstream forming extruder 58 . The forming extruder 58 includes a forming die that is thin and elongated such that it produces a continuous finished gum product ribbon (at step 57 in FIG. 3 ) suitable for subsequent rolling and scoring operations. Specifically, the forming extruder 58 may include twin screws that break up the loaves and force the loaves through an elongate and thin forming die to produce the ribbon 60 .
Upon exiting the forming extruder 58 , the continuous gum ribbon 60 may be subject to a dusting operation 62 in which a duster 64 sprinkles powdered sweetener on the surface of the continuous gum ribbon 60 so as to prevent sticking and to facilitate better processing during subsequent rolling and scoring operations. It is understood that while such dusting will add some component to the eventual packaged gum, a “finish gum product” is considered to be produced at the very first step illustrated in the output of the gum mixing extruder 14 and the dusting at this point is primarily a processing aid adding only some additional component to the gum.
After passing through the duster 64 , the gum ribbon 60 is processed and run through a series of progressive rollers 66 that roll the continuous ribbon sheet to a uniform reduced thickness 68 . Once the gum ribbon 60 is progressively rolled to the desired thickness, then a scoring roller 70 may be employed as well as a lateral dividing roller 72 . These rollers 70 , 72 score and divide the gum ribbon 60 into individual scored sheets 74 as indicated at step 76 in FIG. 3 .
From here, the scored sheets 74 are conveyed to a further gum conditioner 78 having a conveyor 80 and an environmental enclosure in the form of a tunnel 82 to facilitate cooling of the individual scored sheets to stiffen the gum material of the sheets sufficiently prior to stacking so as to maintain shape rather than allow material creep. The gum conditioner 78 conditions individual sheets 84 sufficient to facilitate stacking of sheets 86 where the sheets can be stacked and stored in a conditioning room 88 . The stacked sheets are then stored in the conditioning room 90 at a lengthy interval to fully condition the gum sheets and achieve a sufficiently cool temperature until such time that the sheets are ready to be divided into individual gum pieces such as stabs or sticks and then packaged as indicated in step 92 in FIG. 3 .
All references, including publications, patent applications, and patents cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) is to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.
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Gum manufacturing machinery and method of manufacturing gum is illustrated in which a gum loafing machine generates loaves of finished gum that are then subsequently run through a gum conditioner to more uniformly set the temperature and viscosity of the gum material prior to further processing. Upon achieving the appropriate conditioning level, a further forming extruder may be used to generate a continuous gum ribbon for subsequent rolling and scoring operations. The gum conditioner may include vertically stacked conveyors that have different operational modes including a first mode that provides a serpentine path for a long residence time and a second mode that provides a cascading path that avoids or bypasses much of the length of some of the conveyors to provide a shorter residence time. The gum manufacturing machinery may be used in an adjustable manner so as to accommodate difference gum recipes for different batches of gum product.
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[0001] This application claims priority based on co-pending U.S. application Ser. No. 60/569,093, filed May 7, 2004, inventor Radi Al Rashed, of same title.
FIELD OF THE INVENTION
[0002] The instant invention relates to low-viscosity, silicone-modified penetrating asphalt sealers, to methods of production thereof and to methods for using the sealers to treat and protect, in particular, heavy traffic asphalt pavement on a large scale against water-associated problems.
BACKGROUND OF THE INVENTION
[0000] Introduction
[0003] Asphalt pavement, comprising asphalt coated particles bound by the asphalt, is known to be highly porous. The porosity exists in the form of pores connected through capillary channels formed in part during the compaction process. The pores and channels are affected by variations in aggregate size, and are formed in part because of an entrapment of solvent during the curing process. Fatigue caused by expansion and contraction due to heat variation also creates gaps between particles within a pavement matrix. These gaps may develop into cracks if not treated. The oxidation process of asphalt coated particles and the exposure to UV light are also known to cause further damage to bonds between asphalt and aggregate, which damage increases porosity as aggregates at the surface become loose.
[0004] The presence of pores and capillaries allows water penetration, a phenomenon that causes additional damage to asphalt pavement. Water reduces the bonding strength between the asphalt and the gravel or any other material under the pavement. Water penetration allows the penetration of chloride ions from deicing salts, a chemical that attacks the asphalt matrix and shortens its life. In addition, freeze and thaw spalling and chipping becomes a problem in asphalt pavement in cold climates because of the fatigue and internal stress build-up due to the expansion of water upon freezing.
[0000] More Particularly Asphalt and Water
[0005] Water penetration through asphalt pavement may cause severe damage to the bonding strength between asphalt and aggregate. Water penetrates because of its unimpeded ability to move freely through capillaries and connected pores and voids. Typically, asphalt pavement is 13% to 20% voids. The typical aggregate to binder ratio is 10/1.
[0006] Because of its ability to move freely through capillaries and connected pores and voids, water causes severe damage to asphalt pavement by several mechanisms. Water or moisture results in a breaking of the bonds between asphalt particles and aggregates. This in turn results in a weakening of the pavement and making it susceptible to problems that lead to a loss in strength and durability. Detachment, wherein a thin film of water results in the separation of an asphalt film from an aggregate surface without breaking the bond, has a high potential because of the ability of water to wet the aggregate surface more than the asphalt binder, due its lower surface tension. This phenomenon generally starts at the surface of the pavement and gradually moves downward as it develops to displacement, a condition where the asphalt film ruptures and the bonds between the asphalt and the aggregate break, which may appear in the form of loose aggregates. See references.
[0007] Under wet conditions, repeated traffic and load applications result in the entrapment of water inside tiny pores. The entrapment leads to distress and continued buildup in pore pressure resulting in disrupting the asphalt film from the aggregate surface, which causes the formation of cracks.
[0008] In cold climates, where repeated cycles of freezing and thawing occur, asphalt pavement with sufficient moisture is particularly susceptible to additional damage. When the temperature drops below the freezing point ice starts to form within the pores and capillaries of the pavement. Since water volume increases by 9% upon on freezing, if water is confined in the pores between freezing bodies and placed under compression, the pores may dilate causing an increase in the internal stress against the surrounding pavement particles. Repeated freeze and thaw cycles can result in the rupture and deterioration of the asphalt pavement due to fatigue stresses. Such deterioration may appear in the form of cracks and surface spalling. With time, fatigue stress can cause big chunks of the pavement to pop out.
[0009] The penetration of water can be greatly influenced by the use of de-icing salts such as sodium chloride granules in cold climates. The concentration of such material within the pavements pores and voids increases with time. The result is an increase in the osmotic pressure, allowing more water to be absorbed under wet conditions at moderate temperatures.
[0000] Oxidation of Asphalt
[0010] The rate of oxidation of asphalt pavement is highly dependent on the voids in the total mixture. If the voids in the total mixture can be brought below 7-8% in-place, however, then the effect of oxidation will be greatly minimized. During the oxidation reaction, asphalt loses a significant amount of its saturate and aromatic components, which causes the asphalt mixture to stiffen at low temperatures, resulting in further crack formation.
[0000] Current Art Techniques
[0011] Maintenance of most asphalt pavements involves repairing localized problem areas, such as potholes or badly cracked pavement sections, and in sealing cracks. This type maintenance is needed to prolong the pavement life and to prevent rapid damage to the pavement due to water penetration and other causes. Some problems with asphalt pavement can be prevented or delayed by using good maintenance practices. Currently, there are three different maintenance methods commonly used: rejuvenators, slurry seals, and surface treatments. The choice between the methods mainly depends on the specific project to be maintained.
[0012] Asphalt sealers currently available in the market are typically intended for use on low traffic asphalt pavement as a protective seal coat of a film-forming nature, which sealcoat acts as a “barrier coat” to protect the asphalt surface. There are two primary types: those made from refined coal tar and those made from asphalt. Refined coal tar—a by-product of the coking process—is complex mixture of thousands of chemicals and has different molecular structure in general from asphalt. The coal tar molecules have a predominantly closed ring (aromatic) structure with a minor degree of un-saturation. Because of their stable molecular structure, the destructive elements of weather and chemicals do not particularly affect the properties of coal tar. Sealcoatings based on a refined coal tar were introduced in the 1950s and until recently have been used extensively to protect off-street pavements. These sealcoatings often are referred to as C.T.P.E (Coal Tar Pitch Emulsions,) denoting that these coatings are water based, obtained by dispersing refined coal tar in a matrix of clay and water. In recent years, asphalt emulsion-based coatings have been introduced with varying degrees of success. In fact, many sealer manufacturers that previously produced only refined coal tar sealers now also produce asphalt-based sealers or even asphalt/refined coal tar blends. The asphalt emulsion based coatings deliver most of the same properties as refined coal tar-based coatings—except for a resistance to color fading due to ulrraviolet degradation and for a resistance to salts and petrochemicals like oils, fats, grease and solvents. These deficiencies are inherent in the asphalt binder itself. Being a petroleum derivative, asphalt has a natural affinity for petrochemicals, so it is easily dissolved by them. Asphalt emulsion-based coatings are made using either a soap emulsion (SS-1-H, for example) or a clay stabilizing emulsion. In recent years, asphalt sealer manufacturers have been quite successful in refining the performance of asphalt emulsion based sealers by using specialty chemicals and pigments. However, the asphalt emulsion-based coatings resistance to petrochemicals and solvents—while improved—has yet to be overcome.
[0013] Silicone-based chemicals have been tested and used as additives to asphalt products to enhance the bonding properties between aggregates especially in cold applied patching and repair materials. Ward, Jr. (U.S. Pat. No. 4,373,960, U.S. Pat. No. 4,453,980, and U.S. Pat. No. 4,479,827) utilizes an organopolysiloxane material with non-emulsified asphalt to produce an asphalt-based binder that is to be mixed with pre-heated aggregates prior to application as a patching material for deteriorated pavements. In his inventions, the organopolysiloxane was at most 0.05% by weight, sufficient to enhance the products free flowing properties.
[0014] A special blend of topped-coke-oven tar and aromatic solvent was introduced by McGoven (U.S. Pat. No. 4,661,378) as a penetrating sealer and rejuvenator for deteriorated asphalt pavements as well as for concrete surfaces. McGoven claimed that such material might penetrate up to 0.4 inch into asphalt pavement when applied on low-traffic pavement at a rate of 0.13 gallon/square yard. However, for heavy traffic asphalt pavement, such as roads, it had to be mixed with sand, pozzolana, or other fine mineral aggregates, which makes a slurry coat having more body than desired as in the case of conventional slurry-seal materials. A similar form of surface treatment consisting of an asphalt emulsion, diatomite, and sand that can be applied under ambient temperature using conventional paving machinery was invented by Kietzman (U.S. Pat. No. 4,548,650), where the filler diatomite to asphalt ration is in the range of 0.008 to 0.3 by weight. In addition to its overlay uses, Kietzman claimed that this material (with a little modification to improve its abrasion resistance, adhesion/cohesion, and tensile strength) could be used as a protection membrane for bridge decks and roads.
[0015] In summary, conventional asphalt sealers currently available in the market have several defects. They are typically surface treatments. In addition to a lack of providing internal protection due to the high viscosity of the surface treatments, which does not allow them to penetrate, they may be considered a non-permanent treatment since they tend to wear-off the surface because of traffic. Because of their film-forming nature combined with their tendency to remain on the surface, these surface treatments cannot be used on roads and highways where slipperiness and skid resistance are of great concern unless they are broadcast with fine aggregates while wet or pre-mixed with fine aggregate in slurry form. This makes the treatment process itself less economical, due to the low coverage rate and frequent shut-down times.
[0016] Sealing heavy-traffic asphalt pavements with a penetrating sealer, including an oxidized asphalt cutback that has been modified with a silicone-based compound that permanently provides internal as well as surface protection, to make a heavy-traffic asphalt pavement more durable, has never been taught, disclosed or practiced to applicant's knowledge, prior to the instant invention. There is a need for a new technology that more thoroughly addresses treatment problems for asphalt pavement in a cost-effective mater.
SUMMARY OF THE INVENTION
[0017] The present invention discloses a complex solvent-based mixture of several ingredients or active chemicals. The mixture was developed for the purpose of essentially eliminating water penetration into asphalt pavement from the surface, through utilizing a chemical repelling agent, as well as for the purpose of eliminating the transmission of water through the asphalt pavement while allowing vapor transmission (breathing).
[0018] The invention is intended for the treatment and protection of heavy traffic asphalt pavement, such as found in bridges, highways, airport runways and taxiways, in a single application that results in an essentially maintenance free and worry free construction when it comes to water, oxidation, and UV problems. The invention should prolong the asphalt service life.
[0019] In accordance with aspects of the present invention, there is provided a composition including a well-balanced mixture of ingredients or chemicals for achieving the above objective(s) and solving the above problem(s). Some of the ingredients or chemicals act independently while the rest work in conjunction with each other via chemical reactions to achieve the goal of the treatment.
[0020] The chemical and physical functionality of ingredients or chemicals of preferred embodiments of the present invention can be summarized as:
Petrochemically compatible surfactant (Preferably Nonylphenol polyethylene Glycol Ether:) behaves as a wetting agent to reduce the surface tension of the mixture and, thus, to allow the product to penetrate more deeply through capillaries of the pavement. Preferably an Antifoaming agent (such as isopropyl alcohol): reduces bubble formation and thus tends to eliminate air entrapment within the solution during manufacturing and application. Active Silicone Compound Providing a Water Repellent and Asphalt Reactant (preferably Methyltrimethoxysilane (CH 3 O) 3 SiCH 3 and/or Dimethyldimethyloxysilicone:) reacts with inherent water to form a siloxane resin which permanently adheres to the surface and inner surface of capillaries and voids, resulting in enlarged asphalt molecules and a significant increase in the surface tension of water, there by inhibiting water from penetrating through remaining capillaries. Fillers, to fill voids and pores of pavement (preferably a combination of very fine Graphite Powder and oxidized asphalt cutback). Fine graphite powder was found to be very effective (if having a mesh size less than 200) in sealing tiny voids, thus eliminating water from generating high pore pressure under wet conditions. More importantly a highly oxidized asphalt cutback (19K from Lion Oil) was found to be a most suitable filler and oxidized asphalt for this invention. Petroleum-based solvent as a carrier preferably a Stoddard solvent.
[0026] The present invention is recommended for the treatment and protection of large-scale heavy traffic asphalt pavement, mainly bridges, asphalt highways, airport runways, taxiways, and parking garages. Application of the invention is preferably through a spraying and a mechanical brushing mechanism, the spraying mechanism being adequate to spray large areas in a short period of time. The recommended coverage of the invention is 100 to 110 ft 2 /gallon in a single one-time application. The application may not require more than 1 hour of closure time, since the very low viscosity of mixture allows it to penetrate very quickly leaving only traces at the surface.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] A better understanding of the present invention can be obtained when the following detailed description of the preferred embodiments are considered in conjunction with the following drawings, in which:
[0028] FIGS. 1 and 1 A illustrate the invention's performance;
[0029] FIG. 2 illustrates application techniques;
[0030] FIGS. 3A, 3B and 4 illustrate an application machine.
[0031] The drawings are primarily illustrative. It would be understood that structure may have been simplified and details omitted in order to convey certain aspects of the invention. Scale may be sacrificed to clarity.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0032] It has been discovered that an oxidized asphalt cutback provides an excellent filler for an asphalt pavement sealer and treatment material. Preferably the oxidized asphalt cutback is combined with a fine graphite powder to form an emulsion that can lead to a significant reduction in the porosity of asphalt pavement by partially filling the voids and pores of the pavement. When coupled with a formed siloxane resin, the mixture results in strengthening of the adhesion between the existing asphalt material and aggregate as well as between any oxidized bitumen particles, functioning as a substitute for lost aromatic compounds of the pavement. The mixture tends to eliminate further oxidation of the asphalt material. As a result of partially sealing voids and capillaries, some moisture transmission is eliminated. Embodiments of the invention can act as a further moisture barrier by coating the surface of exposed aggregate, preventing moisture from being absorbed therein, especially in the case of limestone aggregate, which is commonly used in asphalt pavements.
[0033] A further preferred aspect of the present invention includes an active silicone compound providing a solvent soluble water repellant and asphalt reactant. Preferrably the silicone compound includes Methyltrimethoxysilane (CH 3 O) 3 SiCH 3 ), and/or Dimethyldimethyloxysilane. Methyltrimethoxysilane and Dimethyldimethyloxysilane are chemical monomers that slowly react with water in the pavement and atmosphere to form an invisible film of siloxane resin which permanently adheres to the surface and inner surface of capillaries and voids. Under wet conditions, the siloxane resin functions as a water repellant by significantly increasing the surface tension of water to such a degree that it is essentially impossible for water to penetrate through remaining capillaries of a treated asphalt pavement. As a result, the siloxane resin maintains a dry surface that effectively resists the damage typically caused by freezes and thaws.
[0034] The performance of the protection process for preferred embodiments of the present invention is believed to be enhanced by the presence of Nonylphenol polyethylene Glycol Ether as a petrochemically compatible surfactant, by virtue of which the viscosity of the chemical mire can be reduced to about 12% of that of the asphalt cutback itself at room temperature.
[0035] Embodiments of the current invention have been tested by Construction Technology Laboratories, Inc. (CTL) to investigate their effect on skid resistance, using two different standard methods. First, the ASTM E303-93 “Standard Test Method for Measuring Surface Frictional Properties Using the British Pendulum Tester” measures the “British Pendulum Number (BPN).” Secondly, the ASTM F609 “Standard Test Method for Static Slip Resistance of Footwear, Sole, Heel, or Related Materials by Horizontal Pull Slip Meter (HPS)” measures the friction coefficient. A sample of the invention was applied to three different areas on an existing asphalt pavement. The tests were performed on those areas as well as on three different areas that were left untreated as controls. Results of both tests indicate that the areas treated with the current invention had British Pendulum Numbers and coefficients of friction comparable to those results obtained from the tests on untreated areas.
[0036] A preferred embodiment of a present invention is formulated by combining six different chemicals in a liquid form. To our knowledge, an optimum quantitative chemical composition of the invention can be achieved if the mixture is prepared using the data given in Table 1 on a weight basis. Such a composition will provide a solution of about 55% solids content that has a very low viscosity of 90 centipoises at 77° F. to assure deep penetration.
TABLE 1 Optimum chemical composition of the invention. Chemical Name wt. % Graphite Powder (<200 mesh) 4.055 Oxidized Asphalt Cutback (60% Solids) 85.230 Isopropyl Alcohol (Anhydrous) 2.033 Nonylphenol Polyethylene Glycol Ether (pure) 0.045 Methyltrimethoxysilane (CH 3 O) 3 SiCH 3 ) 4.572 Stoddard solvent 4.065 Total 100
[0037] Altering the chemical composition of the above invention by adjusting the weight percentages of one or more of the chemical ingredients, to a certain degree, will not have a great effect on the overall performance of the invention, especially as long as the method of application is adjusted accordingly. For instance, a reduction in the solids content would result in a diluted form of the invention. In such case, the material should be applied to the asphalt pavement at a higher rate.
[0038] The overall performance of the invention in treating heavy traffic asphalt pavements should be acceptable if the content of the chemicals remain within the ranges given in Table 2.
TABLE 2 Minimum and maximum weight percentage of chemicals through which the invention will remain effective. Minimum Maximum Chemical Name wt. % wt. % Graphite Powder (<200 mesh) 0.000 8.000 Oxidized Asphalt/Cutback Emulsion (60% Solids) 75.000 90.000 Isopropyl Alcohol (Anhydrous) 0.500 3.500 Nonylphenol Polyethylene Glycol Ether (pure) 0.001 0.200 Methyltrimethoxysilane (CH 3 O) 3 SiCH 3 ) 3.000 6.000 Stoddard solvent 2.000 8.000
[0039] Preferred production processes for the present invention utilize a multi step mixing of the chemicals to minimize interactions that may cause the material to coagulate during manufacturing. For this purpose, a reactor vessel with a high-speed sheer mixer is preferably utilized to maintain the product in an emulsion form, thus minimizing the settling of solid particles.
[0040] Although, the invention may also be produced in fewer steps, with certain precautions, to our best knowledge the chemicals are preferably mixed in three different stages for the preferred embodiment. The product of the first stage is called the “Base Emulsion”. The product of the second stage is called the “Catalyst”. Both the “Base Emulsion” and the “Catalyst” are considered as intermediate products for the purpose making the finished product.
[0041] Disclosed below is a preferred procedure as well as, to our knowledge, the best chemical composition for making the preferred embodiment of the invention in its ready-to-use form.
[0000] Stare One: Making of the “Base Emulsion”
[0042] Batch size=1000 US Gallons, Net weight=7818.9 LB
TABLE 3 Materials required for the manufacturing of a 1000 gallons of Base Emulsion Chemical Weight (LB) Oxidized Asphalt Cutback (60% Solids) 7463.8 Graphite Powder (<200 mesh) 355.1 Total Weight 7818.9
Mixing Procedure
[0043] 1. Place the asphalt cutback in the mixing vessel and start the mixer at a medium speed.
[0044] 2. Add the graphite powder gradually. Do not add more than 20% at a time.
[0045] 3. Increase the mixing speed to about 1500 rpm and mix for 10 minutes before adding the next portion of the graphite powder.
[0046] 4. Repeat steps 2 and 3 until all the graphite powder is consumed and continue mixing for 30 minutes.
[0047] 5. Cover the mixing vessel and allow the material to cool to room temperature and settle for 24 hours before using in the production of the concentrate.
[0000] Stage Two: Making of the “Catalyst”
[0048] Batch size=1000 US Gallons, Net weight=7449.7 LB
TABLE 4 Materials required for the manufacturing of a 1000 gallons of the Catalyst Chemical Weight (LB) Stoddard solvent 2826.2 Isopropyl Alcohol (Anhydrous) 1413.5 Nonylphenol Polyethylene Glycol Ether (pure) 31.3 Methyltrimethoxysilane (CH 3 O) 3 SiCH 3 ) 3178.7 Total Weight 7449.7
Mixing Procedure
[0049] 1. Place all the Stoddard solvent in the reactor and start the mixer at a low speed.
[0050] 2. Gradually add the Isopropyl Alcohol and mix for about 10 minutes.
[0051] 3. Add the Nonylphenol Polyethylene Glycol Ether and mix for 10 minutes.
[0052] 4. Gradually add the Methyltrimethoxysilane and continue mixing for an additional 15 minutes.
[0000] Stage Three: Making of the “Finished Product”
[0053] Batch size=1000 US Gallons, Net weight=7777.6 LB
TABLE 5 Materials required for the manufacturing of a 1000 gallons of a Preferred Embodiment of the Invention in its ready-to-use form. Chemical Weight (LB) Base Emulsion 6944.20 Catalyst 833.37 Total 7777.57
Mixing Procedure
[0054] 1. Place the exact amount of the Base Emulsion in the mixing vessel and start mixing a medium speed.
[0055] 2. Weight the exact amount of the catalyst in a separate container then add it in three steps to the mixing vessel. Allow at least 5 minutes of mixing between portions.
[0056] 3. Increase the mixing speed gradually to 1500 rpm, and mix for 10 minutes.
[0057] 4. Repack in 5-gallon pails or 55-gallon drums and seal well.
[0000] Method Of Application
[0058] To our best knowledge, the preferred embodiment of the invention should be applied at a coverage rate of 1 gallon per 100-110 square feet. The preferred method of application, such that the invention can effectively penetrate into the asphalt pavement, would be as follows:
[0000] Heavy-Traffic Areas
[0059] For heavy-traffic asphalt pavement, such as roads, bridges, and highways, the material is best mechanically brushed at the surface, in order to prevent it from accumulating at the surface, especially between surface aggregates. Brushing tends to eliminate the forming of small pools, hence maintaining the slip-resistance of the surface ( FIG. 2 ).
[0060] An application machine has been specially designed for this purpose, by which machine a preferred embodiment of invention is sprayed at the surface of the pavement and then forced inside the pavement by a cylindrical brush rotating at a high speed (see below.)
[0061] For the invention to effectively penetrate into the pavement, the surface is preferably first cleaned and freed from any contaminants that might block the material from penetrating through the surface openings. The pavement may be cleaned using the same mechanical brushing system in a single pass prior to applying the invention to the surface.
[0000] Low-Traffic Areas
[0062] For low-traffic asphalt pavement, such as parking garages, sidewalks and driveways, the material can be applied by either spraying or rolling. However, it is preferable that the surface be cleaned first, and dry. Cleaning can be achieved by using high-pressure compressed air, for instance, which removes dust, loose particles and other contaminants that might prevent the invention from penetrating.
[0000] Application Machine
[0063] An application machine of a trailer type ( FIG. 3 ) has been specifically designed for the purpose of applying preferred embodiments of the invention on heavy-traffic asphalt pavement, where it efficiently forces more material into the pavement and eliminates accumulation at the surface. It comprises essentially a computerized spraying mechanism and a mechanical brushing system powered hydraulically by a gasoline engine.
[0064] As part of the spraying mechanism, a radar sensor is installed to measure speed. The sensor sends a signal to a programmable controller that adjusts the flow rate of the material via a sinusoidal valve as a function of the vehicle speed (2-9 miles/hour), thus maintaining a desired coverage rate through an 8-feet wide spraying bar that uniformly sprays the material through nine evenly spaced nozzles.
[0065] The brushing system is hydraulically driven and equipped with a hydraulic load-control to enhance the penetration process by applying pressure at the surface. While rotating at high speed (100-500 rpm) in the opposite direction to the wheels, the bristles of the rotary brush continuously sweep any excess material between surface aggregates and evenly distribute it at the surface.
[0066] As a maintenance measure, a flushing system can be added to the machine in order to clean the spraying mechanism (pump, valves, and pipes) from any residue after each application, thus preventing clogging. A detailed schematic diagram of the application is illustrated in FIG. 4 .
[0067] In preferred embodiments of the present invention, these active ingredients and chemicals are combined together through a multi-stage manufacturing process to produce a unique product that is able to solve water-associated problems in asphalt pavement permanently by a double action technique that maintains the pavement essentially internally dry. Although the present invention is of a penetrating nature, its water repelling efficiency exceeds the established federal specifications. Its internal waterproofing technology is superior because it waterproofs internally as well as at the surface.
[0068] Once fully cured, the present invention maintains a uniform black color across treated pavement with a non-shine (matt) look that tends to eliminate reflection of sunlight during the day or headlights at night.
[0069] The foregoing description of preferred embodiments of the invention is presented for purposes of illustration and description, and is not intended to be exhaustive or to limit the invention to the precise form or embodiment disclosed. The description was selected to best explain the principles of the invention and their practical application to enable others skilled in the art to best utilize the invention in various embodiments. Various modifications as are best suited to the particular use are contemplated. It is intended that the scope of the invention is not to be limited by the specification, but to be defined by the claims set forth below. Since the foregoing disclosure and description of the invention are illustrative and explanatory thereof, various changes in the size, shape, and materials, as well as in the details of the illustrated device may be made without departing from the spirit of the invention. The invention is claimed using terminology that depends upon a historic presumption that recitation of a single element covers one or more, and recitation of two elements covers two or more, and the like. Also, the drawings and illustration herein have not necessarily been produced to scale.
REFERENCES
[0070] 1 Majidzadeh, K. and Brovold, F. N., “ Sate of the Art: Effect of Water on Bitumen - Aggregates, ” Special Report 98, HRB, National Research Council, Washington, D.D. (1968)
[0071] 2 Fromm, H. J., “ The Mechanisms of Asphalt Stripping from Aggregate Surfaces, ” Proc., Association of Asphalt Paving Technologists, Vol. 43, pp. 191-223 (1974)
[0072] 3 Bhairampally, R. K., Lytton, R. L., and Little, D. N., “ Numerical and Graphical Method to Assess Permanent Deformation Potential for Repeated Compressive Loading of Asphalt Mixtures, ” Journal of the Transportation Board, No. 1723, National Research Council, Washington, D.C. (2000)
[0073] 4 Mack, C. “Bituminous Materials,” Vol. 1, Interscience Publishers, New York (1964)
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A solvent-based solution including methods of making and using for treating and protecting for heavy traffic asphalt pavement, particularly against water-associated problems, such as repeated freeze/thaw cycles, and damage caused by exposure to UV light. The mechanism of protection include an internal coating and partial internal sealing of voids and pores with a special blend of pre-oxidized asphalt emulsion that has been modified with moisture-insensitive silicone-based compounds and surfactants to enhance penetration depth and effectiveness. The sealer works from within the asphalt pavement as well as at the surface. A water-repelling function prevents water from penetrating from the surface while allowing vapor transmission across the pavement through connected voids and capillaries. The sealer should also enhance the bonding strength between asphalt coated particles, thus eliminate chipping. As a result, the sealer should prolong the life of exiting and of new asphalt pavement as well as reduce maintenance cost.
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BACKGROUND OF THE INVENTION
The present invention relates to a fuel injection control apparatus, and more particularly to a fuel injection control apparatus which is employed in a fuel injection type engine.
There has been known a fuel injection control apparatus which has an air flow meter for detecting an amount of suctioned air into an engine, a sensor for detecting an engine speed. The prior fuel injection control apparatus determines the amount of the fuel to be injected according to the amount of the detected intake air and the amount of the detected engine speed. In such a prior fuel injection control apparatus, when a vehicle is in the decelerated condition, the amount of the injected fuel is too small compared with the necessitated amount of fuel, and this happens to cause a lean mixture. In other words, when a throttle valve fully closes and the vehicle is in the decelerated condition, a compensation plate within an air flow meter closes by the angle which is greater than that in the proper condition. As a result, the air flow meter indicates the amount of the suctioned air which is less than the amount of the actually suctioned air. If the amount of the detected intake air is small, the amount of the injected fuel also decreases according to the decrease in the amount of the detected air. Thus, if a lean mixture is supplied into an engine, this causes the vibration of a vehicle body to impair the drivability of the vehicle, because an engine brings a torque change.
To dissolve the above-described disadvantages, there has been proposed a fuel injection control apparatus which sets the smallest amount of an injected fuel and regulates the amount of the injected fuel so that the amount of the injected fuel may not become less than the smallest amount. In general, the smallest amount of the injected fuel varies according to an engine speed. In detail, when the engine speed is relatively low, the smallest amount of the injected fuel necessitates a relatively great value in order not to generate the engine torque fluctuation. Contrary to this, when the engine speed is relatively high, it is required to decrease the noxious content contained in the exhaust gas, instead of dissolving the problem of the engine torque fluctuation. Hence, when the engine speed is relatively high, the smallest amount of the injected fuel is necessitated a relatively small value. There has been such a fuel injection control apparatus as the apparatus varies the smallest amount of the injected fuel, which is set according to the variation of the engine speed.
However, even in the case that the smallest amount of the injected fuel varies according to the engine speed, when a throttle valve temporarily opens and the engine speed temporarily increases, the smallest amount of the injected fuel is set to the smallest amount which is set for the high engine speed as the engine speed temporarily increases. After the engine speed temporarily increases, the engine speed promptly drops. In this condition, the smallest amount of the injected fuel for the high engine speed is set and the relatively small amount of fuel is injected. This causes the engine torque fluctuation to generate the vibration of the vehicle body.
SUMMARY OF THE INVENTION
The present invention was made in view of the foregoing background and to overcome the foregoing drawbacks. It is accordingly an object of this invention to provide a fuel injection control apparatus which decreases a vibration of a vehicle body when the engine speed varies.
To attain the above objects, a fuel injection control apparatus according to the present invention has a first means which detects an amount of an intake air suctioned into an engine, and a second means which detects an engine speed. Further, the apparatus has a third means which determines an engine speed zone. When the detected engine speed is less than a first predetermined engine speed, it is determined that it is in a low engine speed zone. When the detected engine speed is greater than a second predetermined engine speed which is set to be greater than the first predetermined engine speed, it is determined that it is in a high engine speed zone. Further, when the detected engine speed is between the first and second predetermined engine speeds, it is determined that it is in an intermediate engine speed zone. A fourth means sets a first value of a minimum amount of an injected fuel when the detected engine speed is in the low engine speed zone, and sets a second value which is less than the first value when the detected engine speed is in the high engine speed zone. When the detected engine speed is in the intermediate engine speed zone, the fourth means maintains one of the first or second value which is already set. A fifth means determines an amount of an injected fuel according to the amount of the intake air and the engine speed detected by the air flow meter and the engine speed sensor respectively. When the determined amount of an injected fuel is less than the minimum amount set by the fourth means, the fifth means determines the minimum amount of the injected fuel set by the fourth means as a final minimum amount of the fuel. When the determined amount of an injected fuel is greater than the minimum amount set by the fourth means, the fifth means determines the determined amount of the injected fuel as a final amount of an injected fuel. Finally, the amount of the fuel calculated by the fifth means is injected by a sixth means into the engine.
BRIEF DESCRIPTION OF THE DRAWINGS
The above objects, features and advantages of the present invention will become more apparent from the following description of the preferred embodiments taken in conjunction with the accompanying drawings, wherein:
FIG. 1 is a partially schematic view of an internal combustion engine installed with a fuel injection control apparatus according to the present embodiment of the invention;
FIG. 2 is a circuit diagram of the electronic control unit illustrated in FIG. 1;
FIG. 3 is a flow chart which illustrates the operation of the apparatus according to the present embodiment of the invention;
FIG. 4 is a flow chart which illustrates the operation of the apparatus according to the present embodiment of the invention; and
FIG. 5. is a graph which indicates the minimum amount of the injected fuel.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is described in detail with reference to the accompanying drawings which illustrate different embodiments of the present invention.
FIG. 1 illustrates a partially schematic view of an internal combustion engine installed with a fuel injection control apparatus according to the present embodiment of the invention. An air flow meter 2 is provided in an intake passage defined within an intake manifold 10 and is designed to calculate the amount of air introduced into an air cleaner (not shown in drawings). The air flow meter 2 comprises a compensation plate 2A which is rotatably mounted in the intake passage, and a potentiometer 2B which detects the opening of the compensation plate 2A. The potentiometer 2B generates an analog output signal which is in proportion to the amount of the introduced air. The amount of the introduced air is outputted from the potentiometer 2B as an electric voltage. An intake air temperature sensor 4 is provided at the position in the vicinity of the air flow meter 2.
A throttle valve 6 is provided in the downstream part of the air flow meter 2. A throttle sensor 18 is provided on the intake manifold 10 at the position adjacent to the throttle valve 6 and detects the opening of the throttle valve 6. The throttle sensor 18 generates a signal which is in proportion to the opening of the throttle valve 6. A surge tank 8 is provided in the downstream part of the throttle valve 6, within the intake manifold 10. A fuel injection valve 12 is mounted on the intake manifold 10 and injects an amount of fuel into the intake passage. The intake manifold 10 is connected with a combustion chamber 14A of an engine. The combustion chamber 14A is further communicated with a catalytic converter (not shown in drawings) which contains a three-way catalyst. The numeral 20 designates a spark plug which generates an electric spark between its electrodes. An engine coolant temperature sensor 24 is mounted on a cylinder block of the engine and detects the temperature of the engine coolant which is filled in an engine coolant jacket. The engine coolant temperature sensor 9 generates an analog output signal which is in proportion to the engine coolant temperature.
The spark plug 20 is connected with a distributor 26 which is connected with an ignitor 28. In the distributor 26, a cylinder distincting sensor 30 and an engine speed sensor 32 are provided. Each of the sensors 30 and 32 comprises a pickup and a signal rotor fixed onto a distributor shaft. If the engine is a four-cylindered engine, the cylinder distincting sensor 30, issues the cylinder distincting signal by every 180° of a crank angle and outputs it into an electronic control unit 34 (herein referred to as ECU). If the engine is a six-cylindered engine, the cylinder distincting sensor 30 issues the cylinder distincting signal by every 120° of the crank angle. The engine speed sensor 32 generates a crank angle signal by every 30° of the crank angle and outputs the crank angle signal to the ECU 34.
FIG. 2 shows a circuit diagram of the ECU 34 illustrated in FIG. 1. The ECU 34 functions as a digital computer and comprises a central processing unit 40 (hereinafter referred to as CPU) which carries out the arithmetic and logic processing means, a random-access memory 36 (hereinafter referred to as RAM) which temporarily stores the calculated data of the CPU 40, a read-only memory 38 (hereinafter referred to as ROM) which stores a predetermined control program and arithmetic constants therein, a first input/output port 42, a second input/output port 44. A bus 50 connects the elements among the RAM 36, the ROM 38, the CPU 40, the first input/output port 42, the second input/output port 44, a first output port 46 and a second output port 48.
The first input/output port 42 is connected with the air flow meter 2, the engine coolant temperature sensor 24 and the intake air temperature sensor 4 through an analog/digital converter 56, a multiplexer 54 and buffers 52A, 52B, 52C. The multiplexer 54 and the analog/digital converter 56 are controlled by the signals which are outputted from the first input/output port 42, and convert the analog data detected by the air flow meter 2, the engine coolant temperature sensor 24 and the intake air temperature sensor 4 into the digital signal. The converted digital signals are stored in the CPU 40 or the RAM 36.
The second input/output port 44 is connected with the cylinder distincting sensor 30 and the engine speed sensor 32 through a waveform shaping circuit 64. Further, the second input/output port 44 is connected with the throttle sensor 18 through a buffer 58. The first output port 46 is connected with the ignitor 28 through a first actuating circuit 70. The second output port 48 is connected with the fuel injection valves 12 through a second actuating circuit 72.
The ROM 38 memorizes maps of a basic spark advance and an amount of a basic fuel injection which are indicated by the engine speed and the amount of the intake air. The CPU 40 reads the basic spark advance and an amount of a basic fuel injection by the signals from the air flow meter 2 and the engine speed sensor 32. The read basic spark advance and an amount of a basic fuel injection are corrected by the various kinds of signals including the signals from the engine coolant temperature sensor 24 and the intake air temperature sensor 4. The ignitor 28 and the fuel injection valves 12 are controlled by the corrected signals. Thus, the spark advance and the amount of the injected fuel are controlled by the program stored in the ROM 38. Next, a fuel injection period τ is explained in conjunction with the flow chart shown in FIG. 3.
The program shown in FIG. 3 is an interruption routine which is carried out at every time when the cylinder distincting sensor 30 issues a cylinder distincting signal. When the routine commences to calculate the injection time period upon the issue of the cylinder distincting signal, in step 111, the engine speed RPM and the amount of the suctioned intake air detected by the engine speed sensor 32 and the air flow meter 2, respectively, are read. The program proceeds to a step 112, wherein a basic fuel injection period τ p' is calculated according to the amount of the suctioned intake air Q and the engine speed RPM. The program proceeds to a step 200, wherein a minimum amount of the injected fuel τ pmin is set. According to the present embodiment, the minimum amount of the injected fuel τ pmin is set to two predetermined values which are selected by the engine speed.
FIG. 5 shows a graph which illustrates the minimum amount of the injected fuel. When an engine speed increases from a low engine speed zone which is less than a first engine speed X (for example, 1600 RPM) to a high engine speed zone which is greater than a second engine speed Y (for example, 2000 RPM), a first predetermined value A (for example, 0.46 msec) is adopted during the low and intermediate engine speed zones defined between the first and second engine speeds X, Y. When the engine speed increases to exceed the second engine speed Y, the second predetermined value B is adopted as the minimum amount of the injected fuel.
Contrary to this, when the engine speed drops from the high engine speed zone to the low engine speed zone, the second predetermined value B is adopted during the high and intermediate engine speed zones. When the engine speed further drops and is in the low engine speed zone, the first predetermined value A is adopted as the minimum amount of the injected fuel instead of the second predetermined value B.
The minimum amount of the injected fuel τ pmin is explained in conjunction with FIG. 4. In step 221, the second predetermined value B of the minimum amount of the injected fuel is stored in a register D. In steps 211 and 212, it is determined to which engine speed zone the engine speed belongs. In step 211, it is determined whether or not the engine speed is less than the second engine speed Y. When the engine speed is greater than the second engine speed Y, the program proceeds to step 223. In this condition, it is determined that the engine speed belongs to the high engine speed zone. Contrary to this, when the engine speed is less than the second engine speed Y, the program proceeds to step 212, wherein it is determined whether or not the engine speed is less than the first engine speed X. If the engine speed is less than the first engine speed X, the program proceeds to step 222. In this condition, it is determined that the engine speed belongs to the low engine speed zone. If the engine speed is greater than the first engine speed X, the program ends. In this condition, it is determined that the engine speed belongs to the intermediate engine speed zone. If it is determined in step 212 that the engine speed is less than the first engine speed X, the program proceeds to step 222, wherein the first predetermined value A of the minimum amount of the injected fuel τ pmin is stored in the register D. As apparent from FIG. 5, the first predetermined value A of the minimum injection amount is designed to be greater than the second predetermined value B. For example, the first predetermined value A is 0.46 millisecond (msec.), and the second predetermined value B is 0.23 millisecond (msec.). In a step 223, the value stored in the register D is set as the minimum amount of the injected fuel τ pmin . When the first predetermined value A is stored in the register D, the minimum amount of the injected fuel is the amount determined by the first predetermined value A. When the second predetermined value B is stored in the register D, the minimum amount of the injected fuel is the amount determined by the second predetermined value B. In the register D, if the engine speed belongs to the high engine speed zone, it is determined in step 211 that the result is NO and the second predetermined value B is stored. If the engine speed belongs to the low engine speed zone, it is determined in the step 212 that the result is YES, and the first predetermined value A is stored in the register D. If the engine speed belongs to the intermediate engine speed zone, it is determined that the result in the step 211 is YES and the result in the step 212 is NO. Hence, the another minimum amount of the injected fuel is not set in the step 223, and the already set minimum amount of the injected fuel τ pmin is still maintained.
Thus, as a result that the minimum amount of the injected fuel is set, when the engine speed gradually drops from the speed higher than the second engine speed Y under the effect of the engine brake, the minimum amount of the injected fuel τ pmin is converted to the first predetermined value A after the engine speed drops down to the first engine speed X. During the high and intermediate engine speed zone, the minimum amount of the injected fuel is set to the second predetermined value B. Hence, when the engine speed drops from the high engine speed zone, the emission of the noxious content, which is contained in the exhaust gas, is decreased.
When the engine speed temporarily increases, the minimum amount of the injected fuel τ pmin is maintained as the first predetermined value A unless the increased engine speed does not exceed the second engine speed Y, and is not converted to the second predetermined value B. Hence, the torque fluctuation, which generates at the time when the engine speed decreases, can be decreased.
While the present invention has been described in its preferred embodiments, it is to be understood that the invention is not limited thereto, and may be otherwise embodied within the scope of the following claims.
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A fuel injection control apparatus for use of an engine. The apparatus varies a minimum amount of fuel to be injected into the engine according to such conditions as the engine speed increases or decreases. When the engine speed increases, a first minimum amount of fuel is set in low and intermediate engine speed zones and the first minimum amount is converted to a second minimum amount of fuel which is less than the first minimum amount in a high engine speed zone. Contrary to this, when the engine speed decreases, the second minimum amount of fuel is set in high and intermediate engine speed zones, and the second minimum amount of fuel is converted into the first minimum amount of fuel in the low engine speed zone. Thus, according to the increase or decrease in an engine speed, a minimum amount of fuel is varied with a hysteresis.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to sewing machines of the type adapted to produce a variety of stitch patterns, and more particularly, to an arrangement in a sewing machine of the above character for executing a compound stitch pattern comprising a sequence of different stitch patterns each of which is capable of unique response to a single control parameter introduced by a sewing machine operator prior to initiation of production of said compound stitch pattern.
A specific application of this invention involves the provision of a compound stitch pattern for mending a fabric tear, the compound mending stitch pattern includes a sequence of different stitch pattern extending transversely and lengthwise of the fabric tear, certain of which are capable of unique response to an operator entered parameter related to the length of the fabric tear so as to provide a composite stitch pattern matching the fabric tear to be mended
2. Description of the Prior Art
U.S. Pat. No. 4,373,459 of W. H. Dunn et al for "Electronically Controlled Sewing Machine Arranged to Sew a Sequence of Stitch Patterns" issued Feb. 15, 1983 discloses an arrangement for stringing together a sequence of different stitch patterns on a sewing machine. Although in this patent each pattern in the string may be modified by an operator introduced modification factor, each such modification must be separately introduced at the time each pattern in the string is selected so that the formulation of a compound stitch pattern would be so tedious and time
U.S. Pat. No. 4,184,441 of J. Brown et al. for "Electronically Controlled Household Sewing Machine Having Patch Sewing Capability" issued Jan. 22, 1980 discloses an arrangement for sequentially sewing successively different stitch configurations which might provide a compound stitch pattern useful for mending or the like but in this patent each successively different stitch configuration must be selected by the sewing machine operator during the stitching of the sequence, thus imposing a further critical timing requirement on the successful execution of a compound stitch pattern.
SUMMARY OF THE INVENTION
The formulation of a compound stitch pattern in a sewing machine is provided for in this invention by an arrangement for successively executing a sequence of different stitch patterns stored in a sewing machine memory with each different stitch pattern being capable of unique modification in accordance with a single parameter entered by the machine operator into the memory.
One object of this invention is to provide a compound stitch pattern suitable for mending a fabric tear and comprising a variety of different stitch patterns stored in the sewing machine memory so as to be executed in predetermined sequence with certain of the stored stitch patterns being uniquely modified responsive to a single operator entered parameter related to the length of the fabric tear to be mended thus automatically to adjust the stored patterns to produce a variant of the compound stitch pattern suitable to repair the length of fabric tear indicated by the operator indicated parameter.
A further object of this invention is to provide means for inhibiting the sewing of a selected compound stitch pattern of the above character until entry has been effected by the sewing machine operator of a parameter to which certain of the stitch patterns are responsive.
DESCRIPTION OF THE DRAWINGS
The above and additional objects and advantages will be apparent from the following description of a preferred embodiment illustrated in the accompanying drawings in which:
FIG. 1 is a front elevational view of a sewing machine having this invention applied thereto,
FIG. 2 is a diagram illustrating the stitches in a compound stitch pattern in accordance with this invention, and
FIG. 3 illustrates a general block diagram of a microcomputer based control system for a sewing machine capable of implementing a compound stitch pattern in accordance with this invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The sewing machine illustrated in FIG. 1 is of the type disclosed in the U.S. Pat. No. 4,373,459, Feb. 15, 1983, which is incorporated herein by reference. This sewing machine includes the capability of sewing successively a series, or string, of stitch patterns selected by a sewing machine operator from a repertoire of stitch patterns. The patterns may be selected by depressing the appropriate pattern selector switch 24 and then entered into the string of patterns to be successively stitched by depression of the enter button 48. Pattern modifying factors, such as pattern width or length, may be entered for each selected pattern by setting and depression of the appropriate override control elements 26 or 28 all in accordance with the detailed teaching in the above referenced U.S. patent.
The present invention differs from that of the referenced U.S. Pat. No. 4,373,459 in that a selector switch 100 is provided for entering into the sewing machine memory 66 instructions for an entire sequence of stitch patterns which are preferrably predetermined in relation to one another to produce a compound stitch pattern such as a mending stitch pattern illustrated in FIG. 2 and described herein below.
Preferrably, selection of the compound stitch pattern by depression of the selector switch 100 enters the string of predetermined stitch patterns of the compound stitch pattern into the sewing machine memory 66 independently of and disassociated from any patterns selected by depression of the pattern selector switches 24, so that operation of the sewing machine thereafter will terminate after production of the compound stitch pattern without joining therewith any conventionally selected string of patterns. Such independent execution of the compound stitch pattern may be attained by entering the component stitch patterns thereof in a memory having stringing capability but separate from that of the conventional string memory of the sewing machine.
The present invention also differs from that of the referenced U.S. Pat. No. 4,373,459 in that each successive stitch pattern of the predetermined string of patterns making up the compound stitch pattern is not influencable by a separately introduced modifying factor, but rather, a single parameter may be introduced by operator depression of input switches 110, 120 for incrementing or decrementing respectively a modifying factor which selected factor may be displayed as at 130, and each pattern of the predetermined string is flagged whether or not and how to be modified in accordance with the single operator entered parameter.
A specific preferred example of the present invention will now be described with reference to FIG. 2 which illustrates a compound stitch pattern adapted to serve as a mending stitch pattern for repairing a fabric tear.
The sequence of successive stitch patterns which is entered in the sewing machine pattern memory 66 by depression of the compound pattern selector switch 100 and the enter button 48 comprises a multi stitch zigzag pattern designated MZ. followed by a succession of fourteen (14) transverse straight stitch patterns with no work feed designated C. alternating each with one of fifteen (15) lengthwise straight stitch patterns designated L.
In this preferred embodiment providing a mending stitch pattern the operator influenced input switches 110 and 120 increase or decrease, respectively a parameter related to the length of the fabric tear which it is desired to repair. The parameter to be entered may, for instance, be the length of the tear expressed in millimeters and the entered parameter may be exhibited by the LEDs 130 shown in FIG. 1.
Those of the stitch patterns in the string of patterns stored by depression of switches 100 and 48 which require response to the parameter stored as a result of operation of the input switches 110, 120 as, for instance, in RAM 140 of the microprocessor, are flagged for such response and are associated with data to be processed by the central processor unit 64.
The multi zigzag stitch pattern MB, for instance, is flagged and associated with data related to the length of each multi stitch zigzag pattern by which the central processor unit can calculate and activate an appropriate number of pattern repeats for the MZ pattern to extend the length of the fabric tear as indicated by the operator inserted parameter. FIG. 2 indicates five such repeats for the multi stitch zigzag pattern MB.
The transverse straight stitches produced by each of the stitch patterns indicated by the reference character C need not respond to the operator inserted parameter since the overall width of the mending stitch pattern is the same regardless of the length of the fabric tear. The transverse straight stitch patterns C, therefore, are not flagged for response to the inserted parameter, but instead they are accompanied by predetermined instruction to shift the bight actuator system 68 either left or right and with the appropriate bight termination. The first two, C1 and C2, being at the widest bight of the multi stitch zigzag pattern MZ, and the remainder decreasing in bight, preferrably in uniform steps to the central needle position of stitch pattern C15.
The lengthwise stitch patterns L are flagged to respond to the operator inserted parameter so that the first, L1, will include sufficient stitches so as to extend over the initial multi stitch zigzag pattern MZ 1. Succeeding lengthwise straight stitch patterns each with predetermined instructions to the feed actuator system 70 to feed either forward or reverse, are associated with data enabling the central processor unit 64 successively to decrement the number of feed steps, i.e. stitches as compared with that of L1 so that a composite spiral pattern of successively smaller rectangles is stitched by the alternating patterns C and L so as to cover the multi stitch zigzag stitches of the patterns MZ.
As a result, a strong covering of stitches is formed over a fabric tear. It may be practical to limit the length of fabric tear which can be repaired by any one execution of the compound stitch pattern. in accordance with this invention; and if a longer tear is desired to be mended successive execution of the compound stitch pattern may be used.
Since entry of a parameter is a requisite to proper execution of the compound stitch pattern of this invention, it is desirable for operation of the sewing machine to be prevented in case no such parameter is entered by an operator. Accordingly, the central processor unit 64 of the microprocessor is preferrably arranged to output a disabling signal 150 to the sewing machine drive in the absence of operator insertion of a fabric tear length.
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An electronic sewing machine storing information concerning a string of different stitch patterns includes a central processor responsive to an operator entered parameter for effecting unique modification of certain stored stitch patterns thus creating a compound stitch pattern useful, for instance, as a mending stitch pattern for repairing various length fabric tears.
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BACKGROUND
The present invention is generally related to output cells for integrated circuits, and more specifically to bus hold and pull-up resistors for output cells.
The complexity of modern field programmable gate arrays (FPGAs) has been increasing dramatically over the last few years. This complexity has allowed an increase in flexibility that has seen the inclusion of multiple circuits provided as functional alternatives for selection by circuit designers. This increased flexibility makes it easier to design an integrated circuit since a required circuit is more likely to be available.
Unfortunately, when two alternatives are provided on an FPGA, the result may be less than optimal. For example, extra die area is consumed, the two cells may conflict with each other, power may be wasted, or other unforeseen problems may arise.
Two cells that may be provided as alternative circuits are bus hold and pull-up circuits. These circuits are commonly used with tri-state output drivers. A bus hold circuit retains the last state on a line. This is particularly useful after a tri-state driver shuts off and before another tri-state driver becomes active. If this line is allowed to float, it may change state due to capacitive coupling from other lines. Even worse, its voltage may approach the threshold voltage of input cells on the line, creating metastability problems. A pull-up circuit pulls the voltage on a line to a supply, typically VCC, in the absence of an active driver on the line. Alternately, it may be used in lieu of an active pull-up device on a tri-state line.
When these cells are conventionally combined, the result is wasted die area since two large resistors are present but only one is used. Also, there is the possibility that both circuits may be enabled. If a bus hold circuit tries to pull a voltage on a line to ground while a pull-up circuit tries to pull it up to VCC, the result is an output voltage between the supplies. As above, this voltage may be near the threshold voltage of one or more input gates on the line, resulting in potential metastable conditions.
Thus, what is needed is an more efficient combination bus hold and pull-up circuit. It would be preferable if the combination saves die area and reduces the possibility of a conflict between the two functions.
SUMMARY
Accordingly, embodiments of the present invention provide circuits, methods, and apparatus that combine a bus hold and a pull-up circuit in a die area efficient manner.
An exemplary embodiment of the present invention combines a bus hold resistor with a pull-up resistor. The resistor is connected between a pad and an inverter. When a user selects a bus hold function for the pad, the inverter is enabled and driven through a second inverting gate by the pad. When a pull-up function is selected, the inverter output is driven high. If neither function is selected, the inverter output is tri-stated. In this way, the die area of a second resistor is saved and potential conflicts between these alternately available functions are avoided.
A better understanding of the nature and advantages of the present invention may be gained with reference to the following detailed description and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a simplified block diagram of a programmable logic device that may benefit by incorporating embodiments of the present invention;
FIG. 2 is a block diagram of an electronic system that may benefit by the incorporating embodiments of the present invention;
FIG. 3 is a schematic of an output cell connected to a tri-state bus, where the output cell incorporates a pull-up resistor;
FIG. 4 is a schematic of an output cell connected to a tri-state bus, where the output cell incorporates a bus hold circuit;
FIG. 5 is a schematic of an output cell connected to a tri-state bus, where the output cell incorporates both a pull-up resistor and a bus hold circuit;
FIG. 6 is a schematic of an output cell connected to a tri-state bus, where the output cell incorporates an embodiment of the present invention;
FIG. 7 is a schematic of an output cell incorporating a further embodiment of the present invention;
FIG. 8 is a schematic of an output cell incorporating yet a further embodiment of the present invention;
FIG. 9 is a flowchart illustrating an embodiment of the present invention; and
FIG. 10 is a schematic of a tri-state inverter that may be used by an embodiment of the present invention.
DESCRIPTION OF EXEMPLARY EMBODIMENTS
FIG. 1 is a simplified partial block diagram of an exemplary high-density programmable logic device 100 wherein techniques according to the present invention can be utilized. PLD 100 includes a two-dimensional array of programmable logic array blocks (or LABs) 102 that are interconnected by a network of column and row interconnections of varying length and speed. LABs 102 include multiple (e.g., 10) logic elements (or LEs), an LE being a small unit of logic that provides for efficient implementation of user defined logic functions.
PLD 100 also includes a distributed memory structure including RAM blocks of varying sizes provided throughout the array. The RAM blocks include, for example, 512 bit blocks 104 , 4K blocks 106 and an M-Block 108 providing 512K bits of RAM. These memory blocks may also include shift registers and FIFO buffers. PLD 100 further includes digital signal processing (DSP) blocks 110 that can implement, for example, multipliers with add or subtract features.
It is to be understood that PLD 100 is described herein for illustrative purposes only and that the present invention can be implemented in many different types of PLDs, FPGAs, and the other types of digital integrated circuits.
While PLDs of the type shown in FIG. 1 provide many of the resources required to implement system level solutions, the present invention can also benefit systems wherein a PLD is one of several components. FIG. 2 shows a block diagram of an exemplary digital system 200 , within which the present invention may be embodied. System 200 can be a programmed digital computer system, digital signal processing system, specialized digital switching network, or other processing system. Moreover, such systems may be designed for a wide variety of applications such as telecommunications systems, automotive systems, control systems, consumer electronics, personal computers, Internet communications and networking, and others. Further, system 200 may be provided on a single board, on multiple boards, or within multiple enclosures.
System 200 includes a processing unit 202 , a memory unit 204 and an I/O unit 206 interconnected together by one or more buses. According to this exemplary embodiment, a programmable logic device (PLD) 208 is embedded in processing unit 202 . PLD 208 may serve many different purposes within the system in FIG. 2 . PLD 208 can, for example, be a logical building block of processing unit 202 , supporting its internal and external operations. PLD 208 is programmed to implement the logical functions necessary to carry on its particular role in system operation. PLD 208 may be specially coupled to memory 204 through connection 210 and to I/O unit 206 through connection 212 .
Processing unit 202 may direct data to an appropriate system component for processing or storage, execute a program stored in memory 204 or receive and transmit data via I/O unit 206 , or other similar function. Processing unit 202 can be a central processing unit (CPU), microprocessor, floating point coprocessor, graphics coprocessor, hardware controller, microcontroller, programmable logic device programmed for use as a controller, network controller, and the like. Furthermore, in many embodiments, there is often no need for a CPU.
For example, instead of a CPU, one or more PLD 208 can control the logical operations of the system. In an embodiment, PLD 208 acts as a reconfigurable processor, which can be reprogrammed as needed to handle a particular computing task. Alternately, programmable logic device 208 may itself include an embedded microprocessor. Memory unit 204 may be a random access memory (RAM), read only memory (ROM), fixed or flexible disk media, PC Card flash disk memory, tape, or any other storage means, or any combination of these storage means.
FIG. 3 is a schematic of an output cell connected to a tri-state bus, where the output cell incorporates a pull-up resistor. This figure includes an output cell for an integrated circuit including a pull-down device M 1 310 connected to a pad 330 . The pad 330 is further connected to a tri-state line 335 , which may be part of a tri-state bus. Three other drivers, which typically reside on other individual integrated circuits, are also connected to the tri-state line 335 and are represented by pull-down devices M 2 340 , M 3 350 , and M 4 360 .
In this figure, only pull-down devices are shown for individual output stages. In this case, R 1 320 pulls the pad 330 and tri-state line 335 high in the absence of any of the drivers M 1 310 , M 2 340 , M 3 350 , or M 4 360 pulling it down. In this type of configuration, R 1 320 is typically a relatively lower value such that the rise time at the pad 330 and line 335 does not become excessive. In other embodiments, active pull-up devices are included in the output stages. In that case, R 1 320 may be relatively larger value.
FIG. 4 is a schematic of an output cell connected to a tri-state bus, where the output cell incorporates a bus hold circuit. This figure includes an output driver including a pull-up device M 1 410 and pull-down device M 2 420 connected to a pad 430 , which is in turn coupled to a tri-state line 435 . The output cell further includes a bus hold circuit including inverter 440 , tri-state inverter 445 , and resistor R 2 450 . Other output drivers are also connected to the tri-state line 435 , and are represented by an output driver including M 3 416 and M 4 465 , which typically resides on a second integrated circuit, and a second output driver including devices M 5 570 and M 6 465 , which typically resides on a third integrated circuit.
When the enable signal on line 447 is such that the inverter 445 is enabled, the inverter 440 senses the voltage or logic stage at the pad 430 , inverts that state and provides it to the inverter 445 . The inverter 445 then again inverts the state and provides it as an output to the resistor R 2 450 . For example, if the voltage at the pad 430 is at ground, a logic low, inverter 440 provides a signal near VCC, a logic high, to the inverter 445 . The inverter 445 then provides a voltage near ground, a logic low, to the resistor R 2 450 . If each of the output stages on line 435 are tri-stated, the resistor R 2 450 then acts to hold the voltage at the pad 430 near ground, that is the logic low state at the pad 430 is retained in the absence of any active driver on line 435 .
FIG. 5 is a schematic of an output cell connected to a tri-state bus, where the output cell incorporates both a pull-up resistor and a bus hold circuit. This figure includes an output driver including a pull-up device M 1 510 and a pull-down device M 2 520 , pull-up resistor R 1 525 , and a bus hold circuit including inverter 540 , tri-state inverter 545 , and hold resistor R 2 550 which is connected to a pad 530 . The pad 530 is in turn connected to tri-state line 535 . The tri-state line 535 also connects to other output drivers, typically on other integrated circuits, represented here are by a first output stage including pull-up device M 3 568 and pull-down device M 4 565 , and a second output stage including pull-up device M 5 570 and a pull-down device M 6 575 .
A problem may arise when pull-up to resistor and bus hold circuit are included in the same output structure. Specifically, when a bus hold circuit tries to hold a low at the pad 530 , the pull-up resistor R 1 525 and bus hold resistor R 2 550 fight each other, and in doing so provide an output voltage at the pad 530 that is and a voltage between VCC and ground or VSS. This is particularly troublesome if an input gate having a threshold voltage is coupled to the line 535 . In this event, the input gate may become oscillatory, that is it may become unstable or enter a metastable condition.
FIG. 6 is a schematic of an output cell connected to a tri-state bus, where the output cell incorporates an embodiment of the present invention. This figure includes an output stage or cell simplified as a pull-up device M 1 610 and pull-down device M 2 620 connected to a pad 630 , and a combined pull-up and bus hold circuit including NOR gate 640 , tri-state inverter 645 and resistor R 2 650 . The pad 630 is in turn connected to tri-state line 635 . Other output gates are shown as being connected to tri-state line 635 including two gates simplified as devices M 3 660 and M 4 665 , and M 5 670 and M 6 675 . Typically, the output driver simplified as devices M 1 610 and M 2 620 , the pad 630 , and the combined pull-up and bus hold circuit are integrated on a first integrated circuit, while the output gate simplified as M 3 660 and M 4 665 is integrated on a second integrated circuit and the output gate simplified as M 5 670 and M 6 675 are integrated on a third integrated circuit. The tri-state bus line 635 may be a PC board trace, a wire connecting two or more integrated circuits, or other appropriate conductor.
The output gate shown as M 1 610 and M 2 620 may be this or any other type of output gate, but is typically a tri-state output driver. One example of a tri-state output driver that may be used is shown in FIG. 10 . Similarly, the output gate shown as M 3 660 and M 4 665 may be this or another type of gate. The same holds true for the gate shown as M 5 670 and M 6 675 .
In this and the other included figures, a certain number of output gates are shown as being coupled to a tri-state line or conductor. In various implementations incorporating embodiments of the present invention, there may be different numbers of integrated circuits and output buffers coupled to the tri-state line or conductor. Also, input gates have not the shown for simplicity, though one or more input gates may be included, for example, each integrated circuit shown may include an input gate, and other input gates may reside on other integrated circuits not shown.
When the combined pull-up and bus hold circuit is to be used as a pull-up, the tri-state inverter 645 is enabled. The ENB signal on line 642 is high, thus forcing the output of the NOR gate 640 to be low. The output of the inverter 645 is high, thus resistor R 2 650 acts as a pull-up resistor for the pad 630 .
When the combined pull-up and bus hold circuit is to operate as a bus hold circuit, the tri-state inverter 645 is again enabled, and the ENB signal on line 642 is low. In this case the NOR gate 640 acts as an inverter, and inverts the logical state detected at the pad 630 . Thus, the logic state detected at the pad 630 is provided by the output of the inverter 645 to the resistor R 2 650 .
Specifically, when the pad 630 is at a logical low, a logical low is provided by the inverter 645 to the resistor 650 . In this way, if each of the drivers on the tri-state line 635 are in the high impedance state, the resistance R 2 658 acts to retain the state at the pad 630 as a low. Similarly, if a high-level is to be held at the pad 630 , a high is received by the NOR gate 640 , which provides a low to the inverter 645 , which in turn provides a high level to the resistance R 2 650 . In this way, the resistance R 2 650 acts to hold the state at the pad 630 as a high when each of the drivers attached to be tri-state line 635 are in a high impedance condition.
When the combined pull-up and bus hold circuit is to be configured as a high impedance, that is neither the pull-up or bus hold function is desired, the tri-state inverter 645 is disabled.
The above is summarized in truth table 680 . Specifically, when the ENA signal on line 647 is low, that is states 692 , the impedance provided by resistance is R 2 650 is an open. When ENA is high but ENB is low, that is state 694 , resistance R 2 650 acts a bus hold resistor. When both ENA and ENB are high, that is state 696 , resistance R 2 650 acts as a pull-up resistor.
The resistance R 2 650 may be a resistor, or other resistive element such as a diode tied active MOS device. This resistance may be formed by using polysilicon layer, base diffusion, implant, source/drain diffusion, or other appropriate structure.
FIG. 7 is a schematic of an output cell incorporating a further embodiment of the present invention. This figure includes an output driver simplified as devices M 1 710 and M 2 720 , a combined pull-up and bus hold circuit including NOR gate 740 , tri-state inverter 745 , and resistance R 2 750 . Also shown are programmable switches 760 , 770 , and 780 .
These programmable switches may be part of the configuration of the output cell. In various embodiments of the present invention, one or more of these switches may be included, or other switches may be included. These switches may include fuses, anti-fuses, pass gates, pass devices, or other programmable or configurable devices, and may be controlled by bits stored in EEPROM, Flash, SRAM, DRAM, MRAM, fuse, antifuse, or other structures.
FIG. 8 is a schematic of an output cell incorporating yet a further embodiment of the present invention. This figure includes an output stage simplified as devices M 1 810 and M 2 820 , resistance R 2 850 , and logic circuit L 1 840 , each connected to a pad 830 .
The logic circuit L 1 840 receives a number of control signals, in this specific example two control signals CS 0 on line 842 and CS 1 on line 847 . Depending on the states of CS 0 and CS 1 on lines 842 and 847 , the logic circuit L 1 840 provides a high, a logic state equal to a logic state detected on the pad 830 , or a high impedance to terminal T 1 852 of resistor R 2 850 .
If a high logic level is provided by the logic circuit L 1 840 , then R 2 850 acts as a pull-up resistor. If the logic circuit L 1 840 provides the same logic state as it detects on the pad 830 , then resistor R 2 850 acts as a bus hold circuit. If the logic circuit L 1 840 provides a high impedance, then the resistor R 2 850 provides no function, and appears as an open circuit.
In this figure, L 1 840 is shown as receiving two control signals. In other embodiments of the present invention, there may be a different number of control signals, for example there may be 1 or 3 or more control signals received by the logic circuit L 1 840 . For example, there may be one control signal that selects between pull-up and bus hold functions, particularly where there is no need for a high impedance option.
FIG. 9 is a flowchart illustrating an embodiment of the present invention. In act 910 , a first terminal of a resistance is connected to a pad. In act 920 , a second terminal of the resistance is connected to a driver. At that point it is determined whether the resistance is to form an open circuit, a bus hold circuit, or a pull-up. If a pull-up is desired, the driver is enabled in act 930 , and in act 940 the output of the driver is driven high.
If a bus hold circuit is desired, in act 950 a logic state at the pad is determined. The driver is enabled in act 960 , and the driver is driven to the logic state determined to be at the pad in act 970 . If an open circuit is desired, the driver is tri-stated in act 980 .
FIG. 10 is a schematic of a tri-state driver or inverter that may be used by an embodiment of the present invention. This driver or inverter may be used as an output driver, for example, the output driver shown as the simplified driver including M 1 610 and M 2 620 in FIG. 6 , or as the tri-state inverter 645 in FIG. 6 .
This figure includes a pull-up device M 2 1020 and pull-down device M 3 1030 , as well as tri-state devices M 1 1010 and M 41040 . Inverter 1015 inverts the enable signal received on line 1045 . An input signal is received on line 1015 and is inverted when the gate is enabled.
When a low enable signal on line 1045 is received, the device M 4 1040 is on and conducting. The inverter 1050 inverts this logic level and provides a low signal level to device M 1 1010 , also turning on that device. In this mode, the input signal received on line 1015 is inverted and provided as the output signal Y on line 1035 .
When the enable signal on line 1045 is low, device M 4 1040 is off. The inverter 1050 inverts the low signal and provides a high level signal to device M 1 1010 , thus also shutting off that device. In this case, a high impedance is presented at the output Y on line 1035 independent of the input signal level on line 1015 .
The above description of exemplary embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form described, and many modifications and variations are possible in light of the teaching above. The embodiments were chosen and described in order to best explain the principles of the invention and its practical applications to thereby enable others skilled in the art to best utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated.
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Circuits, methods, and apparatus that combine a bus hold and a pull-up circuit in a die area efficient and conflict free manner. An exemplary embodiment of the present invention combines a bus hold resistor with a pull-up resistor. The resistor is connected between a pad and an inverter. When a user selects a bus hold function for the pad, the inverter is enabled and driven through a second inverting gate by the pad. When a pull-up function is selected, the inverter output is driven high. If neither function is selected, the inverter output is tri-stated. In this way, the die area of a second resistor is saved and potential conflicts between these alternately available functions are avoided.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims benefit of U.S. provisional Patent Application 62/326,599, filed Apr. 22, 2016, which is hereby incorporated by reference in its entirely.
STATEMENT AS TO FEDERALLY SPONSORED RESEARCH
[0002] This invention was made with government support R01 AR064840 awarded by the National Institutes of Health. The government has certain rights in the invention.
TECHNICAL FIELD
[0003] This description generally relates to magnetic resonance imaging (MRI).
BACKGROUND
[0004] MRI provides soft-tissue images with superior contrast. Thus, MRI has become a widely-used modality for joint imaging.
SUMMARY
[0005] In one aspect, some implementations provide a method for determining metallic particle deposition in tissues near metallic implants using magnetic resonance imaging (MRI) data, the method including: accessing MRI data acquired from a joint area that has received a replacement implant, the MRI data including a series of spatially mapped spectral data points, each at a particular offset frequency; generating MRI images of the joint area from the MRI data; receiving information encoding a region of interest that encompasses a suspected metal particle deposition area over at least one of the MRI images generated from the MRI data; constructing magnetic field maps using the MRI data, each magnetic field map representing off-resonance frequency shifts over the joint area; removing a background of off-resonance field inhomogeneity from the magnetic field map such that the region of interest is free from off-resonance field inhomogeneity caused by the implant itself; identifying clusters from the magnetic field maps with the background of off-resonance field inhomogeneity removed, the clusters defined over a first dimension of offset frequencies and a second dimension of cluster volumes; and computing a quantitative metric by combining information from the identified clusters according to both the first dimension and the second dimension.
[0006] Implementations may include one or more of the following features.
[0007] The MRI data may include a series of three-dimensionally encoded spectral volumes, each spectrum volume corresponding to a particular offset frequency, and the spectrum volumes acquired with overlapping offset frequencies. The MRI data may include a series of two-dimensionally encoded spectrum slice sets, each spectrum slice set corresponding to a particular offset frequency, and the spectrum slice sets acquired with overlapping offset frequencies.
[0008] Constructing the magnetic field maps may include: constructing the magnetic field maps by fitting the series of spatially mapped spectral data points against a model that describes the radiofrequency spectral profile applied when acquiring the MRI data. Fitting the series of spectral data points may include: fitting spectral profiles of each spatial quantum of the series of spatially mapped spectral data points against the model, the model including parameters that includes an offset frequency for each pixel of the constructed magnetic field map. Constructing the magnetic field maps may be based on a difference in phase information from the MRI data acquired with different echo times.
[0009] The method may further include: forming a tissue mask by examining a spectral integrity of the series of spatially mapped spectral data points to determine spatial areas that correspond to tissue. Examining the spectral integrity of the series of spatially mapped spectral data points may include: quantifying the spectral integrity by computing a ratio of a cumulative highest magnitude of a first number of spectrum volumes to a sum of a second number of spectrum volumes, wherein the first number and the second number jointly represent a total number of the spectrum volumes.
[0010] The method may additionally include: applying the tissue mask to the magnetic field maps prior to removing the background of background of off-resonance field inhomogeneity.
[0011] Computing the quantitative metric may include applying a nonlinear weighting to sum information from the clusters in both the first dimension and the second dimension. Computing the quantitative metric may include applying a linear weighting to sum information from the clusters in both the first dimension and the second dimension.
[0012] In another aspect, some implementations provide a system for determining metallic particle deposition in tissues near metallic implants using magnetic resonance imaging (MRI) data, the system including: an MRI scanner system configured to acquire MRI data from a joint area that has received a replacement implant, the MRI data including a series of spatially mapped spectral data points, each at a particular offset frequency; a data processing system in communication with the MRI scanner system, the data processing system comprising at least one processor configured to perform the operations of: accessing the MRI data acquired from the joint area; generating MRI images of the joint area from the MRI data; receiving information encoding a region of interest that encompasses a suspected metal particle deposition area over at least one of the MRI images generated from the MRI data; constructing magnetic field maps using the MRI data, each magnetic field map representing off-resonance frequency shifts over the joint area; removing a background of off-resonance field inhomogeneity from the magnetic field map such that the region of interest is free from off-resonance field inhomogeneity caused by the implant itself; identifying clusters from the magnetic field maps with the background of off-resonance field inhomogeneity removed, the clusters defined over a first dimension of offset frequencies and a second dimension of cluster volumes; and computing a quantitative metric by combining information from the identified clusters according to both the first dimension and the second dimension.
[0013] Implementations may include one or more of the following features.
[0014] The MRI data may include a series of three-dimensionally encoded spectral volumes, each spectrum volume corresponding to a particular offset frequency, and the spectrum volumes acquired with overlapping offset frequencies. The MRI data may include a series of two-dimensionally encoded spectrum slice sets, each spectrum slice set corresponding to a particular offset frequency, and the spectrum slice sets acquired with overlapping offset frequencies.
[0015] Constructing the magnetic field maps may include: constructing the magnetic field maps by fitting spatially mapped spectral data points against a model that describes the radiofrequency spectral profile applied when acquiring the MRI data. Fitting the series of three-dimensionally encoded spectral volumes may include: fitting spectral profiles of each spatial quantum of the series of spatially mapped spectral data points against the model, the model comprising parameters that includes an offset frequency for each pixel of the constructed magnetic field map.
[0016] Constructing the magnetic field maps may be based on a difference in phase information from the MRI data acquired with different echo times.
[0017] The data processing system may be configured to perform the operations of: forming a tissue mask by examining a spectral integrity of the series of spatially mapped spectral data points to determine spatial areas that correspond to tissue.
[0018] Examining the spectral integrity of the series of spatially mapped spectral data points may include: quantifying the spectral integrity by computing a ratio of a cumulative highest magnitude of a first number of spectrum volumes to a sum of a second number of spectrum volumes, wherein the first number and the second number jointly represent a total number of the spectrum volumes.
[0019] The data processing system may be configured to perform the operations of: applying the tissue mask to the magnetic field maps prior to removing the background of background of MRI field inhomogeneity. Computing the quantitative metric may include applying a nonlinear weighting to sum information from the clusters in both the first dimension and the second dimension. Computing the quantitative metric may include applying a linear weighting to sum information from the clusters in both the first dimension and the second dimension.
[0020] The details of one or more aspects of the subject matter described in this specification are set forth in the accompanying drawings and the description below. Other features, aspects, and advantages of the subject matter will become apparent from the description, the drawings, and the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] Embodiments will now be described, by way of example only, with reference to the drawings, in which:
[0022] FIG. 1 shows an example of a flow chart to compute a quantitative metric to evaluate metallosis based on magnetic resonance imaging (MRI) data.
[0023] FIGS. 2A to 2B show examples of a representative image from a 3-D Multi-Spectral Imaging (MSI) MRI image data set as well as the corresponding field map for the representative image.
[0024] FIGS. 3A to 3B show a zoomed image of the field map of FIG. 2 within an identified region of interest, as well as a residual tissue off-resonance map from the same identified region of interest and with background field-suppressed.
[0025] FIGS. 4A to 4C show the magnitude image corresponding to the residual tissue off-resonance map from FIG. 3 , along with an example of a clusters identified with a threshold of 500 Hz offset and 250 mm voxel size as well as a 3D rendering the identified clusters in 3D.
[0026] FIG. 5 compares examples of the computed quantitative score with histology readout, indicating a statistically significant correlation.
[0027] FIG. 6A to FIG. 6F illustrate another example of computing the mScore and generating a fused mapping of metallosis.
[0028] FIG. 7 highlights case studies for six (6) symptomatic subjects with suspected metallosis, displayed in six respective columns.
[0029] FIG. 8A to FIG. 8D illustrate the comparison between two off-resonance mapping methods.
[0030] FIG. 9A to FIG. 9B show examples of mScores computed for a cohort of subjects as well as the correlation with histologic necrosis scores.
[0031] Like reference symbols in the various drawings indicate like elements.
DETAILED DESCRIPTION
[0032] Joint replacement is commonly practiced for functional improvements of a human joint. The replacements may include implants made of polyethylene or metal. Wear-induced tear may develop over the articulating surfaces of these replacement implants. Load conditions may exacerbate the tear, which may accelerate once initiated. In many cases, the tear includes the development of local debris. Adverse local tissue reactions (ALTRs) may be caused by a direct toxic effect when high levels of wear debris or ions are generated. The ALTRs may also be caused by an immune reaction often attributed to type-IV delayed type allergic hypersensitivity. Histologic studies of ALTRs show soft tissues with patterns of diffuse and perivascular infiltration of T and B lymphocytes, accumulation of plasma cells, and necrosis.
[0033] Early detection of ALTRs and an expedited revision of, for example, a total hip replacement may be crucial to achieve successful clinical outcome and minimize operative and rehabilitation costs. Revisions of hip resurfacing arthroplasty patients with an ALTR tend to have longer operative times, more surgical complications, and worse measures of clinical outcome than revision of traditional metal-on-polyethylene implants. In general, difficult revision surgeries have 63% higher operative costs and 27% higher rehabilitation costs, as may be found for ALTR patients. Once an ALTR has been identified and revision surgery is elected, the length of hospital stay and the amount of hospital charges are expected to be reduced, by as much as 39% and 22%, respectively. It has been shown that elective revision hip arthroplasty surgeries may have saved $131.8 million in 2005, and may save as much as $560 million in 2030.
[0034] In this context, a non-invasive means to monitor the progression of the wear and tear associated with joint replacement by quantitatively tracking, for example, metal debris deposition would be advantageous. Metallic debris causes unique conditions compared to polymeric (plastic) debris because the metallic debris tend to cause increased risk for larger inflammatory response or tissue reaction. Total hip replacement, for example, may have failure rates of 6% and 13% at 5 and 10-year benchmarks, which can be related to metallic debris deposition from installed implant components. Most often, metallic debris particles are composed of cobalt-chromium alloys, which have a strong paramagnetic magnetic susceptibility relative to biological materials. On MRI, however, it is difficult to distinguish polymeric from metallic deposits while joint replacement can include implants made of metal and polyethylene. For example, both polymeric debris and metallic debris appear as lower signal regions on proton-density or T1 weighted images. While in cases of symptomatic total hip replacements it may be possible to identify debris based on magnitude MRI data, it remains clinically advantageous to differentiate metallic debris from polymeric debris.
[0035] This disclosure describes system and methods developed to capture MRI signals indicative of metallic debris. In particular, some implementations leverage the off-resonance effect caused by the presence of metal debris to capture spatially resolved signals spectrally away from the Larmor frequency of protons in the main magnet of the MRI scanner system. In some instances, the intensity values and the corresponding offset frequency values of signals from a particular locale are analyzed in a quantitative manner. In one example, a quantitative metric is generated by the non-invasive approach based on MRI. Comparison of this quantitative metric with histology results can lead to a strong correlation. In particular, the regional quantitative metric disclosed herein is shown to statistically correlate with local histology metallosis scores in subjects undergoing total hip revision surgery. This statistically significant correlation demonstrating the utility of this example quantitative metric as well as the potential of the non-invasive MRI approach disclosed herein.
[0036] FIG. 1 shows an example of a flow chart 100 to compute a quantitative metric to evaluate metallosis based on magnetic resonance imaging (MRI) data. Initially, a patient with joint replacement implant is placed inside the bore of a magnet of an MRI scanner system and a 3-dimensional multi spectral imaging (3-D MSI) MRI data is acquired from the joint area of the patient ( 102 ). The 3-D MSI is one example of imaging methods to identify a specific physical characteristic parameter at each pixel in an MRI image. In this example, multiple data sets from the same spatial volume may be generated, each data set corresponding to a particular offset frequency from the Larmor frequency of protons in the magnet of the MRI scanner system. For illustration, data sets corresponding to offset frequencies from −10 kHz to +10 kHz may be obtained, each data set encoding MRI imaging data with a slightly varying center frequency around the Larmor frequency. In this illustration, the spatial slice of the patient's joint may be selected by a judicious combination of slice selecting radio-frequency (RF) pulses and associated gradient pulses such that only one spatial slice is selected by transmitting the RF pulses. The received signals, however, can include off-resonance signals due to the presence of metallic debris. The received signals may be classified into different bins, each corresponding to a particular offset frequency. In this manner, MRI data sets from multiple offset frequency may be obtained accordingly. An example of the MRI imaging sequence to capture the multi-spectral data is the Multi-Acquisition with Variable Resonance Image Combination (MAVRIC) 3D-MSI implementation that utilizes overlapping Gaussian spectral windows such that the offset frequencies in neighboring spectral locations overlap.
[0037] The acquired 3D-MSI data may be reconstructed to reveal the anatomical details. Further referring to FIG. 2A , an example of the anatomical image ( 202 ) from a 3D-MSI data set is shown. In this illustration, a MAVRIC SL imaging sequence is used, same as the one used for FIG. 6 and FIG. 7 . Image acquisition parameters may be as follows: coronal scan plane, 36-40 cm field of view (FOV), 7 ms echo time (TE), 4 s repetition time (TR), echo train length (ETL) of 20, 5 mm slice thickness, (512×256×24−32) in-plane data matrix, 24 spectral bins, spectral width of 2.25 kHz (full-width-half maximum), and a 1 kHz spectral bin separation, with a receiver bandwidth of ±125 kHz (500 Hz/pixel). Other instances may use Slice Encoding for Metal Artifact Correction (SEMAC) sequences.
[0038] Based on the reconstructed anatomical image, regions of interest of suspected metallosis may be obtained ( 104 ). Here, an operator may specify the region of interest (ROI) that encompasses the suspected metallosis. As shown in FIGS. 3A and 6B , for each subject, a region of suspected metallosis was identified on a MAVRIC SL images by a board certified musculoskeletal radiologist with over decades of experience of interpreting MR images of arthroplasty. After the ROI has been selected, the 3D-MSI data set may be denoised and valid tissue voxels may be identified ( 106 ). In some instances, the valid tissue voxels may be identified through a voxelwise spectral integrity test. For example, tissue masks may be determined for each volume by examining the 3D-MSI spectral integrity at each voxel. In one illustration, a given voxel in the dataset may be expected to have 3 to 5 dominant spectral bin contributions, depending on the severity of local induction field gradients. In this illustrative example, spectral integrity can be quantified by computing the ratio of the cumulative of a first number of highest magnitude spectral bin signals to the sum of signals from a second number of spectral bins. When the total number of spectral bins are, for example, six, the first number can be three, and the second number can be three as well. A ratio of 3.0 has been empirically found to provide a reliable masking for the purposes of tissue masking. In a typical application, the implant region may be identified in this integrity mask by finding the largest contiguous region of poor spectral integrity (<3.0) in the volume. This “implant” volume can then dilate by, for example, an additional 3 mm to ensure high quality spectral signal is utilized in the analysis of remaining tissue regions. The cumulative goal of these pre-processing steps was to remove voxels that have poor MRI signal integrity from the off-resonance analysis. In these instances, voxels that correspond to non-tissue areas may not have sufficient signal-to-noise (SNR) ratio to undergo further analysis, for example, phase difference assessment, and may be dismissed from phase analysis. Thereafter, magnetic field map may be constructed.
[0039] While the magnitude image ( 202 ) shows the anatomical structures of the joint in FIG. 2A , a field map ( 204 ) may be generated based on the 3D-MSI data set, as shown in FIG. 2B . In some instances, the MRI data set may include data acquired from Multi-Acquisition with Variable Resonance Image Combination (MAVRIC) 3D-MSI implementation that utilizes overlapping Gaussian spectral windows. In these instances, a magnetic field map can be constructed from the 3D-MSI data set ( 108 ). This 3D-MSI dataset can provide 3-5 spectral data points per image voxel which characterize this spectral windowing function. These spectral profiles can be approximated by the Gaussian model:
[0000]
S
b
(
A
,
Δ
v
,
σ
)
=
A
e
-
(
Δ
v
-
v
b
)
2
2
σ
2
.
(
1
)
[0040] For each voxel in the image, acquired bin data can be fit to Eqn. 1 so as to identify the parameters A, Δν, and σ. This spectral profile is analytically differentiable, which readily enables parameter optimization at each voxel using iterative steepest descent approaches. Since this generalized approach performs a fit to an anticipated model within the MSI spectral domain, it is advantageously free from sensitivity to off-resonant bin noise and ghosting. In the example of FIG. 2B , the model-based field map 204 can be computed using an analytic steepest-descent iterative approach. The field map of FIG. 6D is likewise generated via this model-based approach.
[0041] The field map may include the background distortion caused by the presence of the metallic substance. The background can be removed ( 110 ), for example, from the region of interest being analyzed. A variety of background removal methods may be used, including, the Projection onto Dipole Fields (PDF) technique that performs an inversion of dipolar field “sources” within voxels labelled as “non-tissue” across the analyzed volume of interest. For the purposes of background removal, this PDF method can be well-suited to identify and remove the implant-induced field. In one sense, the implant can be well-approximated as a sum of high susceptibility source dipoles that sum to form the implant-induced perturbation field. Further referring to FIG. 3 , a zoomed region 302 corresponding to the ROI is shown, along with the same zoomed region but with background removed ( 304 ).
[0042] A fundamental limit of particulate map detection stems from local fat-water chemical shifts, which are present in MSI-derived off-resonance maps. The presence of chemical shift contamination establishes an off-resonance detection threshold, below which particulate deposits cannot be distinguished from normal fat/water tissue transitions (225 Hz at 1.5T).
[0043] Based on the ROI with background removed, spatial clusters of N varying sizes and M off-resonance thresholds may be identified ( 112 ). In particular, FIG. 4 shows an example of a cluster being identified ( 404 ) for the ROI with background removed ( 304 ). Here, this particular cluster being identified corresponds to an offset frequency of 300 Hz and a volume of 250 mm 3 . Magnitude image 402 for this cluster has a hypo-intense area, indicated by the white arrow, which correspond to the saturated region in example 404 . This area corresponds the central focus of the suspected metallic debris pocket. Based on images 304 , 404 , and 402 , volumetric surface rendering of the implant region and the metallosis cluster can be generated, as shown in image 406 .
[0044] In this manner, clusters of field offsets can be identified at N levels of offsets, for example, 300 350 400 450 500 Hz, and M cluster volume thresholds, for example, 60/120,240,360,480 mm 3 . The volume of identified clusters at these settings forms an N×M matrix ( 114 ). After applying an exponential weighting to the matrix elements (which can be used to tighten mScores for a wide spectrum of metallosis severity), the elements are summed to form the mScore ( 116 ).
[0045] In one proof-of-concept demonstration, tissue samples (˜1 cm 3 ) were extracted during revision surgery from regions of suspected particulate debris in pre-operative MRI. Histological scoring was performed on these samples, focusing on the Fujishiro metal particle score which ranges from 0 (no metal particles) to 4 (significant metal particles). Due to the uncertainty of precise sample locations extracted during surgery, a relatively large volume (120 cm 3 ) surrounding the indented extraction point was utilized for mScore analysis. The example demonstrated in FIGS. 2-4 resulted in a computed mScore of 21 and had a Fujishiro metallosis histology score of 4/4. This demonstration may indicate that there can be a correlation between the histology analysis and the mScore, if the sample locations match.
[0046] FIG. 5 presents the cohort mScore against histology analysis. In a cohort of 15 subjects undergoing total hip revision surgery, regional mScores were computed using pre-operative 3D-MSI imaging data and then correlated with histological metallosis scores from local tissue samples retrieved during surgery. Referring to FIG. 1 , based on this regional identification from 104, the regional identification may be used to guide extraction of a 1 cm 3 tissue sample during the surgical revision procedure. These regions may be denoted as areas of low signal intensity within the synovial envelope on the MAVRIC SL images. Extracted samples can be fixed in formalin, processed for routine histology, and representative sections were graded by a board-certified pathologist with more than decades of experience specializing in orthopaedic pathology and biomaterials. The utilized histological metallosis metrics have previously been described by Fujishiro and Willert. Briefly, these evaluation methods semi-quantitatively grade the presence and extent of histiocytes, particle types, and tissue particle load under high magnification (400×). Tissues were also evaluated using Campbells ALVAL (aseptic lymphocytic vasculitis associated lesion) score. The Fujishiro null-valued group exhibits a tight clustering of low mScores, while the Fushishiro 4/4 valued group has a much broader spread of scores, with a much higher mean. The relatively broad distribution of mScores within the two Fujishiro groups may indicative of the large systematic uncertainties. While localizing a small tissue sample extraction during surgery on the MRI images (for mScore analysis) can present substantial logistical difficulties (e.g., the metallosis pockets detected in the larger mScore analysis volumes may be missed during histological tissue extraction), the results provides proof that the mScore has inherent diagnostic and prognostic value, just like the traditional histology analysis. Indeed, the two observables correlated well with one another. A Wilcox/Ranked-Sum analysis of the cohort yielded a p-value of 0.025, as shown in FIG. 5 . This strong statistical correlation demonstrates that the presented methods offer a promising potential MRI-based biomarker for metallosis assessment near total hip arthroplasty. The mScores shows more variance than histology results from the tissue samples. This is attributable to the more quantitative and likely more sensitive analyses that become feasible using the full MRI dataset.
[0047] FIGS. 6 to 9 illustrate more examples of the mScore computing process. FIG. 6A shows the large field of view multi-spectral images (MSI) while FIG. 6D shows the off resonance map from the same large field of view. After application of the region of interest (ROI), the extracted image is shown in FIG. 6B . Voxel-wise 3D-MSI MR data for the corresponding region is then used to construct an off-resonance map shown in FIG. 6E . Background extraction using the PDF method then exposes the local tissue off-resonance distribution, as shown in FIG. 6F , which is then fused with FIG. 6B to generate the metallosis fusion image of FIG. 6C . In particular, FIG. 6C reveals the suspected metallosis after thresholded cluster analysis. In the examples from FIGS. 6 to 9 , the mScores were computed using off-resonance thresholds of Ti=[350 400 450 500 550 600] Hz and cluster size thresholds of Sj=[0.3 0.6 1.2 1.8 2.4] cm 3 . The choice of a minimum off-resonance threshold of 350 Hz can provide a conservative buffer above the chemical shift threshold, so as to reduce false-postive detection. Clusters can be identified using the spatially-correlated 3dclust algorithm provided by the AFNI toolbox.
[0048] Given a cluster size array Ci,j, mScores were computed according to:
[0000]
mScore
=
∑
i
,
j
e
-
(
T
i
+
α
S
j
)
C
i
,
j
,
(
2
)
[0000] where α can be used to balance the weighting between Ti and Sj. Data shown in FIGS. 6-9 used an empirically chosen value of α=160. In addition to regions of suspected metallosis, mScore analysis was also performed for 16 of the 27 subjects in soft tissue regions where no metallosis would reasonably be expected. For subjects with unilateral hip replacements, these regions were identified on the opposing hip joint. Subjects with bilateral hip replacements had control volumes identified from lower regions on the distal femoral stem outside of the femoral cortex, where metallosis is less likely to be identified. This control analysis may serve to assess a false-positive incidences of the disclosed methods.
[0049] FIG. 7 shows the mScore computing processes for a cohort of six (6) symptomatic subjects. In each column, the top graph shows the magnitude image from the 3D-MSI MR data; the central graph shows the zoomed magnitude image from the 3D-MSI data corresponding to the region of interest (ROI); and the bottom row shows localized background removed off-resonance maps (bottom row) with computed mScores. Clear regions of locally isolated positive off-resonance are seen in all cases, which translates to mScores of various amplitudes depending on the 3-dimensional size and off-resonance amplitude of the pockets.
[0050] FIGS. 8A to 8D compare two off-resonance mapping methods and highlight the advantage of model-based 3D-MSI off-resonance mapping. A selected 3D-MSI in FIG. 8A shows a region of suspected metallosis. The background-removed off-resonance map computed with the conventional center-of-mass (COM) method of FIG. 8B indicates a large region of potential metallosis. However, the model-based residual map, as outlined above in association with block 108 of FIG. 1 , shows far muted off-resonance signature. When examining the MSI spectral profile in the indicated position (X in COM map of FIG. 8B ), a region of unanticipated elevated signal is seen in far off-resonant bins (arrow in FIG. 8D ). This elevated signal, which is suspected to be caused by image ghosting artifacts in the off-resonant bins, slightly shifts the COM off-resonance estimate. When the model-based algorithm is utilized, the computed model is not impacted by the false magnitude elevations of the distant off-resonant bins. The ghosting artifacts of off-resonant bins in the lower signal region of suspected metallosis would have generated a false positive mScore in this case using the COM field map. The model-based approach thus reduces this risk of false-positive findings.
[0051] The choice of field mapping algorithm can be consequential in the elimination of false positive mScores across the control analysis cohort. Using the COM off-resonance mapping method, 25% of the 16 control cases yielded significant false positives (mean mScore=1.79). When applying the presented spectral modelling approach, all 16 control cases properly yielded null mScores.
[0052] FIGS. 9A-9B demonstrate preliminary results from another proof of concept study. FIG. 9A provides a histogram of the mScores computed across the symptomatic cohort of six (6) subjects. The variety of scores is substantially distributed, with a mean of 4.4 and standard deviation of 8.8. While variations of magnetic susceptibility in different alloys of cobalt chromium could explain some of this variation, the different alloys of cobalt chromium used by implant manufacturers can vary by only roughly 30%. The far more extreme variation seen the mScore analysis is therefore more indicative of the differing concentrations and volumes of metallic wear products. FIG. 9B displays a plot of this mScore versus Natu necrosis score trend.
[0053] The specific embodiments described above have been shown by way of example, and it should be understood that these embodiments may be susceptible to various modifications and alternative forms. It should be further understood that the claims are not intended to be limited to the particular forms disclosed, but rather to cover all modifications, equivalents, and alternatives falling within the spirit and scope of this disclosure.
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A method includes: accessing MRI data acquired from a joint area, the MRI data including a series of spatially mapped spectral data points; generating MRI images of the joint area; receiving information encoding a region of interest that encompasses a suspected metal particle deposition area over at least one of the MRI images; constructing magnetic field maps using the MRI data, each representing off-resonance frequency shifts over the joint area; removing a background of off-resonance field inhomogeneity from the magnetic field map such that the region of interest is free from off-resonance field inhomogeneity; identifying clusters from the magnetic field maps with the background of off-resonance field inhomogeneity removed, the clusters defined over a first dimension of offset frequencies and a second dimension of cluster volumes; and computing a quantitative metric by combining information from the identified clusters according to both the first dimension and the second dimension.
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BACKGROUND OF THE INVENTION
I. Technical Field
The present invention relates to mammographic equipment. More particularly, the present invention relates to a breast compression apparatus having a perforation matrix through which a needle is inserted to identify the location of breast lesions.
II. Background Art
Special roentgenography, or x-ray, techniques for photographically studying the mammary gland, or breast, have resulted in more frequent success in detecting small, non-palpable breast lesions that require excisional biopsy. Breast lesions detectable by x-ray techniques may include carcinoma, calcification, proliferative changes, fibroadenomas, fibrocystic changes or normal tissues. Biopsy of lesions in the initial non-palpable phase is vital to improving treatment effectiveness.
If mammograms reveal a suspicious non-palpable lesion, they may be followed up by a localization procedure which is performed shortly before surgery. The localization procedure generally includes compressing the breast having the non-palpable lesion in a vice-like compression device having a perforation grid. A needle is inserted through one of the perforations and an x-ray is taken with the needle implanted in the general vicinity of the lesion. The x-ray film is then developed while the patient remains in the breast compression device until it is determined whether the needle is accurately placed at the lesion. If the initial location is wrong, the needle is re-implanted and the process is repeated until the lesion is located. Due to the pain and length of time that the breast must be maintained in the compression device, only two or three attempts to locate the lesion are generally tolerable in a single session. When the lesion is located by the needle, a J-shaped marker wire may be inserted through the needle to encircle the lesion. The needle may then be removed and the biopsy performed by a surgeon using the marker wire as a guide to locate and excise the lesion.
Breast compression devices may be applied to permit a medial, or lateral, approach or more usually cranial, or vertical, approach. In either, the breast must remain stationary relative to the perforation grid which necessitates that the patient stay in a fixed position while the localization technique is performed and the x-ray film is developed. If two or more insertions are required, remaining immobile can become increasingly uncomfortable.
An example of a compression device used in needle localization is described in Tabar, Laszlo and Peter V. Dean, "The Investigation of Lesions of the Breast", American Clinics of North America, Vol. XVII No. 3 (December 1979), pp. 616-7. The compression plate for preoperative localization of breast lesions disclosed therein comprises a rigid "Plexiglass", a trademark of Rohm and Haas, for thermoplastic polymethyl methacrylate-type polymers, plate which is held by mechanical claping means between the compression plate and a base plate. Both the compression plate and the base plate are secured to the mammographic equipment and the patient is expected to remain immobile during the localization procedure.
A further development of compression devices for preoperative localization is described in Goldberg, Ronald P., Ferris M. Hall, Morris Simon, "Preoperative Localization of Non-Palpable Breast Lesions Using a Wire Marker and Perforated Mammographic Grid", Radiology 146:833-835, March 1983. The compression device disclosed therein has a perforated grid comprising a freestanding apparatus made of "Plexiglass" that is usable with standard mammographic x-ray equipment. Two base plates form a tunnel into which mammographic film can be inserted while the breast is held compressed. The breast is positioned between the tunnel and the upper "Plexiglass" plate which has multiple perforations that are arranged as a centimeter grid. Some of the perforations are marked with a lead-containing paint so that they can be identified both visually and radiographically. The top plate may be adjusted to change the amount of compressive force applied and to allow for breasts of different sizes. The top plate is fixed in position by a set of detachable bull dog clamps that attach to four threaded rods extending upwardly from the base plates. The device is usable in either the lateral or cranial orientation.
The primary disadvantage with the above devices is their rigidity and the lack of comformability of the pressure plate which results in discomfort. Clamp or vice-like compression force applying mechanisms also add to discomfort and rely solely upon the application of compression to prevent slippage. The compression plate and base generally are smooth planar members that do not conform to the body. Movement of the breast within the compression device is a serious problem, especially if the compression force is not sufficient.
The breast compression and needle localization devices should be sterilized between uses, at least those portions which contact the breast. If the breast compression device is an integral part of the mammographic equipment, sterilization requires disassembly of the device from the machine. Sterilization of the perforated needle localization plate is particularly important and cannot be done without disassembly of the equipment.
Another disadvantage of breast compression and needle localization devices which are incorporated as an integral part of the mammographic equipment is that the patient must remain at the machine during the plate development process and usage of the machine cannot be shared with other patients.
These and other disadvantages are overcome and problems are solved by the present invention's provision of an improved breast compression apparatus including a needle localization matrix as summarized below.
SUMMARY OF THE INVENTION
According to the present invention, a breast compression device for use in mammographic radiological investigations is provided wherein a sleeve and breast compression plate are interconnected by first and second straps. The sleeve has an opening for receiving a mammographic film cartridge. The breast compression plate has a plurality of perforations which are preferably disposed in a matrix of closely spaced perforations. The straps used to interconnect the sleeve to the plate are flexible, with each strap being secured on one end to the plate at spaced locations on the plate and are secured on their other end to spaced anchoring locations on the sleeve. The length of the straps extending between the plate and the sleeve may be adjusted to exert a biasing or compressive force against a breast located between the plate and the sleeve.
The straps may be anchored to the sleeve in a range of locations to permit the positioning of the plate relative to the sleeve. In the illustrated embodiment, the straps are detachably connected to the sleeve.
The straps preferably include a first interengaging surfaces and the sleeve includes second interengaging surface complementary to the first interengaging surfaces at the spaced anchoring locations whereby the first and second interengaging surfaces may be detachably secured to one another in a range of locations to adjust the location and compressive force applied by the plate. The first interengaging surfaces on the straps preferably extend along the length of the straps and the second interengaging surfaces on the sleeves extend in a direction generally perpendicular to the length of the straps. The first and second interengaging surfaces are preferably "Velcro" fasteners wherein one of said surfaces includes a plurality of loops forming a felt-like surface and theother interengaging surface comprises a plurality of closely spaced hooks which are adapted to detachably grip the loops of the other interengaging surface. "Velcro" is a registered trademark of Velcro U.S.A.
According to another aspect of the present invention, the breast compression device includes a cartridge sleeve adapted to receive a mammographic film cartridge having an upper plate with a textured upper surface, a laminated base plate and first and second sides connecting the upper plate to the base plate.
The device further includes a compression plate comprising a semi-rigid planar member having a plurality of perforations formed in a grid pattern. The compression plate includes buckles at spaced points thereon which have an arcuate bar on the exterior sides thereof upon which first and second straps are detachably secured.
The straps are secured to the cartridge sleeve by means of first and second interengaging means formed on the straps at a spaced point from the buckles. The straps are detachable from the sleeve at the interengaging means to permit adjustment of the length of the first and second straps which extend between the sides of the cartridge sleeve and the plate. The straps may also be positioned by attaching the straps to the sleeve in a range of locations perpendicular to the length of the straps.
The ability of the apparatus to hold the breast in place in the apparatus is enhanced by the inclusion of textured surfaces on the sides of the sleeve and plate which contact the breast. Also, the top plate is semi-rigid permitting it to conform to a limited extend to the breast.
The apparatus of the present invention is easy to attach and may be quickly and accurately applied to a breast. The "Velcro" fasteners permit the straps to be firmly secured to the sleeve with sufficient compressive force to hold the breast stationary within the apparatus, especially since the surfaces in contact with the breast are textured and the plate is intended to conform to a limited extent to the breast. The straps are flexible which allows for maximum versatility in applying the device to a broad range of breast sizes.
Another important advantage of the apparatus of the present invention is that the apparatus may be easily disassembled and sterilized by merely disconnecting the "Velcro" straps and soaking the components in an antiseptic solution. The plate and sleeve are formed of a polymeric material that is strong yet lightweight and easy to maintain in a clean and sanitary condition.
These and other advantages of the present invention will become more apparent upon studying the attached drawings in view of the following specification and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view showing the breast compression and needle localization apparatus of the present invention attached to a patient for lateral needle insertion.
FIG. 2 is an exploded perspective view of the apparatus of the present invention also showing a mammographic film cartridge in phantom.
FIG. 3 is a cross-sectional view taken along the line 3--3 in FIG. 2.
FIG. 4 is a side elevational view of the apparatus of the present invention attached to patient for vertical needle insertion.
FIG. 5 is a plan view of the breast compression plate having a matrix of needle localization perforations and including the first and second buckles on opposite ends thereof.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to FIGS. 1, 2 and 4, the breast compression device of the present invention is generally indicated by reference numeral 10. The breast compression device 10 is shown attached to the breast 11 of a patient 12. An x-ray film cartridge 14 is shown inserted in a cartridge sleeve 16 on the exterior lateral side of one breast 11. A compression and needle locating plate 18 is biased into engagement with the interior side of the breast 11 by first and second straps 20 and 22. The plate 18 includes a perforation matrix 24 which includes a plurality of closely and evenly spaced perforations 25. The perforations 25 are adapted to receive a needle 26 which is inserted through the plate 18 into the breast 11 at the suspected location of a non-palpable lesion.
The first and second straps 20 and 22 preferably comprise a strip of "Velcro" material which is adapted to be secured to a complementary strip of "Velcro" material attached to the cartridge sleeve 16. In the illustrated embodiment, the straps 20, 22 are either made up of or have attached thereto the loop tape 28 portion of the "Velcro" fastener. The hook tape 30 of the "Velcro" fastening system is preferably secured to the cartridge sleeve 16. The loop tape 28 is the felt-like portion of the "Velcro" fastening system and the hook tape 28 is the portion of the fastening system having a series of closely spaced barbs or hooks.
Referring now to FIGS. 2 and 3, the components of the breast compression device are shown in greater detail. The cartridge sleeve 16 is preferably formed of a low atomic weight molded plastic having a low level of x-ray attenuation. Most preferably, the cartridge is formed of a polystyrene material such as "Royalite 24", a trademark of Rohm and Haas. However, it is anticipated that the cartridge may be formed of an acrylic, polyethylene or polyvinyl.
The cartridge sleeve 16 includes an upper plate 32 which extends across the top of the film cartridge 14. The upper plate 32 has an upper surface 34 which is preferably textured to reduce the tendency of a breast to slide thereon. The cartridge sleeve 16 includes a base plate 36 disposed on the opposite side of the film cartridge 14 from the upper plate 32. The upper plate 32 and base plate 36 are interconnected by first and second side plates 38 and 39. First and second side plates 38 and 39 are preferably reinforced or formed to be slightly thicker than the upper plate 32.
A front opening 40 is formed in the sleeve 16 through which the cartridge 14 is received. A lip 42 is formed adjacent the front opening 40 to aid in insertion and removal of the cartridge 14 in the sleeve 16. The rear edge 44 of the sleeve 16 is preferably concave to facilitate placement of the cartridge sleeve 16 against the body of the patient 12 in either the vertical or horizontal plane. Spacers 46, as shown in FIG. 3, are preferably placed at the rear edge 44 of the cartridge 16 to both space the base plate 36 relative to the upper plate 32 and to provide an end stop for insertion of the cartridge 14 in the sleeve 16.
The base plate 36 is preferably a rigid reinforced supporting surface. The base plate in the illustrated embodiment includes reversely bent flanges 48 extending inwardly from each of the first and second sides 38 and 39 to the middle of the base plate 36. The reversely bent flanges 48 are secured together by means of a reinforcement lamination 50 which is adhesively secured to the flanges 48. The upper plate 32, first and second sides 38 and 39 and reversely bent flanges 48 are all preferably formed in one piece as an integral molded part having molded corners. The reinforcement lamination 50 is preferably formed of the same material as the other portions of the sleeve 16.
Non-skid elastomeric feet 52 may be secured to the bottom of the base plate 36 to aid in positioning the sleeve 16 relative to the x-ray machine so that it will not slide during preparations for or the taking of x-rays.
Referring now to FIGS. 2 and 5, the compression plate and needle localization plate 18 will be described in greater detail. It is preferred that the plate 18 be formed of the same material as the sleeve 16 and that its lower surface is textured similar to the top of the sleeve 16 to prevent relative movement of the breast therebetween. The plate 18 includes first and second buckles 54 and 55 which are secured to first and second buckle flanges 56 and 57 which are formed integrally with the plate 18. First and second buckles 54 and 55 are connected to first and second buckle flanges 56 and 57 by means of rivets 58 or other fasteners.
As shown in FIG. 5, the buckles 54, 55 each include an arcuate bar 60 on their exterior ends which includes a convex cylindrical surface 61 over which the straps 20, 22 are secured. The convex cylindrical surface 61 of the arcuate bar 60 permit the straps to exert a pulling force in a range of angular directions relative to the plate 18. This is an important feature since the contour of bodies of different patients vary substantially and the breast compression device must be versatile to accommodate different body shapes.
The plate has a rear edge 64 which is preferably radiused and has curved corners 65 at opposite ends. The rear edge 64 is radiused and the corners 65 curved for the comfort of the patient. The front edge 66 of the plate 18 is preferably contoured to reflect the shape of a compressed breast 11 as a guide to the proper application of the device.
The plate 18 includes indicator perforations 68 at the midpoint of the perforation matrix 24 which facilitate counting perforations if necessary to change the perforation through which the needle 26 is inserted. By using the indicator perforation 68, the perforation matrix 24 may be broken into four quadrants, thereby reducing the number of perforations that must be counted to locate a particular perforation 25.
The straps 20, 22 are preferably connected to the buckles 54, 55 by threading the strap through the buckle and reversely bending the strap. Preferably, the entire strap length includes the loop tape 28 whereby when the strap is doubled back, a coupler 70 comprising a double-faced member formed of the "Velcro" hook tape 30 is used to secure the strap around the buckle.
In operation, the breast compression device 10 of the present invention is placed on a supporting surface which may either be a table or a stretcher and the breast 11 of the patient 12 is laid on the cartridge sleeve 16. The plate 18 is then placed on the opposite side of the breast from the sleeve 16 and first and second straps 20 and 22 are pulled outwardly to anchor the loop tape 28 of the straps to the hook tape 30 on the first and second sides 38 and 39 of the sleeve 16. It should be noted that the hook tape 30 extends across the width of the sleeve 16 to permit the straps 20, 22 to be secured anywhere along the length of the hook tape 30. In this way, widely varying body sizes may be accommodated by the same apparatus. It is anticipated that more than one size of plate 18 will be provided to accommodate varying breast sizes. The arcuate bar 60 of the buckles 54, 55 further aids in aligning the plate 18 relative to the breast 11 and sleeve 16.
The straps 20, 22 are pulled to exert a compressive force on the breast 11 by the plate 18. The straps 20, 22 may also be tightened from the plate end of the strap if more convenient by merely reattaching the coupler 70 from the loop tape 28 of the straps. The plate 18 is semi-rigid and will conform to a limited extent to the shape of the breast 11 as the straps 20, 22 pull down upon the ends of the plate 18. If the straps 20, 22 are formed of the loop tape 28 or include loop tape 28 across their entire length, the amount of compression and length of the straps may be adjusted by simply detaching the straps from the hook tape 30 and refastening the loop tape 28 at a different point to the hook tape 30.
Once the breast compression device 10 is attached to the patient's breast 11, the film cartridge 14 may be inserted in the front opening 40 of the cartridge sleeve 16 and exposed to the gamma rays of standard x-ray equipment. A preliminary x-ray may be taken of the breast after attachment of the device 10 and the lesion may be located by inserting a needle through the perforation 25 and the perforation matrix 24 located closest to the lesion. After the needle is inserted, another x-ray may be taken to determine whether or not the needle has been inserted at the lesion. If this is accomplished, a marker wire may be inserted through the needle and implanted in the breast adjacent the lesion to guide a surgeon to the proper location in the breast for the excisional biopsy. If the initial needle placement is not accurate, another perforation 25 may be selected by merely counting from the needle perforation 25 to the desired closer perforation.
After the lesion has been located and marked as appropriate, the breast compression device 10 may be removed and sterilized. Sterilization is accomplished merely by soaking the sleeve 16, plate 18 and first and second straps 20, 22 in a suitable antiseptic solution. The device of the present invention can be used repeatedly, and, if necessary, the straps may be replaced or repaired if the "Velcro" becomes worn.
The above description of a new, improved breast compression and needle localization apparatus is intended as an example and not in a limiting sense. It will be appreciated that the component parts, materials and relative dimensions given above may be modified without departing from the spirit and scope of the invention. The scope of the invention is to be determined based upon the full scope of the following claims and all equivalents thereof.
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A breast compression plate is connected to a cartridge sleeve for containing a mammographic film cartridge with adjustable tension in a range of positions with detachable straps. The plate is a semi-rigid planar member having a plurality of perforations disposed in a matrix for locating a needle used to determine the position of breast lesions. The plate has spaced buckles which are secured to the straps. The straps have a series of loops formed on one side which are gripped by a plurality of closely spaced hooks secured to spaced ends of the cartridge sleeve. The series of loops extend along the length of the straps to permit changing the length of the straps extending between the plate and the cartridge sleeve, thereby permitting lateral positioning and tension adjustment. The plurality of hooks extend across the cartridge sleeve generally perpendicular to the length of the straps on opposite ends of the sleeve to permit positioning of the plate perpendicularly relative to the length of the straps.
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BACKGROUND ART
This invention relates to a picking control device in a loom in which in an air jet loom, even when the flying characteristic of weft yarn is varied, stable picking operation can be continued.
In the air jet loom, when the flying characteristic of weft yarn used for weaving is varied, picking sometimes becomes unstable. It is considered that such unstable picking as just mentioned principally results from change in air resistance of yarns since yarn properties such as coarseness of yarns, sizes of fuzz and the like are varied lengthwise of weft yarn.
In view of the above, various procedures have been proposed in an attempt of continuing the stable picking operation even when the flying characteristic of weft yarn is varied. The most typical procedure is designed so as to monitor a loom mechanical angle (hereinafter referred to as "arrival angle") wherein in picking, an end of weft yarn arrives at the anti-picking side, and controls a loom mechanical angle (hereinafter referred to as "start angle") for starting the picking operation and jet pressure of picking main nozzle and sub-nozzle.
In the aforementioned method, when the flying characteristic of weft yarn lowers so that the lagging of the arrival angle is detected, a control is made so as to make fast the picking start angle and increase the jet pressure in order to correct the lagging of the arrival angle. On the other hand, with respect to the leading of the arrival angle, the picking start angle is retarded and the jet pressure is decreased to thereby maintain the arrival angle constant whereby a better result can be obtained, than the case where only one of the start angle and jet pressure comprises an object to be controlled.
A further proposal is that an upper limit value is set to the jet pressure, and only when the jet pressure controlled by a deviation of the arrival angle exceeds the upper limit value, a control is made so that the start angle is held fast (Japanese Patent Laid-open No. 2 (1990)-118138 publication).
Incidentally, generally, when the jet pressure is excessively low, unevenness of the deviation of the arrival angle for each picking increases, and as a result, the flying of the weft yarn becomes unstable and a weft stop is apt to occur. Conversely, when the jet pressure is excessively high, at the time of termination of picking, a so-called cutting of the weft yarn at the time of termination of picking is apt to occur as well as occurrence of fuzz stripes on the fabrics and in addition, air consumption is excessively large, which is uneconomical. Accordingly, it is desired that the optimum value of the jet pressure be set to a low value at which no weft stop occurs.
On the other hand, when the start angle is excessively fast, the warp shedding is not sufficiently formed and weft engagement is apt to occur but it is advantageous that the start angle is as fast as possible in view of securing the sufficient flying time of weft yarn. The optimum value is present in the case where the start angle is fast in consideration of the above matter.
That is, the jet pressure and the start angle are advantageously as close as possible to these optimum values, reducing occurrence of inferior weaving such as restriction cutting, weft engagement with warp yarn and the like. Thus stable operation can be continued.
However, employment of the aforementioned prior art poses a problem in that it is difficult to coincide the jet pressure and the start angle with the optimum value and the stable operation cannot be continued with a sufficient scope. That is, in the case where correction signals (i.e., based upon a fast or slow arrival angle); are merely applied in parallel to control systems for controlling the start angle and the jet pressure or when one exceeds the upper limit value, a correction signal is applied to the other, such that stable picking could be realized, however the jet pressure and the start angle at that time are possibly greatly shifted from the respective optimum values since no means are provided for setting them to the optimum value. In other words, the operation is sometimes continued in the state where the jet pressure and the start angle are greatly deviated from the respective optimum values, at which time a scope for achieving the stable picking is small, and most likely, air consumption unreasonably increases.
SUMMARY OF THE INVENTION
In view of the problem as noted above with respect to prior art, it is an object of this invention to provide a picking control device for a loom wherein a set pressure or a set start angle (or set speed) having an optimum value is corrected and controlled for allowing output the of the other whereby at least one of the jet pressure or start angle (or speed of the loom) is maintained at an optimum value for setting the arrival angle to the target level, and a stable picking operation can be continued with sufficient scope and appropriate air consumption.
For achieving the aforesaid object, the first invention according to this application is principally configured by comprising a pressure controller for controlling jet pressure of a picking nozzle, a timing controller for controlling operation time of a picking member and a condition setting section, said condition setting section comprising a deviation detection means for calculating a deviation of an arrival angle from an arrival angle of filling yarns and a set arrival angle, a pressure correction means for outputting a pressure correction signal for correcting a set pressure in response to the deviation of arrival angle to the pressure controller, and an angle correction means for outputting an angle correction signal for correcting a set start angle in response to the deviation of arrival angle to the timing controller, said pressure correction means and said angle correction means outputting a pressure correction signal and an angle correction signal on condition that the angle correction signal and pressure correction signal are not present.
The second invention is principally configured by using a speed controller for controlling a speed of a loom in place of the timing controller of the first invention, the condition setting section comprising a speed correction means for outputting a speed correction signal for correcting a set speed to the speed controller, said speed correction means outputting a speed correction signal on condition that a pressure correction signal is not present.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an overall systematic view showing one embodiment of a control device according to the present invention;
FIG. 2 is an overall structural view of a loom control system to which is applied the control device shown in FIG. 1;
FIG. 3 is a diagram for explaining the operation of FIGS. 1 and 2; and
FIG. 4 is a systematic view of essential parts showing a further embodiment of the control device according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of this invention will be described hereinafter with reference to the drawings.
The loom comprises an air jet loom as shown in FIG. 2. The weft yarn W released from a supply package 1 is picked into a warp opening Wp via a drum type weft length-measuring and storage device (hereinafter merely referred to as the storage device) D and a main nozzle MN. Sub-nozzles SNi (i=a, b . . . n) divided into plural groups are disposed along the travel route of the weft yarn W.
The storage device D includes an engaging pin drive D1 and a release sensor D2. The weft yarn W wound about and stored on a drum D3 is subjected to picking by driving the engaging pin drive D1 to a release position and opening open-close valves Vm, Vsi (i=a, b . . . n) to actuate the main nozzle MN and the sub-nozzles SNi in response to picking signals Sd, Sm and Ssi (i=a, b . . . n) from a timing controller 20, and the picking length Wn is measured by the release sensor D2.
The main nozzle MN and sub-nozzles SNi are connected to a common air source AC via the open-close valves Vm and Vsi and pressure regulating valves PVm and PVs, and jet pressures Pm and Ps are controlled by control signals Spm and Sps from a, pressure controller 10. On the anti-picking side of the loom is disposed a weft feeler ES for detecting the picked weft yarn W, and an output thereof is input into a condition setting section 30. Furthermore, a loom mechanical angle θ from an encoder EN connected to a main shaft of the loom is branched and input into the condition setting section 30 and the timing controller 20.
The picking control device for the loom comprises pressure controller 10, timing controller 20 and condition setting section 30 as shown in FIG. 1, the condition setting section 30 comprising a deviation detection means 31, a pressure correction means 32 and an angle correction means 33.
The pressure controller 10 comprises a pressure setter 11, an adder 12, and two control amplifiers 13, 13, and an output thereof is input, as control signals Spm and Sps, into the pressure regulating valves PVm and PVs. A set pressure Po from the pressure setter 11 and a pressure correction signal Sp from the condition setting section 30 are input into the adder 12.
The timing controller 20 comprises a start angle setter 21, an adder 22, a comparator 23, an engaging pin control circuit 24, and open-close valve control circuits 25m, 25s, 25s . . . A set start angle θo from the start angle setter 21 and an angle correction signal Sa from the condition setting section 30 are input into the adder 22, and an output of the adder 22 and a loom mechanical angle θ from the encoder EN are input into the comparator 23. The picking length Wn from the release sensor D2 is input into the engaging pin control circuit 24, and an output thereof is input, as a picking signal Sd, into the engaging pin drive D1. Outputs of the open-close valve control circuits 25m, 25s, 25s . . . are input, as picking signals Sm and Ssi, into the open-close valves Vm and Vsi.
A deviation detection means 31 in the condition setting section 30 comprises an arrival angle detector 31a, a comparator 31b and an arrival angle setter 31c, and an output from the picking feeler ES and a loom mechanical angle θ from the encoder EN are input into the arrival angle detector 31a. An arrival angle θe from the arrival angle detector 31a and a set arrival angle θeo from the arrival angle setter 31c are input into the comparator 31b. The comparator 31b calculates an arrival angle deviation .sub.Δ θe as .sub.Δ θe=θeo-θe, and outputs a leading signal S1 when .sub.Δ θe>0 and a lagging signal S2 when .sub.Δ θe<0 to the pressure correction means 32 and the angle correction means 33, respectively.
The pressure correction means 32 and the angle correction means 33 are formed by the same circuit configuration, each of which comprises AND gates 32a, 32b, 33a, 33b, counters 32c, 33c, and inverters 32d, 33d.
Accordingly, a leading signal S1 and a lagging signal S2 from the deviation detection means 31 are branched and input into the AND gates 32b, 33a and the AND gates 32a, 32b, and outputs of the AND gates 32a and outputs of the AND gates 32b, 33b are connected to addition terminals U and subtraction terminals D of the counters 32c, 33c. Minus terminals M, M indicating that contents of the counter 32c, 33c is zero or negative are feedback-connected to the AND gates 32b, 33b through the inverters 32d, 33d, and the terminal M of the counter 32c and the minus terminal N of the counter 33c are cross-connected to the AND gates 33a, 33b and the AND gates 32a, 32b, respectively. Outputs of the counters 32c, 33c are in the form of a pressure correction signal Sp and an angle correction signal Sa, respectively, with respect to the pressure controller 10 and the timing controller 20.
When the contents of counter 32c, 33c is zero or negative, output δP, δθ of the counter is stopped.
The control operation carried out by the aforementioned control device will be described hereinafter.
It is now assumed that the pressure correction signal Sp and the angle correction signal Sa from the condition setting section 30 are not present, their values being zero. Picking is started, for the weft yarn W, at the set start angle θo set to the start angle setter 21 of the timing controller 20, and the weft yarn W arrives at the anti-picking side at the set arrival angle θeo set to the arrival angle setter 31c of the deviation detection means 31, and the weft yarn W is picked by the set jet pressure Po to the pressure setter 11. That is, since at that time, the arrival angle θe is θe=θeo, the arrival angle deviation .sub.Δ θe is .sub.Δ θe=θeo-θe=0, and accordingly, in the comparator 31b, neither leading signal S1 or lagging signal S2 is output.
The comparator 23 of the timing controller 20 compares the start angle θs (θs=θo) input through he adder 22 with the loom mechanical angle θ, and at the time of θ=θs (=θo), a signal for starting the engaging pin control circuit 24 and the open-close control circuits 25m, 25s, 25s . . . is output to actuate the engaging pin drive D1 and the open-close valves Vm and Vsi so that the picking of the weft yarn W can be started. The return operation of the engaging pin is controlled by the engaging pin control circuit 24 corresponding to the picking length Wn from the release sensor D2, and the open time control of the open-close valves Vm and Vsi is carried out by the open-close control circuits 25m, 25s, 25s . . .
On the other hand, the pressure controller 10 controls so that the jet pressures Pm and Ps of the main nozzle MN and the sub-nozzles SNi realized by the pressure regulating valves PVm and PVs coincide with the set pressure Po set to the pressure setter 11. At that time, however, the set pressure Po and the set start angle θo have been set to the optimum pressure and optimum loom mechanical angle, respectively, necessary for realizing the normal picking operation (see area A in FIG. 3).
When the flying characteristic of the weft yarn W is enhanced (as shown in the area B of FIG. 3) for some reason, and the arrival angle θe is faster than the set arrival angle θeo, the deviation detect means 31 detects the arrival angle deviation .sub.Δ θe (.sub.Δ θe=θeo-θe >0) to output the leading signal S1 to the pressure correction means 32 and the angle correction means 33.
Then, the leading signal S1 is input into the AND gate 32b of the pressure correction means 32 and the AND gate 33a of the angle correction means 33, and the former has been closed through the inverter 32d since the content of the counter 32c has been zero whereas the latter has been open. Accordingly, the leading signal S1 arrives at the addition terminal U of the counter 33c through the AND gate 33a to increase the content of the counter 33c in a positive direction by a predetermined quantity. As a result, the minus terminal M of the counter 33c assumes a low level to close both the AND gates 32a and 32b of the pressure correction means 32 and open the AND gate 33b through the inverter 33d. Thereafter, the leading signal S1 and the lagging signal S2 from the deviation detection means 31 arrive at the addition terminal U and the subtraction terminal D of the counter 33c from the angle correction means 33 but do not arrive at the counter 32c of the pressure correction means 32.
On the other hand, an increase in a positive direction in the counter 33c is converted into a suitable start angle correction quantity δθ, which is then output as an angle correction signal Sa to the adder 22 of the timing controller 20. So the timing controller 20 can take place the picking operation with the start angle θs as θs=θo+δθ, the start angle θs at that time being corrected in a slow direction with respect to the set start angle θo. Thereby, the arrival angle θe is immediately corrected to the set arrival angle θeo.
When the flying characteristic of the weft yarn W further increases to become faster, the leading signal S1 is continuously output from the deviation detection means 31, and therefore, the content of the counter 33c further increases accordingly and the angle correction signal Sa from the angle correction means 33 outputs a larger start angle correction quantity δθ to the timing controller 20 whereby the arrival angle θe is maintained at the set arrival angle θeo.
When the flying characteristic of the weft yarn W is turned to the decreasing trend as in area C of FIG. 3, a lagging signal S2 is output from the deviation detection means 31 whereby the content of the counter 33c decreases and therefore the start angle correction quantity δθ with respect to the timing controller 20 also gradually decreases.
When the flying characteristic of the weft yarn W further decreases so that the content of the counter 33c is zero as shown in area D of FIG. 3, the start angle correction quantity δθ is δθ=0, and the start angle θs by the timing controller 20 returns to the set start angle θo which is the optimum value. At this time, the counter 33c is zero whereby the And gate 33b is closed and the AND gate 32a is opened.
When the flying characteristic further lowers, the lagging signal S2 arrives at the addition terminal U of the counter 32c of the pressure correction means 32 through the newly opened AND gate 32a, and therefore the content of the counter 32c is increased in a positive direction. Then, the pressure correction signal Sp is output from the pressure correction means 32, and accordingly, the pressure controller 10 can correct and control the jet pressures Pm and Ps of the main nozzle MN and sub-nozzles SNi increasing to (Po+δP) and maintain the arrival angle θe at the set arrival angle θeo. Here, δP represents the pressure correction quantity determined by the content of the counter 32c and expressed by the magnitude of the pressure correction signal Sp. When the counter 32c increases in a positive direction, the AND gate 32b is opened through the inverter 32d and the AND gates 33a and 33b are closed.
If the flying characteristic then lowers, the content of the counter 32c is likewise increased by the lagging signal S2 to increase the pressure correction quantity δP, and the pressure controller 10 can maintain the arrival angle θe at the set arrival angle θeo.
If the flying characteristic of the weft yarn W assumes the up trend as shown in area E of FIG. 3, the leading signal Si instead of the lagging signal S2 is output but at that time, the AND gate 32b has been opened and the AND gate 33a has been closed and therefore the leading signal S1 can arrive at the subtraction terminal D of the counter 32c through the AND gate 32b. Accordingly, the pressure correction quantity δP decreases and the jet pressures Pm and Ps also decrease, and the pressure controller 10 maintains the arrival angle θe at the set arrival angle θeo.
Even in the case where the flying characteristic of the weft yarn W is varied in either direction as described above, either angle correction means 33 or pressure correction means 32 is actuated so that either the start angle θs or the jet pressures Pm, Ps can be corrected and controlled through either the timing controller 20 or the pressure controller 10 to maintain the arrival angle θe at the set arrival angle θeo.
Since the angle correction means 33 and the pressure correction means 32 are operated in the condition in which the other one of them does not output the pressure correction signal Sp and the angle correction signal Sa, at least one of the jet pressures Pm, Ps, and the start angle θs are to coincide with the set pressure Po and the set start angle θo, which are the optimum values. In addition, correction is made only in a high direction from the optimum value of the jet pressures Pm, Ps or in a slow direction from the optimum value of the start angle θo.
When the content of counter 32c (33c) alternates from positive to negative (from negative to positive) radically, the pressure correction signal Sp (the angle correction signal Sa) is not output from this counter 32c (33c).
In the foregoing explanation, the leading signal S1 or the lagging signal S2 is output as one pulse signal each picking of the weft yarn W, and the contents of the counter 32c on the counter 33c are increased or decreased by a predetermined quantity every pulse. On the other hand, an increase and decrease in quantity every time of the counters 32c and 33c may be proportional to the magnitude of the arrival angle deviation .sub.Δ θe calculated by the comparator 31b. For example, the comparator 31b may change the pulse width of the leading signal S1 and the lagging signal S2 according to the magnitude of the arrival angle .sub.Δ θe, and the counters 32c and 33c may decide the increase and decrease in quantity every time according to the pulse width thereof. Further, the arrival angle deviation .sub.Δ θe is A/D converted and then introduced from the comparator 31b to the counters 32c and 33c so that the increase and decrease quantity proportional to the arrival angle deviation .sub.Δ θe may be accumulated in the counters 32c and 33c. Furthermore, counters for counting the leading signals S1 and lagging signals S2 output every picking of the weft yarn W are provided so that the contents of the counters 32c and 33c may be increased and decreased whenever the leading signals S1 and lagging signals S2 are output by a predetermined quantity.
Other Embodiment
The angle correction means 33 of the condition setting section 30 shown in FIG. 1 can be replaced by a speed correction means 34 shown in FIG. 4, and the timing controller 20 replaced by a speed controller 40. Here, the speed correction means 34 has the same circuit configuration as that of the angle correction means 34, and a speed correction signal Sv is output from a counter 34c corresponding to the counter 33c to the speed controller 40. When the content of counter 34c is zero or negative, the speed correction signal 34 is not output from this counter.
The speed controller 40 comprises a speed setter 41 for setting and outputting a set speed Vo, an adder 42 for inputting the set speed Vo and a speed correction signal Sv, and an inverter 43 for controlling the speed of a main motor M by a command speed Vs from the adder 42. The main motor M drives a main shaft MS through a belt Ml, and a brake MB and an encoder EN are connected to the main shaft MS. The loom mechanical angle θ from the encoder EN is fed back to the inverter 43 and used as a speed feedback signal and is introduced into the arrival angle deviation detection means 31 and the timing controller 20 similarly to the previous embodiment. In this case, the timing controller 20 is independent of the condition setting section 30, and the picking operation is carried out at the fixed start angle θs (θs=θo).
In the control operation by the present control device, when the flying characteristic of the weft yarn W becomes large, the content of the counter 34c of the speed correction means 34 is increased in a positive direction by the leading signal S1 from the deviation detection means 31 so that the speed correction signal Sv is output. Therefore, the speed controller 40 corrects and controls the command speed Vs to Vs=Vo+δV so that the speed of the main motor M is corrected in a high direction. The reference character δV denotes the speed correction quantity corresponding to the content of the counter 34c. So, if the lower optimum value is set in advance as the set speed Vo, the speed of the main motor M, that is, the operation speed of the loom is corrected in a high direction whereby the arrival angle θe can be maintained at the set arrival angle θeo.
Thereafter, the speed correction means 34 can output the speed correction signal Sv on condition that the pressure correction means 32 does not output the pressure correction signal Sp to continue the stable picking, in exactly the same manner as that of the previous embodiment.
While in the foregoing explanation, the jet pressures Pm and Ps of the main nozzle MN and sub-nozzles SNi has been always in the relation of Pm=Ps, it is to be noted that the relation may be of Pm=a Ps (a is constant which is not 1) by insertion of a suitable ratio setting element into the input side of the control amplifiers 13, 13. It is further to be noted that the pressure regulating valves PVs may be disposed every group of the sub-nozzles SNi so as to realize the jet pressures which are different for each group. That is, the jet pressures of each picking nozzle formed from the main nozzle MN and sub-nozzles SNi may serve to control the pressure controller 10 collectively, or by the main nozzle MN alone or by dividing the sub-nozzle SNi into suitable groups.
While the timing controller 20 starts the operation of the picking members comprising the main nozzle MN, sub-nozzles SNi and engaging pin drive D1 at the time when the loom mechanical angle θ coincides with the start angle θs, it is to be noted that a suitable time difference may be provided in operation time of these picking members if necessary. That is, the operation of the main nozzle MN may be started prior by a predetermined time to the operation of the engaging pin drive D1 and vice versa. Further, the sub-nozzles SNi may be operated with a suitable time difference with respect to the operation time of the main nozzle MN.
The weft feeler ES may be disposed at a suitable position in the midst of woven fabrics instead of being disposed on the anti-picking side of woven fabrics. Furthermore, the weft feeler ES may be omitted, and the condition setting section 30 may use the loom mechanical angle θ when the picking length Wn from the release sensor D2 reaches a predetermined quantity, in place of the arrival angle θe.
As described above, according to this invention, there are provided a pressure controller, a timing controller (or a speed controller) and a condition setting section, said condition setting section comprising a deviation detection means, a pressure correction means and an angle correction means (or a speed correction means), said pressure correction means and said angle correction means (or speed correction means) being designed so that both correction means are not operated, an arrival angle deviation is input to either of said pressure correction means or said angle correction means, and one of them is not operated, the arrival angle deviation is input to the other operating correction means. So either pressure correction signal, angle correction signal (or speed correction signal) is not output whereby jet pressures controlled by the pressure controller and the start angle controlled by the timing controller (or the speed of the loom controlled by the speed controller) make it possible to provide a continuous stable picking operation in the state where at least one of them is maintained at the optimum value. Therefore, there are the excellent effects that in the operation, possible occurrence such as restriction cut, warp engagement and the like is very small, a sufficient scope is obtained, and an adequate air consumption can be realized.
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A picking control device for a loom comprising a pressure controller for controlling jet pressure of a picking nozzle, a timing controller for controlling operation time of a picking member, angle corrector for correcting the start angle of the weft yarn and a condition setting section which is operated on the condition that one of the signals from the pressure controller or angle corrector is not present so that at least one of the jet pressure, start angle or speed of the loom is maintained at an optimum value. This allows for effective picking with adequate air consumption and helps to prevent weaving defects such as cutting of the weft yarn at the time of termination of picking, warp engagement and the like.
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BACKGROUND OF THE INVENTION
The invention relates to a cooler, in particular, a cooler for electrical components, in the form of a heat pipe.
Coolers of this type are fundamentally known and are based on the principle of vaporization and condensation of a coolant, or heat transport medium, housed in the closed interior of the cooler. Generally these coolers have a round structure (U.S. Pat. No. 3,537,514). Lengthwise grooves are used as the capillary structure. These round coolers must be connected to a flat carrier on which the components to be cooled are located. These carriers yield additional heat transfer or thermal resistance.
Furthermore, it is also known to have a flat design for this cooler (U.S. Pat. No. 5,642,775). These known coolers consist of a block in which tubular channels are formed. Production is complex and expensive.
Furthermore, it is also known to have a cuboidal cooler (U.S. Pat. No. 4,957,803); its housing consists of a plurality of metal layers stacked on top of one another and connected superficially to one another, which are structured and arranged such that within the body, slots yield crossing channels which are joined to one another at the crossing points. This known design is only suited as a thermal spreader. There are no differing vapor channel and capillary structures. In addition, heat transport over long distances is necessary.
The object of the invention is to devise a cooler with improved properties.
SUMMARY OF THE INVENTION
The cooler as claimed in the invention is characterized by a simple and economical production. Transmission of heat energy from the outside, into the vaporization area, into the cooler, or from the condensation area to the outside over a short distance is possible by posts which are located in the area of the capillary structure and which are formed by the metal layers. Furthermore, the cooler has a vapor channel area or a vapor channel structure with a large flow cross section, yielding optimum cooling output.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is detailed below using the following figures:
FIG. 1 shows, in a simplified perspective view, a cooler in the form of a flat, plate-shaped or cuboidal heat pipe;
FIG. 2 shows a section along line I—I of FIG. 1 ;
FIGS. 3 and 4 show other possible embodiments of the cooler of the invention;
FIG. 5 shows in an enlarged partial representation, and in a side view, the heat pipe, as claimed in the invention, formed by a stack of several metal layers;
FIGS. 6 and 7 each show in a simplified view, and in an overhead view, two individual or metal layers for example of copper for the capillary area ( FIG. 6 ) and the vapor channel area ( FIG. 7 );
FIG. 8 shows, in a partial schematic, a section through the capillary area, or through the vapor area, of FIGS. 6 and 7 ;
FIGS. 9 and 10 show, in an overhead view, structured metal layers for the capillary area, or the capillary structure, ( FIG. 9 ) or for the vapor channel area or the vapor channel structure ( FIG. 10 ) in another possible embodiment of the invention;
FIGS. 11 and 12 each show, in a partial representation, the two stacked metal layers of FIG. 9 for the capillary area;
FIG. 13 , in a partial representation, shows an overhead view of a partial structure of the capillary area formed by two successive metal layers of FIGS. 11 and 12 ;
FIGS. 14 , 15 and 16 show representations similar to FIGS. 11 , 12 and 13 for the vapor channel area;
FIGS. 17 and 18 show, in an enlarged partial representation, and in an overhead view, similar to FIGS. 11 and 12 , individual metal layers for the capillary area of another possible embodiment;
FIG. 19 shows, in a partial representation, an overhead view of a partial structure of the capillary area formed by two successive metal layers of FIGS. 17 and 18 ;
FIGS. 20 , 21 and 22 show representations similar to FIGS. 17 , 18 and 19 , but for the vapor channel area;
FIG. 22 shows the two layers of FIGS. 20 and 21 on top of one another for forming the vapor channel area;
FIG. 23 shows, in the representation of FIG. 1 , another possible embodiment of the invention;
FIG. 24 shows a section along line II—II of FIG. 23 , for the sake of simplicity only, the capillary area, or the capillary structure being shown;
FIG. 25 shows a section along line III—III or IV—IV of FIG. 23 , for the sake of simplicity only the capillary area or the capillary structure being shown;
FIG. 26 shows, in a simplified representation, and in an overhead view, one metal layer for the capillary area;
FIGS. 27 and 28 each show, in a simplified representation, and in an overhead view, two additional embodiments of one metal layer for the vapor channel area; and
FIG. 29 shows, a representation similar to FIG. 24 , another possible embodiment.
DETAILED DESCRIPTION OF THE INVENTION
In FIGS. 1–22 , a heat sink or cooler for dissipating the heat of a heat source is labeled 1 . The cooler 1 is built as a heat pipe, but in contrast to the known heat pipe arrangements, the cooler 1 has a very flat plate-shape with flat surfaces on the top and bottom. In the embodiment shown in FIG. 1 , the cooler 1 is shown in an overhead view with a rectangular peripheral line, or with the shape of a very flat cuboid, which is rectangular in an overhead view.
Generally the cooling or vaporizer area (first area) is labeled 2 , and the second area for heat dissipation, or the condenser area, is labelled 3 . The two areas are offset against one another in the lengthwise direction L, of the plate-shaped cooler 1 , and on either side of a center plane M, which inter sects the cooler 1 , and its lengthwise sides vertically. The heat dissipated on the area 2 , to the cooler 1 is labelled with an arrow P 1 , and the heat dissipated by the cooler 1 , on area 3 , is labelled by an arrow P 2 . The heat source is formed by the semiconductor power components which are provided on the closed flat top and/or bottom of the cooler 1 , on area 2 , the flat top and/or bottom being formed by one metal layer 7 (metal foil or plate).
In FIG. 2 , these semiconductor power components, or chips, which produce heat loss, are labelled 4 – 6 . For electrical insulation on the top and/or bottom of the cooler 1 , there is provided, at least in the area of chips 4 – 6 , one ceramic layer 7 ′, which is connected in a suitable manner to the closed metal layer 7 , which forms the top and bottom of the cooler.
The inner structure of the cooler 1 , and how it works, in general, follow from FIG. 2 . The inner structure consists of three areas which each extend over the entire cooler, and which are stacked on top of one another, between the top and bottom metal layer 7 , more specifically it consists of two outer capillary structures or areas 8 , and a middle vapor channel, or vapor channel area, or vapor channel structure 9 . The capillary areas 8 are formed by a host of channels which extend between the two areas 2 and 3 and are connected, in at least these areas to the vapor channel or the vapor channel area 9 . The vapor channel is a continuous channel which extends over the entire length and width of the cooler 1 , or is formed, in the manner detailed below, by a structure of several individual channels, the entire cross section of the vapor channel being much larger compared to the overall cross section of the capillary areas 8 .
The interior of the cooler 1 is partially filled with a coolant which vaporizes when heated. In the simplest case water, also in mixture with an additive, for example, methanol, is suited as the coolant.
How the cooler 1 works is based on the fact that the heat which has flowed onto the area 2 vaporizes the coolant there within the cooler and the vapor then flows in the vapor channel 9 from the area 2 in the direction to the area 3 , i.e. in the direction of the arrow A of FIG. 2 . On the area 3 , the heat is dissipated to the outside according to arrow P 2 . This leads to condensation of the coolant, which as condensate travels into the capillary areas 8 , and from there under capillary action flows back opposite the arrow A of FIG. 2 on the area 2 , where then again vaporization of the medium takes place by the absorbed heat P 1 , etc. The cooler 1 , with reference to the vaporizable coolant provided in the interior of this cooler, forms a closed system, as is inherently known of heat pipe systems.
FIG. 3 shows again in a simplified representation, the cooler 1 , and on the area 3 , cooling elements, or cooling sheets 10 , being provided on the outside, which with a large surface cause dissipation of the heat to the outside according to arrow P 2 , and through or around, by an air stream generated by fan flows.
FIG. 4 shows in a similar representation to FIG. 3 , an auxiliary cooler 11 which is located on the area 3 and through which a coolant or heat-transporting medium of an external cooling system flows, for example, cooling water of an external cooling circuit. This auxiliary cooler 11 can be formed directly on the area 3 of the cooler 1 by several metal layers which are stacked on top of one another and which are joined superficially to one another and in the housing of the auxiliary cooler 11 form internal, closed cooling channels through which the external coolant flows. In particular, it is possible to form the auxiliary cooler 11 as a so-called microcooler, as is described for example in DE 197 10 783.
As is indicated in FIG. 5 with 12 and 13 , the cooler 1 is formed by a plurality of metal layers, for example copper layers or plates, or cutouts from a copper foil, which are structured such that within the cooler 1 between these layers, and/or through these layers, the capillary structures 8 through the metal layers 12 , and vapor structures 9 through the metal layers 13 , with the corresponding channels which extend at least in the lengthwise direction L result.
FIGS. 6–22 show different embodiments for the cooler 1 which differ essentially only by the different structuring of the metal layers 12 and 13 .
According to the embodiment of FIGS. 6–8 , to form the capillary structures 8 metal layers 12 a and 12 b are used which are each provided with a plurality of continuous parallel slots, the slots 14 a in the metal layers 12 a extending transversely to the lengthwise direction L and the slots 14 b in the metal layers 12 b extending in the lengthwise direction L.
For the vapor area, or the vapor channel structure 9 , there are metal layers 13 a and 13 b , which in turn have slots 15 a and 15 b , which correspond to slots 14 , and slots 15 a in the metal layer 13 a perpendicular to the lengthwise axis L and slots 15 b in the metal layer 13 b in the lengthwise direction L. The design is such that the axial distance of two adjacent slots 14 a and 14 b is the same not only on the metal layers 12 a and 12 b , but is also equal to the axial distance of two slots 15 a and 15 b on the metal layers 13 a and 13 b . In any case, the width of the slots 15 a and 15 b is roughly 1.5–10 times greater than the width of the slots 14 a and 14 b . Furthermore, the thickness of the metal layers 13 a and 13 b , is roughly 1–3 times the thickness of the metal layers 12 a and 12 b.
The stacking of the metal layers 12 a and 12 b forms capillary structures 8 with crossing channels, which are connected to one another, at the crossing points, and which are formed by the slots 14 a and 14 b . Likewise, by stacking the metal layers 13 a and 13 b on top of one another, a vapor structure 9 is achieved with crossing channels, which are connected to one another at the crossing points, formed by the slots 15 a and 15 b . This approach results in that after joining the metal layers by the latter within the body of the cooler 1 produced in this way, continuous post-like areas 16 are formed, which extend from the top metal layer 7 , which tightly seals the upper capillary area 8 , as far as the lower metal layer 7 , which tightly seals the lower capillary area 8 , and which deliver the necessary strength for the cooler 1 , and also ensure optimum heat conduction into and out of the cooler 1 . These post-like structures 16 are indicated in FIG. 5 with a broken line.
The metal layers 12 and 13 , can also be structured differently to form structures 8 and 9 . Another example is shown in FIGS. 9–16 . FIG. 9 shows a structured metal layer 12 c for the capillary structures 8 . This metal layer 12 c is provided in its middle area, i.e. within a closed edge area 17 , in the manner of screen with a plurality of openings 18 which are each made hexagonal and which adjoin one another similarly to a honeycomb structure. These openings 18 are each formed by crosspieces 19 , which pass into one another and which surround each opening 18 in the form of a hexagonal ring structure. On the edge area 17 the openings 18 are only partially formed.
On three corners of the hexagonal ring structure of each opening 18 , the crosspieces 19 form an island 20 with an enlarged area, i.e. in the embodiment shown with a circular surface. The islands 20 are distributed such that on each opening 18 , in an assumed peripheral direction one corner with an island 20 , follows one corner without one such island 20 . Furthermore, the structuring is chosen such that two crosspieces 19 of each opening 18 , lie parallel to the lengthwise axis L, of the rectangular metal layer 12 c , and in one axial direction parallel to the lengthwise axis L one island 20 , is followed by an opening 18 , one corner point without an island, one crosspiece 19 which extends in the direction of the lengthwise axis L, and then a new island 20 , etc.
Furthermore, structuring of the metal layer 12 c is not completely symmetrical to a center axis which runs perpendicularly to the lengthwise axis L, but the openings 18 are offset relative to the center axis such that it does not intersect the crosspieces 19 , which run parallel to the lengthwise axis L, but intersects the islands. In this way, to form the capillary structures 8 , it is possible to provide in alternation, one metal layer 12 c in the form shown in FIG. 9 , as a layer N ( FIG. 11 ), and as the subsequent layer N+1, one metal layer 12 c in a layer turned around the center axis ( FIG. 12 ), following one another in order to obtain the structure shown in FIG. 13 in which the islands 20 of these layers N and (N+1) lie on one another, while in the middle of each opening 18 , of one layer, there is an area of the adjacent layer on which three crosspieces 19 meet one another without an island 20 , as is shown in FIG. 13 . With the described structuring of the metal layers 12 c therefore using the same metal layers, very finely structured capillary areas 8 with channels widely branched in all three solid axes can be produced simply by turning every other layer.
FIG. 10 shows a representation like FIG. 9 , with a metal layer 13 c for producing the vapor channel structure 9 . The metal layer 13 c in its structuring corresponds to the metal layer 12 c , and differs from it simply in that some of the crosspieces 19 , which run transversely to the lengthwise axis L, were omitted, such that the remaining crosspieces 19 , together with the islands 20 , form zig-zag band-like structures 21 ′, which extend in the lengthwise direction L, with passages 21 , which lie in between and which extend in the lengthwise direction. According to FIG. 16 , the vapor channel area 9 is formed by at least two metal layers 13 c being stacked on top of one another, and connected to one another, such that every other metal layer 13 c is turned around the center axis so that also in the vapor area 9 , the islands 20 of the individual layers 13 c , come to rest on one another and in this way form continuous, post-like structures 16 . The passages 21 yield flow channels with larger effective flow cross section for the vapor area 9 .
FIGS. 17–22 show as further embodiments, metal layers 12 d for forming the capillary structures 8 , and the metal layers 13 d , for forming the vapor channel structure 9 . FIGS. 17 and 18 in turn show the same metal layer 12 d , but FIG. 18 in a layer turned around the center axis relative to FIG. 17 . Likewise, FIGS. 20 and 21 show the same metal layer 13 d , but in FIG. 21 in a layer turned around the center axis relative to FIG. 20 .
The metal layer 12 d is structured in the manner of the screen within the closed edge area 17 , with a plurality of angled openings 22 which are oriented with the angle bisector of their angle segments parallel to the lengthwise axis L.
To form the respective capillary structure 8 , at least one metal layer 12 in an unturned form and one metal layer 12 in a turned form, are placed on top of one another, and are connected to one another, such that then the partially overlap ping openings yield passages 23 , via which the channels formed by the openings 22 , in the individual layer, are joined to one another, into a widely branched channel structure, and in addition, post-like areas 16 result.
As FIGS. 17 and 18 show, the openings 22 are each located in several rows which follow one another in the direction of this lengthwise axis and which run perpendicular to the lengthwise axis L, the openings 22 each being offset from row to row on gaps.
The metal layer 13 d , shown in FIGS. 20 and 22 , differs from the metal layers 12 d , simply in that, in addition to the openings 22 , there are continuous openings which are bordered on the end by the edge area 17 , and which extend in the lengthwise direction L, such that in turn band-like structures 24 ′ result, which extend in the lengthwise direction and which also have openings 22 . By placing one unturned metal layer 13 d , and one turned metal layer 13 d , on top of one another on the band-like structures, additional channels are formed which are connected to one another via the passages 23 , and also the post like areas 16 , which adjoin the areas 16 in the capillary areas 8 and are added to the continuous posts 16 between the metal layers 7 .
FIG. 23 is another representation according to FIG. 1 . FIG. 23 shows a cooler 1 a in the form of a heat pipe. In this embodiment, the cooler 1 a , or its body, is in turn formed from several copper or metal layers which are joined to one another lying stacked one top of one another to the cooler 1 a . The metal layers 12 e for the capillary areas 8 are made such that they are each provided on one surface side with several groove-like depressions 25 which extend in the lengthwise direction and which are produced by etching, stamping, or by machining which removes material or shavings, or in some other way. The depressions 25 each end in a continuous opening 26 , which is provided at a distance from a closed edge area. The metal layers 12 e are then turned alternatingly to form the capillary areas 8 , and are placed unturned on top of one another such that each depression 25 of one layer 12 e is added to one depression 25 of the adjacent layer 12 e to form a channel, as is shown in FIG. 24 . On the two ends, or areas 2 and 3 , these channels then empty according to FIG. 25 , into spaces which are formed by openings 26 in the metal layers 12 e and via which the channels are connected to the vapor channel 9 .
The metal layers 13 e , which form the vapor area, or the vapor structure, are made, for example, according to FIG. 27 , similarly to layers 12 e , simply with depressions 27 of greater width and/or depth, or by the fact that according to FIG. 28 , in the metal layers 13 e there is one opening 28 with a large area each.
FIG. 29 shows a representation similar to FIG. 24 . The cooler 1 a is disclosed in which the metal layers 12 e for forming the capillary structure, are not turned alternatingly, but are each in the same orientation so that the depressions 25 form especially fine channels.
In the above described embodiments it was assumed that the channels which form the capillary structures are free channels. It is also possible to place an auxiliary material which supports and/or causes a capillary effect in these or other structured or shaped channels, also in channels with large effective cross sections, for example, in the form of a powder, for example in the form of a powder consisting of at least one metal and/or metal oxide, for example copper and/or aluminum and/or copper oxide and/or aluminum oxide, and/or in the form of a powder consisting of at least one ceramic, and/or in the form of a powder from mixtures of the aforementioned substances, as is indicated by 29 in FIG. 24 .
Copper is suited for the metal layers, the metal layers being joined superficially to one another using DCB technology or active soldering. Aluminum or an aluminum alloy is also suited for the metal layers. In this case, the metal layers are connected to one another by vacuum soldering. The thickness of the metal layers can roughly be between 100 and 1000 microns and the structure widths in the area are between 50 and 1000 microns.
REFERENCE NUMBER LIST
1 , 1 a cooler
2 , 3 area
4 – 6 component
7 metal layer
7 ′ ceramic layer
8 capillary area
9 vapor channel area
10 cooling element
11 auxiliary cooler
12 , 12 a , 12 b metal layer
12 c , 12 d , 12 e metal layer
13 , 13 a , 13 b metal layer
13 c , 13 d , 13 e metal layer
14 a , 14 b slot
15 a , 15 b slot
16 posts
17 edge area
18 opening
19 crosspiece
20 island
21 opening
21 ′ structure
22 opening
23 passage
24 opening
24 ′ structure
25 depression
26 opening
27 depression
28 opening
29 auxiliary material
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The invention relates to a novel design of a cooler in the form of a heat pipe, with a housing in which an interior space closed to the outside is formed to hold a liquid, vaporizable coolant or heat-transport medium.
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The U.S. Government owns rights in the present invention pursuant to grant number DMR-9403832 from the National Science Foundation and Alabama NASA-EPSCOR program.
BACKGROUND OF THE INVENTION
The present invention relates generally to the fields of chemical vapor deposition (CVD) using low pressure techniques and the growth of diamond films. More particularly, it concerns the use of microwave plasma-assisted CVD (MPCVD) to grow epitaxial diamond films at high temperatures (>1600° C.).
The growth of homoepitaxial diamond films for integrated and optoelectronic applications is currently an active area of diamond research. (Ravi, 1993). Metastable synthesis of high quality single-crystal diamond from the vapor phase is complicated by several technological and theoretical factors. Among these are the incorporation of large concentrations of optically active defect centers (Collins and Lawson, 1989; Clark et al., 1992) (many involving nitrogen), and the lack of an accurate model for nucleation, growth, and surface chemistry during diamond film deposition.
The primary goal for large-scale production of diamond-based electronics is to develop the most reliable and economical deposition technology possible. Chemical vapor deposition (CVD) using low pressure techniques, such as microwave plasma-assisted CVD (MPCVD), are attractive for their reasonable capital investment, process flexibility and automation, and their demonstrated ability to produce high quality epitaxial films. (Sato and Kamo, 1992). In addition, given a sufficient growth rate (≧20 μm/hr), diamond homoepitaxy could be used in the enlargement, modification, or repair of existing natural and high pressure/high temperature synthesized (HPHT) crystals for use in many applications, such as repair of diamond anvils for high pressure research. (Vohra and Vagarali, 1992).
The most common characterization techniques for determining the phase purity and crystallinity of diamond films is by Raman spectroscopy. (Bachmann and Wechert, 1991; Knight and White, 1989). The absolute position and full width at half-maximum (FWHM) of the first order zone-center phonon mode (found at ˜1332.5 cm -1 in natural type IIa diamond) have been shown to be a semiquantitative means of evaluating the degree and range of crystalline order, and residual stress present in diamond films. (Knight and White, 1989; Boppart et al., 1985). More difficult, but fully quantitative methods of determining the crystallinity and crystallographic orientation of a film or crystal are Laue, x-ray, or electron diffraction techniques. (Bachmann and Wechert, 1991). Defect and impurity complexes are usually studied by photoluminescence (PL) or cathodoluminescence (CL), and are labeled by the characteristic energy E zpl (Energy of the "zero phonon line") of the zero phonon (purely electronic) transition of the center. (Clark et al., 1992).
The most common defect/impurity complexes found in both bulk and thin film diamond involve nitrogen (substitutional or interstitial) and lattice vacancies. Recent studies using isotope labeled precursor gases have indicated the enhanced incorporation of nitrogen-related defects at the film/substrate interface, as determined by intensity maxima in the ZPLs of two defect centers at 2.16 eV (575 nm) and 2.21 eV (560 nm). (Behr et al., 1993).
It has been generally understood that the growth of epitaxial diamond could not be accomplished with low pressure CVD and combustion processes at substrate temperatures in excess of 1200° C. (Bachmann and Lydtin, 1991). This belief, based in part on thermal desorption studies of diamond powders, was that the upper temperature limit would be due to the desorption of atomic hydrogen and the subsequent reconstruction and graphitization of the diamond surface. (Matsumoto et al., 1981; Pate, 1986). This belief was further reinforced by observations of graphitic inclusions and/or growth on diamond and non-diamond substrates held at temperatures above 1000°-1100° C. in low pressure CVD environments. (Spitsyn et al., 1981; Zhu et al., 1989).
The highest substrate temperature for the epitaxial growth of diamond was reported by Snail and Hanssen (1991). They reported diamond growth with a substrate temperature range of 1150°-1500° C. on natural diamond seed crystals using a laminar, premixed oxygen-acetylene flame in air. Growth rates of 100-200 μm/hr were observed for lower temperatures. However, the seed crystals subjected to higher deposition temperatures had larger misorientations and the diamond growth at 1500° C. exhibited a low growth rate and strong graphitic character in the center of one of the seed crystal's faces. Additionally, this reference discusses an open atmosphere method of producing diamond films which leads to contamination of the diamond film by graphite and nitrogen and is therefore disfavored.
SUMMARY OF THE INVENTION
The present invention seeks to overcome these and other drawbacks discussed above by providing a high temperature process for forming relatively pure diamond films, epitaxially and non-epitaxially, at high growth rates, >50 μm/hr. This is the lowest estimated rate, and the actual rate may be as high as 400 μm/hr. with growth rates above 100 μm/hr. being within the scope of this invention. The quality of the diamonds is also very good, having a FWHM of 2-5 cm -1 which is comparable to the best films produced by other methods. The production of high quality diamond films with high growth rates would have applicability for electronic and optical devices due to their high thermal conductivity and laser damage threshold.
In one respect the present invention includes a method for the deposition of diamond films onto a substrate comprising: generating a plasma of a diamond forming gas adjacent to a substrate under conditions such that the diamond film forms on the substrate wherein the temperature of the substrate is greater than about 1600° C.
In another respect, this invention is a method for the deposition of diamond film onto a substrate comprising: generating a plasma of methane and hydrogen gas adjacent to a diamond substrate, the diamond substrate, having a temperature in the range from about 2200° C. to about 2500° C., under conditions such that the diamond film forms on the surface of the diamond substrate.
In yet another respect, this invention is a method for the production of diamond film, comprising: encompassing a substrate with a plasma under conditions such that the diamond film forms on the surface of the substrate, wherein the substrate is heated by the plasma to a temperature of greater than about 1600° C.
In still another respect, this invention is a method for the production of monocrystalline diamond, comprising: encompassing a diamond anvil substrate, the substrate having a tip extending into the plasma, with a plasma under conditions such that the monocrystalline diamond forms on the tip of the substrate.
Also contemplated within the scope of this invention is a synthetic diamond prepared by encompassing a substrate with a plasma under conditions such that the diamond film forms on the surface of the substrate, wherein the substrate is heated by the plasma to a temperature of greater than about 1600° C.
BRIEF DESCRIPTION OF THE DRAWINGS
The following drawings form part of the present specification and are included to further demonstrate certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments presented herein.
FIG. 1 shows a schematic of a system in accordance with the methods of this invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention discloses a method for the deposition of diamond films onto a substrate that is maintained at a high temperature, i.e. at least 1600° C., by generating a plasma of a diamond forming gas adjacent to the substrate.
As used herein the term "plasma" refers to a completely ionized gas which contains equal numbers of ions and electrons. The plasma employed in aspects of the present invention is green, which indicates the presence of the C 2 radical. While not wishing to be bound by any theory, it is hypothesized that significant concentrations of C 2 radicals in the plasma may be important to facilitate the rapid formation of high quality diamond films. Therefore, the method used for forming the plasma should take this into account.
Although it is envisioned that the most useful way of generating a plasma will be by microwave radiation, other standard techniques for generating plasmas that are typically used for CVD may also be employed, for example, by application of direct current or radio frequency radiation, or employing a DC plasma jet or arc. The method employed in the representative examples provides for the formation of a plasma ball which encompasses the diamond substrate. This is primarily due to the placement of the substrate on a molybdenum screw which facilitates the breakdown of the diamond forming gas into a plasma by its metallic composition and sharp edges. However, other techniques for generating plasmas should also be operable if care is taken to maintain appropriate temperature of the substrate avoiding thermal runaway.
The present invention also envisions the importance of employing a deposition process that is not run in an open atmosphere as this leads to contamination of the diamond film.
Substrates envisioned by this invention will generally require a melting temperature of about 100° C. to 200° C. higher than the temperature at which it is to be maintained during the diamond deposition. Representative examples of such substances include diamond, boron nitride and molybdenum, with diamond and cubic boron nitride being preferred.
As used herein the term "geometrical structure" refers to the shape of the substrate. Although the substrates used may have any geometrical structure, it is envisioned that particular structures will be more useful. For example, a cubic structure, as is found in cubic boron nitride, an extended planar structure or a brilliant cut structure, such as the single-bevel modified brilliant design as described in Example I, are envisioned as being particularly useful with the brilliant cut being most preferred. While not wishing to be bound by any theory, it is postulated that the non-planar substrate, i.e. the anvil employed in Example I, perturbs the plasma such that gas phase conditions were modified in a manner that facilitates the depositions of diamond as opposed to deposition of graphitic carbon. Therefore, substrates which have sharp points or protrusion into the plasma may be the most useful for facilitating rapid diamond deposition. These sharp points also allow for very high surface temperatures to be attained on the substrate.
As used herein the phrase "diamond forming gas" refers to compounds that are generally employed in the art of CVD for the purposes of depositing diamond onto substrates. Diamond forming gas generally contains a carbon containing substance and a carrier substance that are gaseous under the plasma conditions. Many appropriate carbon containing substances, such as hydrocarbons, are known in the art. Organic compounds containing 5 or fewer carbon atoms are preferred due to their higher volatility, availability, and cost. Examples of hydrocarbons that are particularly useful are acetylene, ethylene, propane and methane, with methane being the most preferred. Carbon compounds that form C 2 radicals under plasma conditions in the practice of this invention are envisioned as being most useful. Additionally, as it is postulated that the role of hydrogen gas is of reduced significance in the deposition of diamond, carbon containing compounds that are more carbon rich, i.e. high carbon to hydrogen ratios, may prove to be very useful.
As used herein the term "carrier substance" refers to substances which can be mixed with carbon containing substances to facilitate diamond film formation. It has been hypothesized that these substances serve many purposes, such as to stabilize the diamond surface, reduce the size of the critical nucleus, "dissolve" the carbon in the gas, generate condensable carbon radicals, etc. (Anthony, 1990.) However, this invention does not require desorbed hydrogen on the diamond surface and some of the limitations on carrier substances noted above may not be applicable to the present invention.
Although a preferred embodiment of this invention involves the use of hydrogen gas as the carrier substance, it is envisioned that other gases used alone or in combination with each other and hydrogen may be even more valuable. Carrier gases which facilitate the production of C 2 radicals and are able to etch the nanocrystalline graphite formed on the surface of the diamond film are envisioned to be most useful. While not wishing to be bound by any theory, it is postulated that gases such as halogens will be particularly useful as they have a lower dissociation energy than hydrogen and therefore their incorporation into the plasma will increase the plasma density and greater facilitate the deposition of diamond onto substrate.
Although there is no set upper limit on the percentage of carbon containing substance in the diamond forming gas that may be employed, compositions of diamond forming gas with up to about 50% by volume of a carbon containing substance are preferred. Percentages of from about 1 to about 10% are more preferred, with percentages from about 1 to about 3% being most preferred.
A preferred embodiment of this invention maintains the temperature of the substrate at above about 1600° C., more preferably above about 2000° C. A preferred embodiment of this invention maintains the substrate below about 3000° C., more preferably below about 2500° C. and even more preferably about 2200° C. It is postulated that the temperature is important to fine tuning the rates of the deposition of diamond versus the formation of nanocrystalline graphite. Thus, it is envisioned that a temperature range that will maximize the former while minimizing the latter will be particularly useful in the present invention.
A preferred embodiment of the present invention encompasses a method for the deposition of diamond films onto a substrate by generating a plasma, preferably by microwave radiation, of methane and hydrogen gas adjacent to a diamond substrate, which is preferably a brilliant cut diamond, while maintaining the substrate at a temperature of from about 2000° C. to about 2200° C. The preferred concentration of methane in the diamond forming gas is from about 1 to about 3%.
The process of this invention can be further illustrated with reference to FIG. 1 which shows a microwave CVD system of this invention. In FIG. 1, process gases 20, such as a mixture containing 2% methane in hydrogen, flow into water-cooled electroplated stainless steel vacuum chamber 10 via conduits not shown at flow rates of, for example, about 100 to 1000 sccm for methane and about 1 to about 100 sccm for hydrogen. The line of gas flow 34 is depicted in dashed line, which flow toward a vacuum pump, not shown.
The vacuum pump (or pumps) provide an initial pressure in the chamber 10 in the range from about 1 to about 100 Torr prior to introduction of process gases 30, and maintain a low pressure during diamond production, generally in the subatmospheric regime and more typically below about 200 Torr, preferably below about 150 Torr, more preferably below about 100 Torr; typically above about 10 Torr, preferably above about 50 Torr. Prior to introduction of process gases 30, the chamber 10 may be purged of contaminants such as air by repeated evacuation by pumping followed by purging with argon.
Microwaves 20 from a microwave generating device not shown, such as 1.2 kW device generating 2.45 Ghz microwaves, radiate the substrate 40, substrate stage 70 (such as a molybdenum stage) and copper heat sink 50. Alternatively, a higher power microwave generating device can be employed, such as a 6 kW source, which would, it is thought, provide the ability to radiate a larger surface. The microwaves 20 excite the process gases 30 to form a plasma region 32 (which typically has a green color during the practice of this invention, indicating presence of C 2 ) depicted in dotted line. It should be appreciated to one of skill in the art that the localization of the plasma region 32 arises due to the action of sharp edges on the substrate stage 70 which facilitates production of the plasma 32. While a molybdenum rod is depicted in FIG. 1 for the substrate stage 70, it should be appreciated other configurations are also contemplated such as screw or spring shapes.
The plasma region 32 heats the substrate 40 to a temperature in the desired range. Temperature of the substrate 40 can be measured optically via instrumentation not shown, such as an optical emission spectrometer. Alternatively, a thermocouple can be used to measure temperature, which can be placed within the substrate stage 70. If the temperature of the substrate 40 rises too high for a given temperature, the microwave power can be lowered or the flow of process gas 30 turned off so that the substrate cools.
The diamond film grows on the surface of the substrate 40. The substrate stage 70 and copper heat sink 50 is cooled via lines not shown of a flow of cooling liquid 60 such as water, antifreeze solution such as ethylene glycol, or mixtures thereof.
It is also contemplated that the system shown in FIG. 1 may include an OLCR collimator head/detector housing an IR laser, such as a high intensity argon ion pumped femtosecond Ti:Al 2 O 3 laser, and IR detector which can be employed when diamond films are produced creating diffused reflection, thereby facilitating measurement of diamond deposition rate.
The following examples are included to demonstrate preferred embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples that follow represent techniques discovered by the inventor to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments that are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention.
EXAMPLE I
Homoepitaxial Diamond Film Deposition on a Brilliant Cut Diamond Anvil
This example describes the deposition of a thick homoepitaxial diamond layer on the (100) tip of a micro-cracked type Ia natural diamond anvil by MPCVD. The crystalline quality, phase purity, and defect distribution of the deposit was studied by micro-Raman and PL spectroscopy. The initial motivation for the present study was the repair and reuse of microcracked diamond anvils by the deposition of a thick homoepitaxial overlayer which can then be repolished to match the anvil's original geometry. This may be possible because the elastic strain field of a diamond anvil under stress extends only to a depth of several tens of microns, while the present work shows that high quality homoepitaxial films as thick as 150 μm can be grown in just a few hours by MPCVD. This methodology may also allow for the growth of millimeter-sized crystals from small seed crystals by homoepitaxial CVD. This would facilitate the production of large single crystals that is much more economical than is currently possible with HPHT synthesis.
The anvil on which deposition was conducted was a 0.3 carat type Ia natural diamond. The crystal was cut and polished in the single-bevel, modified brilliant design by D. Drukker & Zn. N.V. The original angles of the bevel and facets from the (100) central flat were 8.5° and 54.7°, respectively, and the dimensions of the central flat and culet were 20 and 350 μm, respectively. Prior to deposition the culet of the anvil had sustained a circular microcrack (a ring crack) during loading in a diamond anvil cell to pressures of over 250 GPa. The damaged regions appeared dark in an optical micrograph.
The homoepitaxial film was grown by MPCVD using a precursor gas mixture of 2% by volume methane in hydrogen at a chamber pressure of 90 Torr. The base pressure before introduction of the process gases was 1 Torr. The substrate temperature started out at 900° C. and increased to 1300° C. during the course of the 8 hour deposition cycle, as measured by an optical pyrometer.
All micro-Raman and PL measurements were carried out at room temperature using a modified Dilor X-Y spectrometer equipped with a liquid nitrogen-cooled CCD detector. Excitation was provided by the 514.5 nm (2.41 eV) line of an argon ion laser. The spectral resolution of the spectrometer was 3 cm -1 for the 1200 g/mm Raman grating, and ˜1.5 nm for the 150 g/mm PL grating. All Raman linewidths quoted are fitted values and are uncorrected for the instrumental broadening of the spectrometer. The micro-optical system has a spatial filter which allows us to reduce the depth of focus to as little as 10 μm by closing down the filter's confocal aperture. This control of the probe depth permits investigation of the properties of the overlayer without interference from the substrate. The lateral spatial resolution for all spectra is ˜1 μm.
The morphology of the homoepitaxial deposit is complex, showing features both related to and seemingly independent of the substrate geometry. The overlayer, as much as 150 μm thick in certain areas, shows the stepped growth surface expected for homoepitaxy on a polished (100) surface, in addition to a bevel of approximately 6°. The analysis of the growth anisotropy is further complicated by the fact that the optimal growth conditions of temperature, methane concentration, etc., are different for faces of different crystallographic orientation.
As shown by optical micrography, the deposit displayed a roughly cubic (100) central flat over 350 μm in diameter, surrounded by four stepped growth faces at an angle of ˜6°, where original had 16 facets at 8.5° around a 20 μm, round (100) flat. The thickness of the deposit was observed by optical micrography. Additionally, the diameter of the culet increased from 350 to ˜800 μm in about 8 hr.
The Raman spectrum from the epilayer showed a strong diamond signal at 1332 cm -1 with no trace of sp 2 bonded carbon. This sp 3 phase purity, along with the stepped growth morphology and optical transparency of the deposit, indicates that the growth is epitaxial. X-ray diffraction measurements indicate that the diamond is monocrystalline. The measured FWHM of the first order Raman peak from the deposit is 3.4 cm -1 and is comparable to that of the substrate. The original microcrack region containing amorphous carbon was still visible under the overlayer when viewed in transmission. The presence of amorphous carbon in the crack regions was confirmed by the 1600 cm -1 band in the pre-deposition micro-Raman spectra. The epitaxial diamond deposition did not fill in the microcracks.
PL studies showed the presence of nitrogen-related optical centers at 1.945 eV (637 nm) and 2,156 eV (575 nm), indicating the presence of residual nitrogen in the deposition chamber. These centers have been attributed to single substitutional nitrogen and an interstitial nitrogen-vacancy complex respectively. The peak at 580 nm is the second order Raman mode, while the bands at 660 and 680 nm are vibrionic sidebands associated with the 1.945 eV (637 nm) center. The small peaks around 525 nm in the predeposition spectra are attributed to residual surface contaminants after sample cleaning. The nature of the features seen in the PL spectra was confirmed by changing the excitation wavelength from 514 to 458 nm. In the top view configuration, it is impossible to determine if there is an enhanced concentration of these nitrogen-related defects at the film/substrate interface.
Further controlled experiments included: inspection of the surface morphology of (100) and (111) faces by SEM, confirmation by x-ray or electron diffraction of the crystallographic orientation of the film, and spatially resolved Raman and PL measurements taken in a side-view configuration, that determined the film quality and defect concentration as a function of distance from the film/substrate interface.
This is the first time homoepitaxial deposition of a high quality diamond layer on a microcracked type IA natural diamond anvil by MPCVD has been accomplished. Raman analysis shows the crystallinity and phase purity of the deposit to be equal to that of the substrate. The rapid growth of the film over the central flat and culet of the brilliant cut anvil was highly anisotropic, but mirrors the geometry of the original anvil in that it shows a well-defined culet, bevel of approximately the same angle, and faceting. PL measurements show optical defect centers with ZPLs at 1.945 and 2.156 eV, due to the unintentional incorporation of nitrogen in substitutional and interstitial sites, respectively. Further analysis in a side-view configuration is necessary to determine if the concentration of either defect is a function of distance from the film/substrate interface. The 1.681 eV center, commonly seen from both polycrystalline and homoepitaxial diamond films is not seen in this film (while it is observed from films grown on isopure type IIa substrates in the same deposition run).
The production of a thick, faceted homoepitaxial diamond film on a natural type Ia diamond anvil, natural diamond containing nitrogen aggregates, by CVD has important implications for the realization of diamond-based electronics, as well as for the rapid and economical repair, modification, or enlargement of existing crystals for applications in other areas such as high pressure research. The present example illustrates the utility of the disclosed method by allowing the deposition of high quality monocrystalline diamond with a growth rate of 20 μm/hr which is vastly improved over currently disclosed techniques with growth rates of only 5 μm/hr.
The aspect of the invention shown in Example I is independent of that shown in Example II. Example I demonstrates the importance of the geometry of the substrate at low temperatures (below, e.g., 1600° C.) in forming monocrystalline diamond. It should be appreciated, however, the anvil used in Example I can be used in higher temperature regimes.
EXAMPLE II
Homoepitaxial Diamond Film Deposition on a Brilliant Cut Diamond Anvil at High Temperatures
This example describes diamond deposition at substrate temperatures of from 2000°-2500° C. The homoepitaxial films were prepared as described in Example I. The films were grown using a precursor gas of 2% methane in hydrogen at a chamber pressure of 90 Torr with flow rates of 500 sccm for [CH 4 ] and 10 sccm for [H 2 ]. The total deposition time was 2 hours. The growth rate at high temperatures is very rapid and leads to the deposition of nanocrystalline graphite on the surface which is removed by etching in an atomic hydrogen plasma. Raman spectroscopy of the diamond layer showed a peak at 1332 cm -1 , the first order diamond Raman signal, and bands at 1430 and 1550 cm -1 , which are due to trace amounts of amorphous carbon on the surface of the layer, confirming that the film is the diamond form of carbon.
A Roughness Analysis of the film gave a roughness parameter of 51 nm. This is the film before polishing. The surface can be polished for further applications, if desired.
The growth was estimated to be at least 50 μm/hr. This is the lowest estimated rate, and the actual rate may be as high as 400 μm/hr. The quality of the diamonds is also very good, having a FWHM of 4.3 cm -1 which is comparable to the best films produced by other methods. Additionally, formation at higher temperatures led to negligible incorporation of graphite into the final product. For example, the film produced by this method was clear, whereas that produced by the method of Example I was black due to the presence of graphite on the outer surface of the product film.
While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the composition, methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents that are chemically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.
REFERENCES
The following references, to the extent that they provide exemplary procedural or other details supplementary to those set forth herein, are specifically incorporated herein by reference.
U.S. Pat. No. 5,112,458
U.S. Pat. No. 5,275,798
U.S. Pat. No. 5,292,371
Anthony (1990) Mat. Res. Soc. Symp. Proc. 162:68.
Bachmann and Lydtin (1991) in Diamond and Diamond-Like Films and Coatings. Edited by Clausing et al. Plenum. New York. pp. 829-853.
Bachmannn and Wechert (1991) in Diamond and Diamond-Like Films and Coatings. Edited by Clausing et al. Plenum. New York. pp. 678-701.
Behr et al. (1993) Appl. Phys. Lett. 63:3005.
Boppart et al. (1985) Phys. Rev. B 32:1423.
Burns and Davies (1992) in The Properties of Natural and Synthetic Diamond. Edited by Field. Academic. London. p. 405.
Clark et al. (1992) in The Properties of Natural and Synthetic Diamond. Edited by Field. Academic. London. pp. 35-80, 687-698.
Collins and Lawson (1989) J. Phys. Condens. Matter 7:6929.
Feng and Schwartz (1993) J. Appl. Phys. 73:1415.
Knight and White (1989) J. Mater. Res. 4:385.
Matsumoto et al. (1981) Carbon 19:232.
Pate (1986) Surface Sci. 165:83.
Ravi (1993) Crit. Rev. Mater. Sci. Eng. B 19:203.
Russel (1994) in Synthetic Diamond: Emerging CVD Science and Technology. Edited by Spear and Dismukes. Wiley. New York. pp. 627-649.
Sato and Kamo (1992) in The Properties of Natural and Synthetic Diamond. Edited by Field. Academic. London. pp. 445-467.
Seal (1987) in High Pressure Research in Mineral Physics. Edited by Mangmani and Syono. Terra Scientific. Tokyo. pp. 35-40.
Snail and Hanssen (1991) J. Crystal Growth 112:651.
Spitsyn et al. (1981) J. Crystal Growth 52:219.
Stemachulte et al. (1994) Phys. Rev. B 25:14554.
Van Eckevort (1994) in Synthetic Diamond: Emerging CVD Science and Technology. Edited by Spear and Dismukes. Wiley. New York. pp. 317-319.
Vohra et al. (1994) in High Pressure Science and Technology-1993. AIP Conf. Proc. No. 309, edited by Schmidt et al. AIP. New York. p. 515.
Vohra and McCauley (1994) Diam. Relat. Mater. 3:1087.
Vohra and Vagarali (1992) Appl. Phys. Lett. 61:2860.
Zhu et al. (1989) J. Vacuum Sci. Technol. A7:2315.
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The deposition of high quality diamond films at high linear growth rates and substrate temperatures for microwave-plasma chemical vapor deposition is disclosed. The linear growth rate achieved for this process is generally greater than 50 μm/hr for high quality films, as compared to rates of less than 5 μm/hr generally reported for MPCVD processes.
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FIELD OF THE INVENTION
The present invention relates generally to highway signs, and more particularly, to a legless sign stand for ballasting a highway traffic sign above a horizontal support surface.
BACKGROUND OF THE INVENTION
Highway signs are generally used for promoting the safe passage of motor vehicles and/or pedestrians. These highway signs help to advise people of, for example, approaching unsafe driving conditions, and are generally provided with various highway legends. Although highway signs are generally configured to flex in response to prevailing winds and wind gusts created by motor vehicles and the like, a prior art highway sign may tip over or move slightly along a supporting surface under the influence of high winds.
Ballasting devices may be used with highway signs to prevent undesirable influences on the signs resulting from wind gusts, for example. One such ballasting device involves the placement of one or more sandbags at the base of the highway traffic sign. Although these sandbags may function to hold the sign in place, they also have several drawbacks. Many applications require at least two of the sandbags to be placed against the stand of the highway traffic sign. Each sandbag may weigh between 35 and 50 pounds. The sandbags must first be filled, and then transported and positioned in place on the highway signs at the job site. This task is manually intensive and significantly adds to the time and labor for setting up the highway signs. The sandbags are seldom filled to consistent weights, and the amount of sand used for ballasting often will be either insufficient or excessive. Sandbags are also susceptible to breakage and the potential danger of loose sand on the roadway. It has been found that sand on a dry driving pavement reduces the coefficient of friction between a tire and the road surface, which results in increasing emergency deceleration distances.
Many sign stands comprise three or four legs for supporting the sign above a horizontal surface. Each of the legs generally extends radially and downwardly from a center of the sign stand. These leg configurations for sign stands may not adequately protect the sign from moving about or tipping over in high wind conditions. Additionally, the supporting legs of such a sign stand are susceptible to damage when impacted by passing automobiles or the like. A need has existed in the prior art for a low profile sign stand which is both simple in construction and durable.
SUMMARY OF THE INVENTION
The legless sign stand of the present invention provides a sturdy ballasting function and is simple in design. The legless sign stand can be prefabricated of recycled materials to required dimensions and weights, and can be transported with relative ease when not attached to a highway traffic sign. The rubber portion is preferably formed from vulcanized reclaimed rubber. Even when the legless sign stand is attached to a highway traffic sign, the entire apparatus may be readily moved without any need for disassembly. In contrast, prior art devices using sandbags may require removal of the sandbags before transportation of the sign and sign stand, and subsequent repositioning of the sandbags onto the highway sign base. Since the legless sign stand of the present invention does not use sand, dangers associated with loose sand on a driving surface are attenuated. Additionally, the legless sign stand of the present invention is not susceptible to substantial damage resulting from an impact with an automobile, for example. An automobile wheel passing over a four legged sign base would likely render the sign base inoperable, but the same trauma subjected to the legless sign base of the present invention would likely result in minimal damage.
The legless sign stand of the present invention includes a rubber base having an upper planar surface and a lower planar surface. A first rigid planar member contacts the upper planar surface of the rubber base, and a second rigid planar member contacts the lower planar surface of the rubber base. Both of the rigid planar members are secured to the rubber base with bolts. Two support brackets are mounted to the first rigid planar member, and a support mast is connected between the two support brackets. The support mast accommodates a clamping member, which is adapted for clamping onto a portion of the highway traffic sign to thereby support the highway traffic sign above a horizontal support surface.
The two rigid planar members are formed of metal sheets. The upper rigid planar member may be rectangularly shaped with each of the four corners bent in a downward direction into the rubber base to reduce the possibility of tire damage, for example.
The support mast is pivotally held between the two support brackets. The support mast can be pivoted between a first position where the support mast is oriented perpendicularly relative to the planar surface of the rubber base, and a second position where the support mast is oriented parallel relative to the planar surface of the rubber base. A pivot pin running through each of the two support brackets and the support mast facilitates this pivoting action.
According to one broad feature of the present invention, only a single rigid planar member is secured to the rubber base. The rigid planar member is secured to the rubber base beneath the upper planar surface of the rubber base. A perimeter of the rigid planar member is covered by a perimeter lip of the rubber base. Thus, a bottom surface of the rigid planar member contacts a surface of the rubber base beneath the upper planar surface, and an upper surface near the perimeter of the rigid planar member is contacted by the perimeter lip of the rubber base.
According to another broad aspect of the present invention, the two support brackets have rounded upper surfaces. Each of the rounded upper surfaces has a first notch for accommodating a latch bar of the support mast when the support mast is oriented perpendicularly relative to the planar surface of the rubber base, and a second notch for accommodating the latch bar when the support mast is oriented parallel relative to the planar surface of the rubber base.
The rubber base includes four stacking lugs protruding above the upper planar surface of the rubber base to facilitate stacking of one legless sign stand on top of another legless sign stand. To further facilitate such stacking, a recessed channel is disposed below the lower planar surface of the rubber base for accommodating the support mast when the support mast is in the storage orientation. The channel extends beneath the two support brackets to thereby facilitate compact stacking by accommodating the two support brackets of a second legless sign stand therebeneath.
The present invention, together with additional features and advantages thereof, may best be understood by reference to the following description taken in connection with the accompanying illustrative drawings.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a perspective view of the legless sign stand and highway traffic sign according to a first preferred embodiment of the present invention;
FIG. 2 is a perspective view of the legless sign stand illustrated in FIG. 1;
FIG. 3 is a bottom planar view of the legless sign stand illustrated in FIG. 1;
FIG. 4 is a side elevational view of the legless sign stand illustrated in FIG. 1;
FIG. 5 is a side elevational view of the legless sign stand of FIG. 1 in a storage orientation;
FIG. 6 is cross-sectional view, taken along lines 6--6, of a portion of the legless sign stand shown in FIG. 2;
FIG. 7 is a top planar view of the legless sign stand according to a second preferred embodiment of the present invention;
FIG. 8 is a first cross-sectional view, taken along lines 8--8, of the legless sign stand shown in FIG. 7;
FIG. 9 is a second cross-sectional view, taken along lines 9--9, of the legless sign stand shown in FIG. 7;
FIG. 10 is a side elevational view of the sign supporting mechanism of the legless sign stand according to the second preferred embodiment;
FIG. 11 is a cross-sectional view, taken along lines 11--11, of a portion of the sign supporting mechanism shown in FIG. 10;
FIG. 12 is a first cross-sectional view of the support mast of the sign supporting mechanism shown in FIG. 10; and
FIG. 13 is a second cross-sectional view of the support mast of the sign supporting mechanism shown in FIG. 10.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Turning to FIG. 1, a highway traffic sign 21 is shown supported above a horizontal support surface by a legless sign stand 23. The highway traffic sign 21, in one preferred construction (as disclosed, for example, in U.S. Pat. No. 4,980,984) comprises a flexible material 25 and four flexible corner pockets 27 located at each of the corners of the highway traffic sign 21. Each of the four flexible corner pockets 27 accommodates a respective end of two battens (not shown) located behind the flexible material 25. A vertical batten runs between the top corner pocket 27 and the bottom corner pocket (not shown), and a horizontal batten runs between the two side corner pockets 27.
The legless sign stand 23 comprises a latch bracket 24, which includes a support mast 29, for accommodating a corner pocket 27. The sign support mast 29 of the legless sign stand 23 preferably grips the bottom corner pocket and a portion of the vertical batten (not shown), to thereby hold the traffic sign 21 in an upright orientation. Alternatively, the traffic sign 21 may be supported using bolts passing through both the vertical batten and an upright member (not shown) of simple construction, used in place of the sign support mast 29 and/or the corner pocket 27.
As shown in FIG. 2, the legless sign stand 23 comprises a rubber base 25 having two handle apertures 37 located therein. Each of the handle apertures 37 can be gripped by the hand of a user, or a tool, to facilitate transportation or repositioning of the rubber base 25. The handle apertures 37 may also facilitate repositioning of the legless sign stand 23 when a highway traffic sign 21 is attached thereto.
An upper metal plate 39 is secured to the top base surface 33 via bolts 41 and nuts 43. A first support bracket or ear 45 and a second support bracket or ear 47, which also comprise a portion of the latch bracket 24, are secured to the upper metal plate 39, preferably by welding. Each of the first support bracket 45 and the second support bracket 47 preferably comprises a shear bolt aperture 49, a shear bolt storage position aperture 50, and a pivot pin aperture 52. These apertures 49, 50, and 52 are used for securing the support mast 29 between the two support brackets 45, 47, as discussed below with reference to FIGS. 4 and 5.
As shown in FIG. 3, the bottom base surface 35 of the rubber base 25 comprises a lower metal plate 51, which is secured to the rubber base 25 using the same bolts 41 and nuts 43 used to secure the upper metal plate 39 to the rubber base 25. The bolt heads 53 preferably contact the lower metal plate 51, and the nuts 43 preferably contact the upper metal plate 39 (FIG. 2). The lower metal plate 51 permits easy mechanical attachment of the upper metal plate 39 and, additionally, adds rigidity to the rubber base 25. In the presently preferred embodiment, the surface area of the upper metal plate 39 is larger than the surface area of the lower metal plate 51. The large surface area of the upper metal plate 39 provides stiffness to the rubber base 25 to thereby prevent the rubber base 25 from bowing and bending in high wind conditions when the highway traffic sign is secured to the legless sign stand 23. In an alternative embodiment, the upper metal plate 39 or the lower metal plate 51, or both, may be omitted. When the upper metal plate 39 is omitted, the two support brackets 45, 47 may be secured via bolts passing directly therethrough and into the rubber base 25. As another alternative embodiment, the size of either the upper metal plate 39 or the lower metal plate 51, or both, may be changed. For example, a smaller sized upper metal plate 39 may be used in combination with a larger sized lower metal plate 51.
FIG. 4 illustrates a pivot pin 59 and a bolt 55 for securing the support mast 29 between the first support bracket 45 and the second support bracket 47. The pivot pin 59 is preferably permanently secured through the pivot pin apertures 52 and the support brackets 45, 47, and through two apertures (not shown) in the support mast 29. The bolt 55 is preferably removably secured, via a wing nut 57, through the two bolt apertures 49 and two apertures (not shown) in the support mast 29. In the presently preferred embodiment, the shear strength of the pivot pin 59 is greater than the shear strength of the bolt 55, so that the bolt 55 will shear upon impact by an automobile, for example, to allow the support mast 29 to pivot about the pivot pin 59 in the direction of the arrow A1 (FIG. 5). The pivoting of the support mast 29 in the direction of the arrow A1 may minimize damage to the legless sign stand 23, and may further prevent damage to the undercarriage of the automobile. The shear bolt 55 may be removed in normal operating conditions to pivot the support mast 29 about the pivot pin 59 into a storage orientation generally parallel with the plane of the rubber base 25, as shown in FIG. 5. In this storage orientation, the shear bolt 55 and wing nut 57 can be reinserted through the apertures 50 and two apertures (not shown) in the support mast 29, thereby locking the support mast 29 in the storage orientation.
FIG. 6 is a cross-sectional view of the rubber base 25 and the upper metal plate 39 shown in FIG. 2, taken along the line 6, 6. Each of the four corners 40 of the upper metal plate 39 is preferably bent downward. In the presently preferred embodiment, each of the corners 40 of the upper metal plate 39 is bent before attachment to the rubber base 25. When the bolts 41 and nuts 43 are tightened, each of the corners 40 bites into the top base surface 33. The corners 40 are thus disposed beneath a plane of the top base surface 33 to prevent the potentially harmful corners 40 from damaging tires of automobiles, for example.
A second preferred embodiment of the present invention is shown in FIG. 7. The rubber base 125 comprises a top base surface 133 and a bottom base surface 135. Two handle apertures 137 are formed on opposing sides of the rubber base 125. As with the embodiment described with reference to FIGS. 1-6 above, the rubber base preferably comprises vulcanized reclaimed rubber, "crumb" rubber, or bonded "crumb" rubber. Four stacking lugs 161 protrude above the top base surface 133 and, preferably, are integrally molded with the rubber base 125. The rubber base 125 further comprises a recessed area for accommodating a recessed metal plate 165. The recessed metal plate 165 is preferably rectangular, and rests in a plane beneath a plane defined by the top base surface 133. A perimeter lip, which is preferably integrally molded with the rubber base 125, surrounds and covers an upper portion of the recessed metal plate 165 along the four sides of the recessed metal plate 165. Preferably, the metal plate 165 is molded into the base i.e. "overmolded" during the base fabrication process.
A plurality of large apertures 163 (eight in the preferred embodiment) are formed through the recessed metal plate 165. These apertures function to mechanically attach the rubber base 125 and the metal plate 165, because during the overmodling process, rubber flows through each of the apertures 163 and sets in place during the subsequent curing step. A first rounded support bracket or ear 145 and a second rounded support bracket or ear 147 are secured to the recessed metal plate 165, preferably by welding. The two support brackets 145, 147 pivotally support a support mast 129 (FIG. 8). A plane defined by the recessed metal plate 165 is extended through the recessed channel surface 167, and a latch bracket handle accommodating aperture 171 is formed through the rubber base 125 within the recessed channel surface 167.
A cross-sectional view of the legless sign stand 123, taken along the line 8, 8 of FIG. 7 is shown in FIG. 8. As shown in FIG. 8, each of the handle apertures 137, and the latch bracket handle accommodating aperture 171, preferably extend from the top base surface 133 and recessed channel surface 167 to the bottom base surface 135. The four edges of the periphery lip of the rubber base 125 are preferably chamfered. This chamfer 169 surrounding the peripheral lip 168 may be formed during the initial molding of the rubber base 125, or may be subsequently machined.
Each of the first rounded support bracket 145 and the second rounded support bracket 147 comprises a rounded top portion, and further comprises a first locking notch 181 and a second locking notch 183. The support mast 129 is secured between the first rounded support bracket 145 and the second rounded support bracket 147 with a pivot pin 185, similarly to the embodiment discussed above with reference to FIG. 4. In the preferred embodiment, each of the rounded support brackets 145 is asymmetrical, in that it includes a raised back stop portion 175 on a side of the first locking notch 181 which is opposite to that of the second locking notch 183.
A latch bar 177 within the support mast 129 is biased by a spring 195 (FIG. 11) toward the pivot pin 185. The latch bar 177 may be moved in the direction of the arrow A2 out of the first locking notch 181. The support mast 129 is no longer secured in an upright orientation when the latch bar 177 is moved in the direction of the arrow A2 out of the first locking notches 181. The support mast 129 may be rotated about the pivot pin 185 in the direction of the arrow A3 to a storage orientation, which is substantially parallel with a plane of the recessed metal plate 165. The sign latch bracket 131, which is preferably secured to the support mast 129 with two bolts 184, 186, is also aligned parallel with the plane of the recessed metal plate 165, and the bracket handle 173 fits into the bracket handle accommodating aperture 171. The support mast 129 and sign latch bracket 131 are shown in phantom positioned parallel to the plane of the recessed metal plate 165, by the reference numbers 130 and 132, respectively. Importantly, the mast 129 is prevented from pivoting in the direction opposite to that of arrow A3 by the back stop portion 175, which is raised sufficiently that the latch bar 177 cannot be pivoted above it, so as to clear it.
As shown in FIG. 8, when the support mast 129 and sign latch bracket 131 are oriented in a plane parallel to the recessed metal plate 165, the support mast 129 and the sign latch bracket 131 do not extend above a plane formed by the tops of the four stacking lugs 161. Thus, the support mast 129 and the sign latch bracket 131 can be pivoted in the direction of the arrow A3 to rest beneath a plane formed by the four stacking lugs 161 to thereby facilitate compact storage. A second legless sign stand 223 is shown in phantom in FIG. 8 beneath the first legless sign stand 123. The first legless sign stand 123 is stacked on top of the second legless sign stand 223 such that the four stacking lugs 261 of the second legless sign stand 223 contact the bottom base surface 135 of the legless sign stand 123. A recessed area 197 of the legless sign stand 123 accommodates a first rounded support bracket 245 and a second rounded support bracket 247 of the second legless sign stand 223.
A cross-sectional view of the legless sign stand 123 shown in FIG. 7, taken along the line 9, 9, is illustrated in FIG. 9. The first rounded support bracket 145 and the second rounded support bracket 147 protrude above a plane formed by the four supporting lugs 161, but compact storage is facilitated by the recessed area 197 of another legless sign stand. The sign supporting mechanism 199 shown in FIG. 10 comprises the first rounded support bracket 145 (FIG. 7) and the second rounded support bracket 147. The pivot pin 185, secured within the two rounded support brackets 145, 147, comprises a bolt 200, an elastic stop nut 201, and two flat washers 202. A cross section of this sign supporting mechanism 199, taken along the line 11, 11 of FIG. 10, is shown in FIG. 11. The latch bar 177 comprises two outer ends 203, which protrude through two corresponding latch apertures 179. The latch apertures 179 allow the two outer ends 203 to move vertically therein. The spring 195 is connected to the latch bar 177 via an aperture 197, and is also connected to the pivot pin 185. The spring 195 biases the latch bar 177 toward the pivot pin 195. A latch bar centering plug 205, preferably comprising plastic or metal and having an outside diameter slightly less than the inside dimension of the support mast 129 is preferably provided to center the latch bar 177 in the apertures 179. The plug 205 includes a center core 207 which is large enough to accommodate the spring 195. A user may grip the two outer ends 203 of the latch bar 177 to pull the latch bar in a direction away from the pivot pin 185 to facilitate rotation of the support mast 129 (FIG. 8) in the direction of arrow A3. In the presently preferred embodiment, the shear strength of the latch bar 177 is less than the shear strength of the pivot pin 185, so that the latch bar 177 will shear upon impact by an automobile, for example, to allow the support mast 129 to pivot about the pivot pin 185 in the direction of the arrow A3 (FIG. 8). This pivoting may minimize damage to the legless sign stand 123 and/or prevent damage to the undercarriage of the automobile.
FIG. 12 shows a first cross-sectional view of the support mast 129, and FIG. 13 shows a second cross-sectional view of this support mast 129. Each of the two latch apertures 179 are preferably slightly larger than a width of the latch bar 177, and are preferably elongated to allow the latch bar 177 to track therein. A pivot point aperture 191 accommodates the pivot pin 185 (FIG. 11), and a bracket fastening aperture 193 accommodates the bolt 184 for attachment of the sign latch bracket 131 within the support mast 129. FIG. 13 shows that the presently preferred cross-sectional configuration of the support mast 129 is square.
Although exemplary embodiments of the invention have been shown and described, many other changes, modifications and substitutions, in addition to those set forth in the above paragraph, may be made by one having ordinary skill in the art without necessarily departing from the spirit and scope of this invention.
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A legless sign stand includes a rubber base having an upper planar surface and a lower planar surface. A first rigid planar member contacts the upper planar surface of the rubber base, and a second rigid planar member contacts the lower planar surface of the rubber base. Both of the rigid planar members are secured to the rubber base with bolts. Two support brackets are mounted to the first rigid planar member, and a support mast is connected between the two support brackets. The support mast accommodates a clamping member, which is adapted for clamping onto a portion of the highway traffic sign to thereby support the highway traffic sign above a horizontal support surface.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of application Ser. No. 08/605,976, filed Feb. 23, 1996, now abandoned, which is a continuation-in-part of earlier application Ser. No. 08/440,134 filed May 12, 1995, now U.S. Pat. No. 5,626,832 which is a continuation of Ser. No. 08/128,206 filed Sep. 29, 1993 now U.S. Pat. No. 5,445,810 which is a continuation of Ser. No. 07/302,690 filed Jan. 19, 1989 now U.S. Pat. No. 5,312,615 which is a 35 USC 371 of PCT/EP88/00447 filed May 16, 1988.
TECHNICAL FIELD
The present invention concerns injectable NMR and X-ray blood pool contrast agents comprising aqueous suspensions of liposomes carrying imaging contrast enhancers, e.g. paramagnetic or, respectively, radio-opaque compounds for imaging the circulation and/or circulation targeted organs. The compositions are formulated to protect the contrast agents from early removal by the reticulo-endothelial (RES) system of the liver and the spleen, so that they stay in the circulation long enough for imaging the blood vessels and blood perfused organs. X-ray and NMR imaging of the circulation and of targeted organs can strongly assist in diagnosing possible ailments in human and animal patients.
BACKGROUND ART
Until now, substances suitable as imaging contrast agents in injectable compositions for blood-pool investigations have been mostly NMR responsive solid mineral and organic particles or water-soluble polymers. The particles can comprise ferromagnetic or superparamagnetic materials as well as paramagnetic species bonded to polymeric carriers. In order to make them sufficiently long lasting for imaging the circulation, the particles should be protected against premature removal from the bloodstream.
Normally, the useful life of particles injected in the circulation is short because of rapid physiological removal therefrom due to opsonization followed by phagocytosis. The opsonization process involves the coating of the particles by an antigen protein, opsonin, recognisable by macrophages. Then, in a second stage, opsonization is followed, by the phagocytosis and metabolization of the coated (opsonized) particles by the Kupffer cells of the liver and spleen. Hence, although unprotected particles are suitable for imaging of the liver and the spleen, their free life in the blood is too short for blood-pool imaging.
The protection of particles against early removal from the circulation is discussed in many documents and significant enhancement of their useful life in the blood has been achieved by coating magnetite particles with a coating which includes amphiphilic substances, for example ethyleneoxide-propyleneoxide block copolymers (see for instance WO-A-94/04197, Sintetica).
The use of dispersions of microvesicles containing concentrated solutions of iodinated or paramagnetic species encapsulated in the vesicles e.g. liposomes as carriers of X-ray opacifiers or NMR contrast agents has been proposed. Thus, EP-A-0 314 764 (Dibra) discloses injectable aqueous suspensions of liposomal vesicles carrying encapsulated at least one iodinated organic compound opaque to X-rays which are useful as contrast agents for X-ray imaging of liver and spleen. The liposomes have a mean size between 0.15 and 3 μm and the ratio of the weight of the iodine encapsulated in the liposomes to the weight of the liposome forming lipids (I/L) is from 1.5 to 6 g/g. The liposome suspensions as carriers of opacifying compounds have been proposed due to their relative biocompatibility and ease of preparation.
Proposals to incorporate opacifiying agents into the liposome membranes have also been made (E. Unger et al., Liposome bearing membrane-bound complexes of manganese as magnetic resonance contrast agents, Proceedings of the Contrast Media Research Symposium, San Antonio Tex. Oct. 3-8, 1993, S168). However, most liposomes are subject to rapid removal from the circulation by the liver and the spleen and, although this property may be advantageous for imaging of these organs it is undesirable when blood pool imaging is contemplated. This since for blood pool imaging the concentrations of opacifying compounds in the blood should be kept at a relatively high level for extended periods of time.
To prolong the life of liposomes vesicles in the blood, different remedies have been proposed. Coating liposomes with copolymers containing hydrophilic and hydrophobic segments has been proposed in, for instance, J. Pharmacy & Pharmacol. 39 (1987), 52P, while incorporation of protective substances in the vesicle forming lipids has been proposed in EP-A-0 354 855 (Terumo) and in WO-A-91/05545 (Liposome Technology). Along the latter line of approach, “stealth factors”, for instance, covalently modified lipids, i.e. lipids carrying grafted thereon externally extending polyethylene glycol (PEG) or polyoxyethylene-polyoxypropylene segments. Also, the incorporation, as “stealth” factors, to the vesicle forming lipids of products such as palmitoylglucuronic acid (PGlcUA) has been reported to improve the half-life of liposomes in the blood (see Naoto Oku et al. in Biochimica et Biophysica Acta 1126 (1992), 255-260).
EP-A-0 354 855 (Terumo) discloses use of agents for inhibiting adsorption of protein on the liposome surface comprising a hydrophobic moiety at one end and a hydrophilic macromolecular chain moiety on the other end. The preferred hydrophobic moieties are alcoholic radicals of long chain aliphatic alcohol, a sterol, a polyoxypropylene alkyl or a glycerin fatty acid ester and phospholipids while prefered hydrophilic moieties are polyethylene glycols (PEG). Non-ionic surface active agents in which PEG and an alcoholic radical of the hydrophobic moiety are bound by ether bond or PEG-bound phospholipids are particularly preferred. Upon formation the agent is admixed with liposome forming phospholipids to produce “stealth” liposomes.
The lifetime of liposomes in the blood may be significantly prolonged by making the vesicles very small, i.e. making them less size-recognisable by opsonin; this approach has been disclosed in WO-A-88/04924 and EP-A-0 442 962.
WO-A-88/04924 discloses liposome compositions containing an entrapped pharmaceutical agent in which the liposomes are predominantly between 0.07 and 0.5 μm in size, have at least 50% mole of membrane-rigidifying lipid such as sphingomyelin or neutral phospholipids and between 5-20% mole of ganglioside GM 1 , saturated phosphatidyl inositol or galactocerebroside sulfate ester. From the disclosure (Examples 8 and 9) it follows that liposomes made with negatively charged phospholipids in which phosphatidyl moiety is linked to glycerol are not very useful for blood pool applications as the same are relatively quickly recognised by RES.
In EP-A-0 442 962 liposomes of 50 nm or less are proposed for transporting through the circulation minute amounts of drugs to selected areas in the body. The trouble with very small vesicles is that their entrapment capacity becomes very low and such small vesicles are not readily compatible with the amounts of contrast media required for imaging the blood-pool with paramagnetic or X-ray compounds. Thus, under the conditions disclosed it would be necessary to inject to live subjects liposome suspensions containing more than 100 mg of lipids/ml which is undesirable for reasons of cost, potential toxicity and very high viscosity. The use of tiny liposome vesicles of the kind proposed in EP-A-0 442 962 for the delivery of drugs (in the order of 50 nm or less) are therefore unpractical for blood-pool imaging. Much the same applies to the proposals of Gabizon et al. in Biochim. et Biophys. Acta 1103 (1992) 94-100 and I. A. J. M. Bakker-Woudenberg et al. ibid. 318-326 directed to liposomes with an average size between 0.07 μm and 0.1 μm and prolonged residence times in the blood.
From the recent publications of M. C. Woodle et al., Journal of Drug Targeting 2 (1994) 397-403 and I. A. J. M. Bakker-Woudenberg et al., ibid. 363-371, it follows that in view of a relatively rapid removal of even those very small liposomes, the presence of the recognised stealth factors is absolutely necessary if these liposomes are to be effective in transporting various targeted drugs. This then presents further problems as the production of liposomes with the “stealth factors” is rather cumbersome. In addition, the “stealth factored” liposomes are known to have very low entrapment capacity and while such liposomes may be suitable to carry specific drugs, and therefore useful in therapy, they are almost useless in imaging.
Hence, the problem of use of standard or unmodified liposomes i.e. liposomes which can carry sufficient amount of opacifier and remain in the blood circulation sufficently long to enable X-ray and NMR imaging remains unresolved. It is generally believed that, in addition to be able to supply sufficent amount of opacifier, for good blood pool imaging the contrast agent should upon administration remain in the circulation between 1 and 2 hours. Thereafter the blood pool contrast agent should be eliminated from the body as quickly as possible. Use of liposomes which would satisfy these criteria is desirable as liposome production techniques are well known; their use in medicine and diagnostic preparations is wide spread; their effects in the living body are reasonably well understood. Hence their use for blood pool imaging or the manufacture of blood pool agents of “stealth” liposomes without “stealth factors” would provide a number of advantages.
Actually, this problem has been unexpectedly solved by the present inventors according to the disclosure hereafter.
SUMMARY OF THE INVENTION
It was surprisingly found that the blood pool agents according to the present invention comprise liposome suspensions which are readily injectable into the circulation of living bodies are sufficiently stable and carry sufficient amount of paramagnetic or X-ray opacifying active material to allow convenient imaging of the blood stream and appended organs. The blood pool agents contain liposomes with astounding so called “stealth” properties without requiring incorporation of the priorly recognised “stealth factors”.
The blood pool contrast agents of the invention comprise liposome suspensions in which:
(a) the liposome forming lipids comprise between 80 and 99 mole % of neutral phospholipids and from about 1 to 20 mole % of negatively charged phospholipids, whose phosphatidyl moiety is linked to glycerol,
(b) at least 80% (by volume) of the liposome vesicles are in the 0.2-1.0 μm range, and
(c) depending on the liposome size the lipid concentration (C Lip ) in the suspensions is below 20 mg/ml for liposomes with average diameter of 1.0 μm and below 100 mg/ml for liposomes with average diameter of 0.2 μm.
Also disclosed is a method for preparing the blood pool agents by encapsulating a concentrated solution of opacifying agent in the vesicles formed according to liposome making means from a lipid mixture comprising between 80 and 99 mole % of neutral phospholipids and 1 to 20 mole % of negatively charged phospholipids whose phosphatidyl moiety is linked to glycerol, and optionally other additives such as cholesterol, normalising the vesicles by repeated extrusion through calibrated semi-permeable membranes until the size of at least 80% of the vesicles is comprised between 0.2 and 1.0 μm, and optionally, separating the vesicles with the contrast agent entrapped therein from non-encapsulated contrast agent, and adjusting the amount of carrier in the suspension to have a lipid concentration (C Lip in mg/ml) therein not exceeding a value given by the ratio 20/D where D is the vesicle volume average diameter expressed in μm.
Use of the X-ray or NMR blood pool agents in imaging of human or animal patients is also disclosed.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plot of the % of injected dose (ID) as a function of time for the suspensions prepared with liposomes with four different sizes after injection into the bloodstream of laboratory rats.
FIG. 2 is a graphical presentation of the % of injected dose (ID) as a function of time for the suspensions prepared with “stealth factors” liposomes and liposomes according to the invention after injection into the bloodstream of laboratory rats.
FIG. 3 is a graph of the % of injected dose (ID) as a function of time for the suspensions prepared with liposomes according to the invention and with liposomes containing dipalmitoylphosphatidic acid (DPPA) after injection into the bloodstream of laboratory rats.
DETAILED DESCRIPTION OF THE INVENTION
The main aspects of the invention are based on the unexpected finding that the liposome suspensions in which (a) the liposome forming lipids comprise between 80 and 99 mole % of neutral phospholipids and from about 1 to 20 mole % of negatively charged phospholipids, whose phosphatidyl moiety is linked to glycerol, (b) at least 80% (by volume) of the liposome vesicles present have the size in the 0.2-1.0 μm range, and (c) depending on the liposome diameter, the maximal lipid concentration (C Lip ) is between 20 and 100 mg/ml. The maximal concentration (readily calculated as 20/the vesicle average diameter D in μm) means that for liposomes with an average diameter of 0.2 μm the maximal lipid concentration in the suspension is below 100 mg/ml, for liposomes with an average diameter of 0.4 μm the maximal lipid concentration is below 50 mg/ml, for liposomes with an average diameter of 0.6 μm the maximal lipid concentration is below 33 mg/ml, for liposomes with an average diameter of 0.8 μm the maximal lipid concentration is below 25 mg/ml, and for liposomes with an average diameter of 1.0 μm the maximal lipid concentration is below 20 mg/ml. Such suspensions are readily injectable into the circulation of living bodies, they have enough stability to remain in the circulation for prolonged periods of time, they display so called “stealth” properties without requiring incorporation of the recognised “stealth factors” and yet posses sufficient entrapping capacity toward solutions of paramagnetic or X-ray contrast agents to provide very convenient contrast agents useful for imaging the blood stream and appended organs.
It shoud be noted that 1 to 20 mole % of negatively charged saturated or unsaturated phospholipids whose phosphatidyl moiety is linked to glycerol, optionally include phospholipids in which the glycerol is replaced by inositol. The other phosphatidyl moiety of the negatively charged phospholipid is attached to a glycerol diester of the usual fatty acids such as myristic acid, palmitic acid, stearic acid, oleic acid and the like. Addition of more than 20 mole % of the negatively charged phospholipids to the liposomes reduces considerably the entrapment capacity of the vesicles and should thus be avoided. The best results in terms of “stealth” properties and entrapment capacity of the liposomes of the invention are obtained when this range is maintained between 3 to 15 mole %.
In the invention, the neutral phospholipids comprise the usual saturated and unsaturated phosphatidylcholines and ethanolamines, for instance, the corresponding mono- and di-oleoyl-, mono- and di-myristoyl-, mono- and di-palmitoyl-, and mono- and di-stearoyl-compounds. The negatively charged phospholipids comprise the phosphatidyl glycerols preferably dimyristoylphosphatidyl glycerol (DMPG), dipalmitoylphosphatidyl glycerol (DPPG), distearoylphosphatidyl glycerol (DSPG) and optionally the corresponding phospholipids where the glycerol is replaced by inositol. In addition, the lipids of the present liposomes may contain additives commonly present in liposome formulations, like the sterols and some glycolipids; the sterols may include cholesterol, ergosterol, coprostanol, cholesterol esters such as the hemisuccinate (CHS), tocopherol esters and the like. The glycolipids may include cerebrosides, galacto-cerebrosides, glucocerebrosides, sphingo-myelins, sulfatides and sphingo-lipids derivatized with mono-, di- and trihexosides.
It is important to note that the phosphatidic acids must be avoided in the formulations of the present liposome suspensions, as even small amounts thereof will destroy the “stealth” properties. It is also noteworthy that the additional incorporation of the priorly recognised “stealth factors” into the liposomes and the suspensions of the invention (which are useful in other liposome formulations) will bring no further improvement in the “stealth” properties of the present suspensions. The incorporation of these factors into the liposomes will thus have insufficient impact on the residence time of the liposomes of the invention in the blood. Actually, the incorporation of recognised stealth factors to the formulations of the present liposome suspensions may even be detrimental as the captured volume E c (entrapped volume/weight of lipid) may be significantly reduced. Hence the liposome suspensions of the invention are simple to formulate and manufacture and are thus even economically advantageous in comparison to other formulations of inferior performance.
It is advantageous to use suspensions in which the vesicles have a size distribution as narrow as possible around a nominal value selected in the given 0.2 to 1.0 μm range and preferably in the range between 0.2 and 0.6 μm. For instance, if the selection desirably involves a suspension of vesicles of, say 0.4 μm, it is preferable that at least 80%, according to volume distribution, of the vesicle have a size of 0.4 μm±10%. The narrow width of the vesicle size distribution band can be considered here as a quality factor, i.e. the narrower the band, the more controllable the properties of the liposome suspensions and the better their intrinsic performance as carrier of blood-pool imaging agents in injectable formulations. Narrowing the vesicle size distribution band of liposome suspensions is normally achieved by “normalisation”, i.e. calibration of the vesicles by extrusion of the liposome suspensions through accurately graded filtration membranes, for instance Nuclepore® polycarbonate membranes.
From the above it is readily apparent that the admissible lipid concentration (C Lip ) in the suspensions of the invention is directly related to the vesicle size and its entrapping potential. For instance, at the lower end of the size range, the admitted maximum lipid concentration is 100 mg/ml. This limit corresponds to 0.2 μm vesicles; for 0.6 μm vesicles, this limit is 33 and for 1.0 μm vesicles this limit is 20 mg/ml. These values are preferred although acceptable results may be obtained when the sizes vary within ±20% on the both ends of the limit. These are admissible in view of the property changes which may result from different lipid compositions. Therefore, the viscosity of the present suspensions will not exceed 50 mPa.s and, preferably, it will be below 25 mPa.s. In fact, in some cases, for instance, when exceptionally large injector needles are used or when the injection can be made slow, these values may be overridden.
In the case of X-ray contrast agents the suspensions are prepared from liposomes carrying iodinated compounds, the lipid concentration (C Lip ) in the suspensions should not be below about a quarter to a half the aforementioned maximal value, as otherwise the amount of opacifying agent carried by the liposomes may become too low for imaging contrast; for instance, for 0.4 μm vesicles, half the maximal value is 25 mg/ml. Hence, with a captured volume (E c ) of about 9 μl/mg of lipids (this value which is about ¾ of the theoretical value is easily attainable with liposomes of the present invention) and using for encapsulation, solutions of non-ionic monomers, with the standard iodine solution of concentration C I =260 g of iodine/l (0.26 mg/μl), the final iodine concentration of the liposome suspension (C IS ) is 25×9×0.26=58.5 mg/ml, is already above the preferred lower limit of iodine concentration for satisfactory imaging opacification. Of course, the foregoing holds when using iodine solutions of non-ionic monomers with standard 260 g/l concentrations for liposome encapsulation; with solutions of higher iodine concentrations (which for mixtures of monomers and dimers can reach 300 g/l or more) the foregoing relations should be adapted accordingly. However, iodine concentrations much higher than 260 g/l are generally less preferred as osmotic pressure gradient across the vesicle membrane may, in some cases, cause iodine leakage into the outside aqueous carrier medium.
If one considers that the volume of a hollow body relative to its surface varies linearly as a function of its physical size, then, in the case of a sphere of radius “r” (=D/2), the ratio of volume to surface will be r/3. In the case of ideally spherical liposome vesicles bounded by an outer lipid membrane of surface density “φ”(g/cm 2 ), the captured volume (E c ) in ml/g (or μl/mg) of lipids is r/3φ. In the lipid bilayer of a unilamellar liposome vesicle, the molecular weight “Mw” of two facing lipid molecules≈2×800, and the area of the corresponding surface element≈50 Å 2 =5×10 −15 cm 2 . Taking the Avogadro's number as 6.02×10 23 , the surface density (φ) of the lipid bilayer= 1600 6.02 × 10 23 × 5 × 10 - 15 ≈ 5 × 10 - 7 g / cm 2 .
For a 100 nm vesicle (diameter D=0.1 μm), the theoretical captured volume (E c =r/3φ) would therefore be approximately 50 × 10 - 7 3 × 5 × 10 - 7 ≈ 3 ml / g of lipids ( or 3 μl / mg ) .
Note that in view of the foregoing E c /D=1/6φ (constant)≈30 when E c is expressed in μl/mg (or ml/g) of lipids and D in μm. In practice, the vesicles are not perfect, even after careful “size normalisation” e.g. by extrusion. Hence, since the vesicle average size follows a statistical distribution order, the captured volume is usually significantly lower, i.e. it rarely reaches ¼-½ of the calculated value, which means that E c /D may be lower than 10 in the best results reported so far.
As it may be seen in the present invention E c /D values in the order of 10-25 or even more can be reached. Thus until now, even in the best circumstances, the captured volume of a practical 100 nm vesicle available did normally not exceed 2 ml/g (μl/mg) of lipids and were generally much less. Hence, theoretically, if the vesicles are filled with a commonly available concentrated iodine solution (for instance, a 530 g/l solution of iomeprol will provide an iodine concentration (C I ) of 260 g/l), the weight of encapsulated iodine available in g per g of lipid (I/L) will be at most 2×0.26=0.52.
Now, as generally admitted in the imaging field, sufficient imaging contrast in the blood-pool advantageously requires an injected dose of at least about 50-100 mg of iodine/kg of body weight and for the safety reasons, this is distributed in an amount of injectable liquid preferably not exceeding 1 ml/kg. Hence, if we wish to distribute (by means of a liposome suspension) 100 mg of iodine in 1 ml of injectable liquid, i.e. to have a concentration (C IS ) of iodine in the liposome suspension of 100 mg/ml using 100 nm vesicles, we should use a liposome suspension of concentration (C Lip )=100/0.52=190 mg of lipids/ml. This value is far too high in terms of viscosity to be considered as useful.
With larger size vesicles, the situation is different. For example, if the foregoing considerations are applied to, say, 1-1.5 μm vesicles, the I/L ratio becomes about 5-6 mg of iodine per mg of lipids (and may even be higher when preparation conditions according to the present invention are used), which means that for having a liposome suspension containing 100 mg of iodine/ml, the lipid concentration can be as low as 15-20 mg/ml. Unfortunately, 1 μm liposome vesicles have a very short life in the blood, even if “stealth” factors are included in the formulations, and furthermore, the viscosity of liposome suspensions involving larger vesicles increases much more rapidly than with smaller vesicles. For instance a 20 mg lipid/ml liposome suspension with mainly 1-1.5 μm vesicles has about the same viscosity [40-50 mPa.s] as a 80-100 mg/ml suspension with 0.2 μm vesicles; and the larger the vesicles, the steeper the viscosity/lipid concentration curve.
It is also of interest to note that the final encapsulated iodine concentration in the liposome suspension, (C IS in mg of iodine/ml), is equal to the iodine concentration (C I in mg/ml) in the encapsulated solution multiplied by the ratio of the volume of encapsulated liquid to the total volume of the suspension (C EC ). The latter being equal to the lipid concentration C Lip (in mg/ml) x the captured volume E c (in ml/mg of lipid). Usually, the captured volume E c , or entrapment capacity, of liposome vesicles is significantly lower than the calculated value, i.e. the E c /D ratio (Ec being in μl/mg and D being in μm) rarely if ever reaches about 15 or more. In the present invention Ec/D may reach 25 or more.
For X-ray opacification, one will preferably encapsulate concentrated solutions of currently available non-ionic organic iodinated opacifiers such as Iopamidol, Iomeprol, Iofratol, Iohexol, Iopentol, Iopromide, Iosimide, Ioversol, Iotrolan, Iotasul, Iodixanol, Iodecimol, 1,3-bis-(N-3,5-bis-[2,3-dihydroxypropylaminocarbonyl]-2,4,6-triiodo-phenyl)-N-hydroxy-acetyl-amino)-propane and mixtures thereof. Solutions of such iodinated compounds currently provide iodine concentrations in the range of 250-300 g/l. As already mentioned, a 530 g/l iomeprol or iopamidol solution corresponds to a C I of 260 g/l of dissolved iodine thus for 0.4 μm vesicles which, according to the previous discussion, can advantageously capture about 10 μl/mg of lipids (I/L=2.6) or even more, a liposome suspension containing about 40 mg/ml (C Lip ) of lipids will provide about 2.6×40=104 mg/ml of iodine (C IS ). This initial iodine concentration (C IS ) of the injectable suspension is sufficient for good opacification in blood-pool X-ray imaging as, once injected in the bloodstream, it will decrease only slowly with time according to the findings of the invention; one may therefore still operate with liposomes of lower lipid concentrations, i.e. providing entrapped iodine concentrations (C IS ) of 60-80 mg/ml and even lower if desired. The same kind of considerations will apply to the entrapment of paramagnetic substances intended as contrast agents for NMR imaging. In this case, the paramagnetic substances will be those having also sufficient water solubility to provide efficient contrast enhancement after dilution in the blood stream. Among such substances, one may cite the linear and cyclic alkylene-amine polycarboxylate chelates of NMR responsive transition elements (e.g. the lanthanides) for instance gadolinium-DTPA (Magnevist® of Schering A.G.), gadolinium-BOPTA (of BRACCO), gadolinium-DO3A (Gadoteridol® or ProHance® of BRACCO Diagnostics Inc.), gadolinium-DOTA (Dotarem® of Guerbet), gadolinium-DTPA-BMA (Omniscan® of Salutar), and the like.
It was particularly astounding to find that the liposome vesicles in the suspensions of the present invention can achieve a lifetime in the blood long enough for blood pool imaging and, simultaneously, provide an entrapment capacity adequate to bring to the circulation a quantity of contrast agent sufficient for good image enhancement. Actually, when iodine loaded suspensions of liposomes according to the present invention are used for X-ray imaging the blood-pool of experimental animals, the amount of iodine still in the circulation one hour after injection can be as high as 50% of the injected dose. After 2 hr, the amount can still be about 40% of the injected dose. This property well enables to apply the present suspensions for satisfactorily imaging the blood-pool in most cases. The reasons why this is so, even in the absence of artefacts to prevent the normal physiological elimination of the lipids in the blood and the disappearance of the iodine through the kidneys is still unexplained.
For preparing the present liposome suspensions one can rely on most techniques known in the art for making liposomes and encapsulating substances therein, provided that the suspensions thus obtained are thereafter correctly calibrated by extrusion through conveniently graded filtration membranes, this being to narrow the vesicle size distribution within appropriate limits. The preferred methods involve the hydration of the lipids in an aqueous carrier liquid at or above the lipid transition temperature, either directly in the solution to be encapsulated, or in unloaded aqueous media, this being followed by transmembrane permeation loading (see WO-A-92/10166).
After extrusion, at least 80% by volume of the vesicles should be within the 0.2-1.0 μm and preferably 0.2 and 0.6 μm range. At best, 80% of the vesicles are ±10% from any nominal value selected between 0.2 to 1.0 μm. Any other broader or narrower distribution within the foregoing limits is admissible. After extrusion, the suspension will be checked to ensure that the concentration of lipids in the liposome suspension is adequate, and this may have to be adjusted to be in conformity with the aforediscussed requirements. Adjustment can be effected by dilution with more carrier liquid if the lipid concentration exceeds the aforegiven limits; otherwise, it can be increased by usual means, for instance by micro- or ultra-filtration on membranes of porosities appropriate to retain the vesicles but permeable to the carrier liquid.
Alternatively, the liposome suspensions may be prepared in media without the contrast agent, and thereafter the vesicles filled by incubation in the presence of a concentrated solution of the contrast agent. In this case, the encapsulation will proceed through trans-membrane permeation. Adjustment of the final lipid concentration will then be done as said previously.
The following practical Examples illustrate the invention in more details:
EXAMPLE 1
A solution was prepared containing 59 mg (0.079 mmol) of dipalmitoyl phosphatidyl glycerol sodium salt (DPPG-Na, Mw 744.96; Sygena), 790 mg (1.0 mmol) of distearoyl phosphatidyl choline (DSPC, Sygena), and 193 mg (0.5 mmol) cholesterol (Fluka) in a mixture of 4 ml of methanol and 36 ml of chloroform. The solution was filtered on a sterile filter membrane of 0.2 μm gauge (Macherey Nagel) and a tracer quantity of 14 C-tripalmitin (10 μl in CHCl 3 ; specific activity 50 μCi/ml) was added as marker. The organic solvents were removed by evaporation in a rotary evaporator (Rotavapor) at 40° C. under reduced pressure and the residue was dried overnight at the same temperature under a pressure of 1 Torr.
There was then added to the dry lipids a quantity of iomeprol (BRACCO) solution (530 mg/ml=260 mg of iodine/ml), so that the solution obtained contained approximately (C Lip ) 15 mg of lipids/ml. Then the solution was heated for about half an hour at 80° C. under gentle stirring to effect hydration of the lipids with consecutive liposome vesicles formation. The liposome suspension was then extruded in succession 5 times through a 2.0 μm polycarbonate filter, then 5 times through a 0.6 μm polycarbonate filter (Nudepore membranes) to effect normalization of the vesicle sizes.
In order to determine the quantity of iodine effectively encapsulated in the liposome vesicles, a 1 ml aliquot of the filtered preparation was dialyzed (dialysis bag from Serva; Mw cutoff≈10.000-15.000) for about 10-12 hrs against 1 l of PBS buffer (Phosphate buffer saline; PO 4 10 mM, NaCl 0.9%). The dialysis operation was repeated once to ensure that all free, non-encapsulated iodine had been removed. To the dialyzed solution (0.9 ml) were added 0.1 ml of a 10% sodium dodecyl sulfate solution and the mixture was heated to 40° C. for 5 minutes. By measuring the optical density of this solution at 260 nm, it was determined at this stage that the final preparation contained 84.41 mg/ml of iomeprol, corresponding to 41.36 mg of iodine per ml. The quantity of lipids effectively present in the preparation was determined by measuring the radioactivity of the sample using a liquid scintillation analyzer (Packard 2200-CA, TRI-CARB®). The lipid concentration (CLip) value found was 14.72 mg/ml, hence the I/L was 2.81.
At this stage, the liposome suspension was microfiltered on an ultrafiltration membrane (Amicon cell) to increase about two times the lipid concentration (to make it about 30 mg/ml).
The mean size of the liposome vesicles and the vesicle size distribution were determined by a Dynamic Light Scattering method (DLS), also known under the name of “Photon Correlation Spectroscopy (PCS) using a Malvern Mastersizer equipment (Malvern Instruments) or a Nicomp 370 HDL-NPSS. The results indicated that the mean size of most vesicles in the present preparation was 0.4 μm with less than 10% above 0.6 μm and under 0.2 μm. Using a particle counter (COULTER Nanosizer), it was found that the mean size of the vesicles was practically 0.4 μm with less than about 20% by weight of the vesicles not within the range of 0.35 to 0.45 μm.
The iodine loaded liposone suspension prepared as above was injected to laboratory rats at the dose of approximately 1 ml/kg of animal (2.81×30=84 mg/kg of animal of encapsulated iodine) and thereafter the animals were subjected to X-ray tomography of the circulation. Satisfactory imaging of the blood vessels was reported including good contrast of left heart portions. The imaging could be pursued for more than about 30 min before fading of the contrast effect became significant.
EXAMPLE 2
Fifty mg of a 9/1 (molar ratio) mixture of distearoylphosphatidyl choline (DSPC) and dipalmitoyl-phosphatidyl-inositol (DPPI) dissolved in 2 ml of a mixture (1/2) of MeOH and CHCl 3 were placed in a 5 ml flask and roto-evaporated at 30° C. under 20-30 Torr. There were then added 5.0 ml of distilled water and the mixture was agitated gently for about ½ hr at 60° C. The resulting liposome suspension was then repeatedly extruded at room temperature through a 0.6 μm microporous membrane (polycarbonate).
To the extruded suspension were added 5 ml of a concentrated aqueous iopamidol solution (520 g/L iodine, 1 g/L Tris, and 0.34 g/L EDTA). The mixture was incubated for ½ hr at 60° C., whereby the dissolved iodine penetrated into the liposome vesicles by trans-membrane permeation, and the suspension was allowed to cool. After eliminating as usual (centrifugation or dialysis) the non-entrapped iodine and replacement of the carrier liquid by a buffer equivalent, the average vesicle size and the liposome size distribution were determined by usual means. Values of about 0.56 μm with less than 10% of the vesicles above 0.6 μm and below 0.2 μm were obtained. The I/L measured as disclosed in the previous example was 4.1. This experiment showed that extrusion of the liposomes can also be done before filling the liposome vesicles with iodine.
When injected into laboratory animals after concentrating about 3-4 times by microfiltration, the foregoing preparation enabled satisfactory imaging of the blood vessels by X-ray.
Equally good results were achieved when in place of iopamidol iohexol, ioversol, iopromide or iotrolan were used.
EXAMPLE 3
The following mixture of lipids was dissolved in 20 ml of organic solvent (18 ml of CHCl 3 and 2 ml of MEOH):
Distearoylphosphatidyl choline (DSPC) 379.8 mg (63.3 mole %);
Cholesterol 92.5 mg (31.7 mole %);
Dipalmitoylphosphatidyl glycerol Na-salt (DPPG-Na) 28.2 mg (5.0 mole %).
The organic solution was filtered on a 0.2 μm polycarbonate filtration membrane and 14 C-tripalmitin (50 μCi/g of lipid) was added thereto. The solution was then evaporated in a round bottom flask under vacuum in a Rotavapor apparatus (40° C./<1 Torr) for 6 hrs. To the solid residue, there were added 32 ml of a concentrated solution (530 g/l) of iomeprol (C I =260 mgI/l; C Lip =15 mg/ml). Hydration, liposome formation and iodine encapsulation were carried out by gentle agitation for 30 min at 80° C.
The liposome suspension was then subjected in succession to a series of extrusions through polycarbonate membranes (Nuclepore®) of various porosity grades, thus leading to four samples (1) to (4), this being according to the following protocol:
TABLE 1
Number of passes
Pore size (μm)
Sample No
5x
2
(1), then
5x
1
(2), then
5x
0.6
(3), then
5x
0.4
—
5x
0.2
(4)
The specific activity of the foregoing samples (117087 dpm/mg lipids) was measured by taking an aliquot, admixing with DIMILUME (scintillation liquid) and the radioactivity being measured by means of a BECKMANN LS-8100 scintillation counter.
The vesicle size and size distribution in the foregoing 4 samples was measured using either of the following particle sizing systems: MALVERN Master Sizer and NICOMP Model 370/HPL. The results are presented below. For the samples (2) to (4), the size distribution was such that less than 20% (by volume) of the vesicles were outside the range 0.2 to 0.6 μm. The I/L values were measured using the same technique disclosed in Example 1.
Samples (1) to (4) were tested for their life-time after injection in laboratory animals. For this, they were injected into the caudal vein of Sprague-Dawley rats at the dose of 1 ml/kg of animal. Blood samples were collected at various periods after injection and tested for radioactivity; after
TABLE 2
Vesicle size
I/L (mg/mg)/
Sample
D (μm)
Ec/D (μl.mg −1 .μm −1 )
(1)
1
3.94/15
(2)
0.6
3.44/22
(3)
0.4
2.81/27
(4)
0.2
1.58/30*
*This value is high and reflects the presence (although less than 20%) of vesicles of size larger than the nominal value.
taking the last blood sample (about 26 hrs after start-up), some of the animals were sacrificed and the blood was gathered in heparinized tubes, as well as the organs, livers, spleens and lungs, which, after having been dried and weighed, were also analyzed as controls. The blood samples were checked as follows: 0.3 ml of blood was admixed with 0.5 ml of a 1:1 “Soluene”-isopropanol solution, then after 1 hr rest, 0.25 ml of H 2 O 2 (30%) was added, followed by 10 ml of scintillation solution (Hionic Fluor). After another 6 hrs rest in the dark, the radioactivity was measured with a Packard Counter.
In Table 3, there is shown for the samples (1) to (4) the amount of lipid (liposomes) remaining in the blood for various periods of time after injection, this amount being expressed in % of the injected dose.
TABLE 3
Time (hrs)
Sample
10 min
1
2
4
(1)
63.47
23.84
9.25
2.23
(2)
76.30
41.28
23.69
9.76
(3)
71.63
48.06
36.19
23.47
(4)
78.85
56.02
44.55
33.20
Table 4 contains the results obtained by multiplying % of the injected dose, after a certain time “t” in circulation, as given in Table 3, by the startingratio of I/L for the samples presented in Table 2. The results are in
TABLE 4
Time (hrs)
Sample
10 min
1
2
4
(1)
250.1
93.9
36.4
8.8
(2)
262.5
142.0
81.5
33.6
(3)
201.3
135.0
101.7
66.0
(4)
149.0
105.9
84.2
62.7
direct proportion to the iodine still present in the blood at time “t”.
The results in the foregoing Tables show that the persistance of the vesicles in the blood is in inverse proportion to their size. Thus, for instance, after 1 hr, there is still about 56% of the 0.2 μm vesicles injected initially in the blood, and only 24% of the 1 μm vesicles, however, suspensions containing liposomes with an average size of 1 μm may be used for blood pool imaging provided the imaging is carried out immediately after administration of the suspension to a patient. In some case this may even be desirable as the liposomes of this size have high I/L. It can also be concluded that the 0.6 μm and 0.4 μm vesicles are particularly interesting for imaging as the amount of iodine still in circulation after, say 1 hr, is the most significant. The importance of the contribution of the 0.4 μm vesicles to the persistance of a relatively high level of iodine in circulation is particularly striking after 2 hr. This shows clearly that the formulations according to the invention containing vesicles in the 0.2-0.6 μm range provide an excellent performance regarding effective blood-pool imaging with encapsulated contrast agents, this being without requiring incorporation of sophisticated “stealth” factors.
The graph of annexed FIG. 1 also illustrates the results of this Example by plotting the % of persistance of the initial injected dose versus time for four different vesicle sizes of samples (1) to (4).
EXAMPLE 4
Four liposome suspensions (A to D) calibrated to 0.4 μm vesicle size were prepared according to the directions of Example 3, using the following lipid formulations:
(A) DSPC 340.9 mg (60 mole %); cholesterol 84.0 mg (30 mole %); palmitoylglucuronic acid (PGlcUA) from Nippon Fine Chemicals 30 mg (10 mole %).
(B) DSPC 244.1 mg (60 mole %); cholesterol 59.8 mg (30 mole %); Phosphatidylethanolamine bound to polyethylene glycol of Mw 2000 (PE-PEG) prepared according to T. M Allen et al., Biochim & Biophys. Acta 1066 (1991), 29-36,147.2 mg (10 mole %).
(C) Formulation identical to that of Example 1.
(D) DSPC (63.3 mole %); cholesterol (31.7 mole %); dipalmitoyl-phosphatidic acid-sodium salt (DPPA-Na) (5 mole %).
The suspensions were subjected to the same checks and analyses as disclosed in the previous Examples, including size distribution (less than 80% of the vesicles outside the range 0.4 μm±10%); and I/L [(A) 0.85, (B) 1.54, (C) 2.81, (D) 2.5]. Note in this connection the adverse effect on the I/L value of the “stealth factors” incorporated to formulations (A) and (B).
The four suspensions were injected into laboratory rats and the blood analyzed periodically as disclosed in Example 3. The results are presented in the graph of annexed FIG. 2 in which the % of the initially injected dose is plotted against time exactly as in FIG. 1 .
The results of the graph of FIG. 2 show that the formulation according to the invention (sample C) exhibit longer residence times in the blood than the formulations containing the recognized “stealth factors” PE-PEG and PGlcUA of the prior art (sample A/PGlcUA & sample B/PE-PEG). In addition, not only the formulations prepared with the known “steath factors” have lower residence times in the circulation but the liposomes of these formulations have a lower entrapment capacity.
Therefore, quite contrary to the belief that “stealth” factors are required even when liposomes are very small size (see M. C. WOODLE et al., and I. A. J. M. BAKKER-WOUDENBERG et al., Journal of Drug Targeting 2 (1994) 397-403 and 363-371, respectively) the present results show that this is not necessary provided that the liposomes employed satisfy certain criteria. This unexpected finding is therefore considered as a further proof of the merit of the invention disclosed.
The results also show the negative effect of the presence of DPPA, i.e. a phospholipid with two negative charges on the phosphoryl moiety. It would appear that all liposome formulations containing DPPA are rapidly taken up by the RES.
EXAMPLE 5
Four lipid formulations (E), (F), (G) and (H) given below, were selected and dissolved each with radioactive tracer added in 4 ml of a 1:1 mixture of CHCl 3 and methanol:
(E) Hydrogenated soy lecithin (SPC-3) from Lipoid K. G., Germany 71.9 mg (60 mole %); cholesterol 17.8 mg (30 mole %); DPPGNa 11.3 mg (10 mole %).
(F) SPC-3 71.8 mg (60 mole %); cholesterol 17.7 mg (30 mole %); DPPG-Na 8.5 mg (7.5 mole %); DPPA-Na 2.6 mg (2.5 mole %).
(G) SPC-3 (57 mole %); cholesterol (28.5 mole %); DPPA-Na (4.5 mole %); PE-PEG (10 mole %).
(H) Like (G), but the PE-PEG replaced by a mol equivalent of PGlcUA.
The solutions were ridden of the solvents under vacuum and the residues converted to corresponding iodine loaded liposome suspensions (E) to (H) exactly as disclosed in Example 3. Then they were normalized by extrusion, as previously described, to a narrow 0.4 μm size distribution. Analyses for specific activity and I/L were carried out as usual; the I/L values were 2.44 for (E), 2.39 for (F), 1.54 for (G) and 0.81 for (H).
The suspensions were tested in rats as disclosed in the previous Examples and the results, plotted as usual in FIG. 3, indicate that (E) was long lasting in the blood as expected. The rapid decay of the formulation (F) demonstrates the dramatic adverse effect of the DPPA on the vesicle stability in the circulation. The curves (G) and (H) show that incorporation of the known “stealth factors” is unable to cure the negative effect of the DPPA. By all means the presence of DPPA or analogues in the liposome suspensions according to the invention should be avoided.
Further experiments were carried out with formulations including less DPPA (down to 1 mole %) and correspondingly more of the aforementioned “stealth” factors PGlcUA and PE-PEG; notwithstanding, the latter were unable to counteract the negative effect of the DPPA. Moreover, it can also be seen from the above I/L results that the conventional “stealth” factors are disadvantageous in the formulations of the present invention as they tend to decrease the capturing capacity of the vesicles (the I/L ratio is low).
If in the previous examples, the DPPG is replaced with an equivalent quantity of diphosphatidyl inositol (DPPI), the liposomes have an equivalent or even longer life in the blood after injection.
EXAMPLE 6
A solution of lipids comprising 152 mg of SPC-3 (63.3 mole %), 37 mg of cholesterol (31.7 mole %), and 11 mg of DPPG.Na (5 mole %) was obtained by dissolving the foregoing ingredients, including a tracer quantity of 14 C-tripalmitin (corresponding to 1310 dpm/mg lipids), in a mixture of methanol (2 ml) and chloroform (18 ml). After removing the volatile solvents with the Rotavapor at 40° C. under about 1 Torr and drying overnight in the same conditions, a dry lipid mixture (˜200 mg) remained in the flask. This dry lipid solid was dissolved in a mixture of 20 ml of CHCl 3 and 20 ml of diisopropyl ether, and 6 ml of a 0.5 M solution of Gd-BOPTA (BRACCO) were thereafter added. The mixture was heated to 60° C. and subjected to ultrasound (Branson Sonifier) for 3 min; then it was again evaporated under reduced pressure in the Rotavapor (60° C.) to give a residue which was dispersed in 20 ml of PBS. Evaporation was continued until all etheral solvents had been completely removed (odorless residue).
Then the liposome suspension was extruded 5 times through a 2 μm membrane and afterwards five more times through a 1 μm membrane. An aliquot (5 ml) was dialyzed overnight against 2 times 1 l of PBS and subjected to analysis as previously reported. Radioactive counting indicated that the lipid concentration C Lip in the liposome suspension was 5.18 mg/ml; the Gd-BOPTA concentration in the suspension, as determined by HPLC according to J. J. Hagan et al. Anal. Chem. 60 (1988), 514-516 (Fluorescence Detection of Gadolinium Chelates separated by Reverse-phase High-performance Liquid Chromatography), after dissolution of the vesicles by addition of SDS was 8.07 mM, i.e. 1.56 mmol Gd/g of lipids. The average size of the vesicles (Malvern) was 0.52 μm±10%. The dialyzed suspension was thereafter concentrated to about 30 mg lipids/ml using an Amicon ultrafiltration cell.
When injected to laboratory animals, this preparation enabled to provide useful contrast in the MRI imaging of the circulation.
EXAMPLE 7
A solution of lipids was prepared by dissolving 114 mg of SPC-3 (63.3 mole %), 28 mg of cholesterol (31.7 mole %), and 8 mg (5 mole %) of DPPG.Na, including a tracer quantity of 14C tripalmitin (corresponding to 1220 dpm/mg of lipids) in a mixture of MeOH (2 ml) and CHCl 3 (8 ml). The solution was subjected to evaporation in a Rotavapor at 40° C. under about 1 Torr to remove the volatile solvents, and it was dried overnight under the same conditions. The dry residue (˜150 mg of lipids) was admixed with 10 ml of 0.5 M solution of gadoteridol (ProHance®, BRACCO Diagnostic Inc.) and hydrated by heating at 65° C. for ¾ hr under gentle agitation. This gave a suspension of MLV (multilamellar) liposomes which was thereafter extruded 5 times through a 2 μm polycabonate membrane and then 5 more times through a 0.6 μm membrane. A 5 ml aliquot of the normalized suspension was dialyzed overnight against 2 successive 1 liter portions of PBS and analyzed as before. Radioactive counting indicated a lipid concentration of 6.52 mg/ml. The average size of the liposome vesicles (Malvern) was found to be 0.44 μm±10%. The gadoteridol concentration in the suspension (found 20.67 mM) was determined by HPLC after dissolution of the vesicles in a sample by the addition of SDS; this did correspond to a ratio mmol Gd/g of lipids of 3.17 and to an entrapment capacity Ec of 6.3 μl/mg of lipids (the theoretical entrapment capacity of 0.44 μm vesicles is equal to 13 μl/mg).
The bulk of the suspension was dialyzed as above and thereafter concentrated up to about 40 mg of lipids/ml (C Lip ) using an Amicon ultrafiltration cell. Upon injection to laboratory animals under the conditions disclosed previously, it enabled to provide useful contrast effects in the MRI of the circulation.
In subsequent experiments the gadoteridol concentration in the suspension after dissolution of the vesicles in a sample as above was found to be 30.18 mM which correspond to a ratio mmol Gd/g of lipids of 4.63 and to an entrapment capacity Ec of 9.2 μl/mg of lipids.
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The present invention concerns injectable blood pool contrast agents for NMR and X-ray imaging purpose. These blood pool agents carry imaging contrast enhancers, e.g. paramagnetic or, respectively, radio-opaque compounds for imaging the circulation and/or circulation targeted organs. The blood pool agent compositions are formulated to protect the contrast agents from early removal by the reticulo-endothelial (RES) system of the liver and the spleen, so that they stay in the circulation long enough to provide good images of the blood vessels and blood perfused organs. X-ray and NMR imaging of the circulation and of targeted organs can strongly assist in diagnosing possible ailments in human and animal patients.
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TECHNICAL FIELD
[0001] This invention relates to the design and construction of high-Q inductors within high frequency integrated circuits.
BACKGROUND
[0002] The present environment sees the rapid proliferation of wireless communications and the wireless products such as modems, pagers, 2-way radios, oscillators and cell phones which include integrated circuits (ICs) having inductors which operate at high frequencies. There is pressure to make these products more and more efficient, compact, light weight and reliable at radio frequency and microwave frequency. It is efficient and economically desirable to fabricate the maximum number of required devices and elements, including inductors, in a single IC and to limit the number and type of processing steps to ones which are consistent with those presently practiced in IC manufacturing. Pushing the performance of conventional integrated circuits into the high frequency range reveals limitations that must be overcome in order to achieve the desired goal. The inductor is one area which has been examined for optimization.
[0003] Quality Factor Q is the commonly accepted indicator of inductor performance in an IC. Q is a measure of the relationship between power loss and energy storage in an inductor expressed as an equation shown as FIG. 1. A high value for Q is consistent with low inductor and substrate loss, low series resistance and high inductance. High frequency is considered be greater than about 500 MHz. To achieve a Q of greater than about 10 would be desirable for that frequency range. The technology of manufacturing ICs over silicon substrates is well established. Unfortunately, a planar spiral inductor fabricated in an IC having a silicon substrate typically experiences high losses at RF, and consequently low Q value. Losses experienced are a result of several factors. Electromagnetic fields generated by the inductor adversely affect the semiconducting silicon substrate as well as devices and conductive lines of which the IC is comprised. The result of this interaction is loss due to coupling, cross talk noise, resistance, parasitic capacitance, reduced inductance and lowering of Q values. Elements of Q with respect to a specific spiral conductor over a silicon substrate are set forth in U.S. Pat. No. 5,760,456, col. 1, line 55-ff.
[0004] One approach to improving the Q factor is to alter the materials of which the IC is comprised. Using substrates other than silicon, such as GaAs and sapphire is possible. However, it would be desirable to maintain manufacturing processes which are as compatible as possible with existing silicon technology, which is well established, rather than to introduce the process changes and to deal with the attendant problems associated with the use of non-silicon substrate materials. U.S. Pat. No. 6,046,109 to Liao et al. describes one approach to improving Q of an IC on a silicon substrate—the creation of isolating regions to separate the inductor from other regions or devices that would otherwise be adversely affected. The isolating regions are created by radiation of, for example, selected silicon semiconductor regions with a high energy beam such as x-rays or gamma rays or by particles such as protons and deuterons, which results in an increase in resistivity of the irradiated area. The depth of penetration of the radiation can be as deep as required to reduce noise, line loss and assure device separation.
[0005] Another approach to improving the Q factor is to alter the shape and dimensionality of the inductor itself in order to overcome inherent limitations of the flat spiral inductor. U.S. Pat. No. 6,008,102 to Alford et al. describes two such shapes, toroidal and helical, which are formed in such a way as to align magnetic fields generated by RF currents within the shaped inductor, thereby minimizing dielectric losses, cross talk and increasing Q.
[0006] U.S. Pat. Nos. 6,114,937, 5,884,990, 5,793,272 and 6,054,329 to Burghartz et al. describe high Q toroidal and spiral inductors with silicon substrate for use at high frequencies. There are described several embodiments which focus on raising Q by increasing inductance. Devices described that are incorporated in the IC in order to raise Q include: a substrate coated with a dielectric layer having a spiral trench which is capped and lined with a ferromagnetic material in which lies the spiral inductor, connected by via to underpass contact; and/or a second spiral inductor either above or adjacent to the first, the two coils being connected to each other by a ferromagnetic bridge and externally, if stacked, by an overpass. The toroidal inductor is similarly formed in dielectric trenches lined with ferromagnetic material, the coils being segmented to reduce eddy currents and the segments being separated from each other by dielectric, increasing the Q. Studs connect the opposite ends. The ferromagnetic bridge and dummy central structures or air core are stated to increase the Q by reducing flux penetration into the substrate thereby increasing inductance. Use of copper, a low resistance material, in thick interconnects reduces parasitic resistance, further increasing Q. (Aluminum has generally been used.) The patent describes results of Q=40 @ 5.8 GHz for a 1.4 nH inductor and Q=13 @ 600 MHz for a 80 nH inductor, twice or triple the Q than conventional silicon-based integrated inductors.
[0007] U.S. Pat. No. 6,037,649 to Liou describes a a three-dimensional coil inductor structure, optionally including a shielding ring, which comprises N-turn coil lines in three levels, separated from each other and the substrate by isolating layers and connected through vias. It is described that the structure of the invention, in which the magnetic field is normal to the substrate, provides lower series resistance than a flat structure, less effect on the other components of the IC, lower parasitic capacitance and higher Q at RF and microwave frequencies.
[0008] U.S. Pat. No. 5,559,360 to Chiu et al. describes a multilevel multielement structure that maintains a constant distance between parallel conductive elements, thereby equalizing each element's resistance. The solution is intended to minimize current crowding, especially at conductor widths beyond 15 microns, and maximize self-inductance between conductive elements, possibly raising the Q to 15 for Al conductor over Si substrate.
[0009] U.S. Pat. No. 5,446,311 to Ewen et al. describes a multilevel inductor constructed on a silicon substrate which is layered with insulating oxide. The inductors are connected in parallel to avoid series resistance and the metal levels are shunted by vias. A Q of 7 at 2.4 GHz is reported.
[0010] U.S. Pat. No. 6,124,624 to Van Roosmalen et al. describes a multilevel inductor comprised of closely spaced stacks of parallel connected elongated rectangular strips in which bridging crossover and/or cross/under is avoided. The levels are separated by silicon dioxide. The structure is stated to raise the Q, possibly over 25 @ 2 GHz, by a reduction of series resistance using various series and parallel connections through vias and by enhanced mutual inductance of layered strips. A staggered stacking is stated to contribute to high Q by reducing parasitic capacitance.
[0011] U.S. Pat. No. 6,146,958 to Zhao et al. describes a reduction in series resistance, hence an increase in Q, by connecting a spiral inductor at a lower level to one at a higher level by a continuous via.
[0012] Another approach to improving the Q factor is to create shielding or zones within the IC which include materials, or open space, that control or limit the extent that electromagnetic lines can penetrate the IC, thereby reducing substrate losses. U.S. Pat. No. 6,169,008B1 to Wen et al. describes forming a 3-5 micron deep trench in the dielectric substrate of an IC, and filling the trench with a high resistivity epitaxy layer which has a lower dopant concentration than the substrate by several orders of magnitude and will therefor act as a dielectric. The epitaxy layer is etched back, a dielectric layer is deposited over all and the inductor windings on the dielectric layer, thereby increasing the resistivity between the substrate and the windings and increasing Q.
[0013] A publication “Large Suspended Inductors on Silicon and Their Use in a 2 micron CMOS RF Amplifier” in IEEE Electron Device Letters, Vol. 14, No. 5 by Chang et al. describes creating a high-Q spiral inductor by selectively etching a 200-500 micron deep cavity underneath a spiral inductor to minimize substrate losses and raise Q.
[0014] U.S. Pat. No. 5,959,522 to Andrews describes a structure having upper and lower high magnetic permeability, i.e. greater than about 1.1, shielding layers between which is a layer comprising a spiral induction coil, optionally including an annular ring. Through an open central area designed to reduce series resistance, eddy currents and dissipative resistive currents the shielding layers are coupled to each other and concentrate the current-induced magnetic flux. The concentration of magnetic flux permits increased inductance in a smaller area. A pattern of radial projections of the shielding layers increases the effective conductance. If the lower shielding level is nonconductive, it also functions as electrical shielding to the substrate, and raise Q.
[0015] U.S. Pat. No. 5,760,456 to Grzegorek et al. describes the interposition of a patterned segmented conductive plane, having an oxide insulating layer covering both top and bottom surfaces, which functions as an electrostatic shield between the substrate level and the spiral inductor level. The conductive plane, which includes a perimeter region electrically connected to a fixed low impedance reference voltage, comprises metal, polysilicon or a heavily doped region of the substrate. Provided its distance from the inductor is sufficient, the design and location of the conductive plane is said to minimize parasitic capacitance, the flow of eddy currents and inhibit the flow of the electric field current to the substrate, increasing the Q, while minimizing the surface area of the inductor also minimizes the series resistance, increasing the Q. It is stated that the invention provides a Q of up to about 6 at a frequency of about 2 GHz.
[0016] U.S. Pat. No. 5,918,121 to Wen et al. maintains the concept of a flat spiral inductor over a silicon substrate and focuses on minimizing loss between the inductor and the substrate by forming an epitaxial area having a resistivity of thousands of ohm-cm, such as silicon lightly doped with such materials as arsenic and phosphorous. The epitaxial area lies surrounded on the top and sides by an oxide insulator and atop the substrate, which has a resistivity of about 10 to about 20 ohm-cm. The planar inductor, which is enclosed on the top and sides by an intermetalic dielectric, lies directly on the that part of the oxide layer which is directly on top of epitaxial area. The stated result is a reduction of loss of induction current to the substrate, and improved Q.
[0017] U.S. Pat. No. 6,153,489 to Park et al. describes forming a trench within the silicon substrate which is filled with an insulating porous silicon, which is a high resistivity material, coating with a dielectric layer on which is formed a lower metal line and a second dielectric layer followed by a spiral inductor pattern which is connected to the metal line by a via. Alternatively, the spiral can be formed within the porous silicon layer. In another alternative a high concentration of dopants of the opposite conductivity type to that of the substrate is implanted in the trench before filling the trench with porous silicon, and forming a polysilicon trench electrode at a point adjacent to and connected with the porous silicon. Instead of ion implanting to form a conductive doped layer, highly doped polysilicon can be used. Application of a reverse bias voltage between the substrate and the doped layer creates a P-N junction depletion layer in the substrate. The resulting structure is stated to further decrease parasitic capacitance and minimize loss from metal levels to substrate, increasing the Q.
[0018] Another approach to improving the Q factor is redesign of IC real estate. U.S. Pat. No. 5,959,515 to Cornett et al. describes effectively reducing the cross-under length of the inductor, i.e. the length of the conductor line between the inner turn of the spiral inductor to the outside connection, by leaving open a center around which is loosely wrapped the turns of the spiral inductor. The patent describes remote placement of devices from the L-C tank circuit to eliminate cross under and parasitic interconnection resistance in a resonator, enhancing Q.
[0019] The structure and process of the present invention is not described in the related art. The well in the present invention is created deep into the substrate. The position of the shield in the substrate with an insulating layer below and a low-k dielectric filling the deep well above it minimizes the parasitic capacitive coupling to the substrate and to devices. Reduction of the parasitic capacitance increases the self-resonating frequency of the spiral inductor, resulting in increased Q. The dielectric layers in the present invention do not need to be thick overall, necessitating high aspect ratio connecting vias, in order to reduce capacitive coupling to the substrate. In the present invention the capacitive coupling between the inductor and the substrate is reduced by increasing the dielectric thickness only directly under the inductor and at a uniform distance from each turn of the inductor. Placing the shield in the bottom of the dielectric-filled well in the present invention lowers the parasitic capacitance between the inductor and the shield, which increases the self resonant frequency of the inductor spiral. The elongated segmented shape of the shield reduces addy currents. The process of the present invention can be smoothly integrated into new and existing technologies. Increasing the spacing between the inductor coil and the substrate using a true, organic dielectric decreases parasitic capacitance, and the placing of a patterned conductive shield (ground plane) on the substrate at the bottom of well terminates any remaining parasitic field before it reaches the substrate. The two contributions taken together increase the Q. Other advantages will be apparent to one skilled in the art.
SUMMARY OF THE INVENTION
[0020] An object of the invention is to provide within an IC structure a high-Q inductor suitable for use in a high frequency environment.
[0021] A further object of the invention is to maximize the value of Q of an integrated inductor by eliminating the losses caused by the penetration of parasitic electrical fields emanating from the inductor into the substrate.
[0022] A further object of the invention is to achieve the above objects using processes and materials which are compatible with those conventionally employed in IC manufacturing.
[0023] These and additional objects are achieved in the present invention in which the capacitive coupling from the inductor to the substrate is eliminated by providing a well filled with organic low dielectric constant (k) material below the inductor and providing a grounded patterned Faraday shield at the bottom of the low-k well. The invention may be fabricated on a bare silicon substrate or on an FEOL, or on SiGe, HRS (high resistivity silicon), or a device wafer such as CMOS or BiCMOS, and the like. Other substrate materials, such as GaAs, quartz, and the like could be used if the method of etching the well is modified accordingly.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] [0024]FIG. 1 is an equation which defines Q.
[0025] [0025]FIG. 2A shows the context in cross section and rotated 90 degrees in which well ( 1 ) shown in 2 B is to be located.
[0026] [0026]FIG. 3A shows in cross-section and rotated 90 degrees the well which is shown in FIG. 2B after applying insulator ( 8 ), conductor ( 9 ) and photoresist mask ( 7 ) and patterning the conductor ( 9 ) and mask ( 7 ) prior to depositing the groundplane (Faraday shield) ( 2 ) shown in 3 B. FIG. 3C shows 3 A after deposition of groundplane ( 2 ) and removal of photoresist mask ( 7 ).
[0027] [0027]FIG. 4A shows the well and groundplane ( 2 ) of FIG. 3B after filling the entire well with a low-k organic dielectric ( 4 ); two sides and the bottom are shown as open for understanding of the shield position. 4 B shows the same in cross-section at 90 degrees rotation after planarizing.
[0028] [0028]FIG. 5 shows the filled well of FIG. 4A in relation to the spiral inductor ( 5 ) integrated in the standard BEOL. FIG. 6 shows the structure of FIG. 5 after adding open vias ( 6 ) in preparation for the alternate embodiment shown in FIG. 7.
[0029] [0029]FIG. 7 shows the structure of FIG. 6 after the organic dielectric ( 4 ) has been removed from the well through the open vias ( 6 ), leaving air dielectric.
DETAILED DESCRIPTION OF THE INVENTION
[0030] A wider choice of material will be available for filling the wells in a structure intended for BEOL if fabrication of the FEOL (front-end-of-line) processing, i.e. the silicon substrate and active devices thereon shown in FIG. 2A, preferably is first completed. In that way the well structure does not risk exposure to subsequent processing that may equal or exceed 400 degrees C. Beginning, then, with the FEOL silicon substrate which is coated with a passivation/insulation layer such as SiO2, Si3N4, or BPSG (boron-phosphorous doped silicate glass), a well is patterned to correspond to an area which is marginally larger than that of the of the intended inductor and directly below it. The pattern for the well is etched through an opening in a mask which will withstand the etchant into the silicon substrate using means such as reactive ion etching (RIE) or wet etching with a solution of TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), EDP (ethylenediaminepyrochatechol) or other etchant selective for the particular substrate composition, until a well which is about 20 microns deep is formed, as seen in FIG. 2B. The side walls of the well should have sufficient slope both to facilitate wall coverage by insulator ( 8 ), conductor ( 9 ) and photoresist ( 7 ) as shown in FIG. 3A and the formation of the ground shield ( 2 ) shown in 3 B and 3 C.
[0031] The bottom and sides of the well are then coated with a second passivation/insulation layer ( 8 ) of SiO2, Si3N4, BPSG or other such material, followed by a layer of conductive material ( 9 ) such as metal, doped a-silicon, doped polysilicon or silicide. Photoresist ( 7 ), such as AZ-4611, is applied over the conductive material and an elongated, segmented pattern for the Faraday ground shield ( 2 ) is opened down to the insulator ( 8 ). The pattern prevents the generation of eddy currents in the shield. A connection to ground ( 3 ) up a side of the well is also exposed, developed and etched as seen in FIG. 3A. Alternatively, the ground shield could be formed by doping the silicon at the bottom of the well through a masked pattern to make the doped area more resistive with respect to the substrate. A low dielectric constant (k) material, such as polyimide 2560 or SiLK ( 4 ), is applied to completely fill the well. The filling of the well is indicated in FIG. 4A; however two walls and the ground shield are left open in the drawing for ease of visualization. The filled well is shown rotated in cross-section in FIG. 4B. For a well which is about 20 microns deep, 25 microns of polyimide would be appropriate to overfill the well and coat the surface of the wafer outside the well. The dielectric is then cured, if polyimide, to 400 degrees C., and if the surface across the wafer and filled well is uneven it is made even by CMP, such as polishing with an alumina slurry, stopping at the passivation/insulation layer on the surface outside the well as shown in FIG. 4B. This step in the process may have to be repeated to ensure coplanarity of the surface of the filled well with the surrounding passivation/insulation layer surface. The planar inductor coil ( 5 ) is formed over the filled well as shown in FIG. 5. Additional process steps are taken to fabricate the complete IC structure desired.
[0032] Decreasing parasitic capacitance between the spiral and the substrate without the addition of prohibitively thick dielectric layering, and providing a Faraday shield ground plane which eliminates any remaining parasitic capacitance in addition to its being shaped to avoid eddy current problems, results in a robust IC structure which includes a low loss spiral inductor having a high Q at RF and microwave frequencies.
[0033] In an alternate embodiment of the invention, after the formation of the inductor coil a pattern is etched between the coils of the inductor to form empty air space in the well below the inductor. Using RIE, the dielectric in the well is removed from under the inductor through open vias, as shown in FIG. 6 and FIG. 7, leaving an air dielectric in the well.
[0034] While the invention has been shown and described in particular embodiments, variations in process steps, materials and structures will be obvious to those skilled in the art.
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Inductor losses to a semiconducting substrate are eliminated in an IC structure by etching a well into the substrate down to the insulating layer coating the substrate and fabricating a grounded Faraday shield in the shape of elongated segments in the bottom of the well. The well lies directly below the inductor and is optionally filled with cured low-k organic dielectric or air.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention is related to the field of headwear and, more particularly, to headwear able to accommodate a range of head sizes, automatically fitting the wearer's head while remaining comfortable for extended use.
[0003] 2. Description of the Related Art
[0004] A baseball style cap generally includes a crown main body, a visor portion that is secured to the forward edge of the crown and extends outwardly therefrom, a headband attached to the lower part of the inside of the crown, and a size controller attached to an underside of the rear of the cap. The size of the cap is adapted to fit the wearer's head using the size controller. This can be inconvenient as the wearer often must adjust the size each time the cap is worn.
[0005] To overcome this inconvenience, cap headbands have been constructed that include an elastic band made of fabric which includes spandex yarn, giving the headband size flexibility while eliminating the size controller. It has been found, however, that such a cap exerts pressure against the wearer's head which can become uncomfortable after the cap is worn for an extended period of time. In addition, the size adjustability of such a cap is limited by the lack of elasticity in the thread used to sew the headband and/or the joint between the headband and the crown.
[0006] Accordingly, a need exists for a free-size cap having a headband that can accommodate a wider range of head sizes without imposing undue pressure on the wearer so as to remain comfortable over extended time periods.
SUMMARY OF THE INVENTION
[0007] In view of the foregoing, one object of the present invention is to provide headwear with a headband that can stretch to accommodate head sizes without a separate size controlling mechanism.
[0008] Another object of the present invention is to provide automatic size-adjusting headwear that does not exert undue pressure on the head when worn.
[0009] A further object of the present invention is to provide a cap having wider size range accommodation through the use of rubber thread and nylon stretch thread sewn in a chain-like pattern along the headband.
[0010] Yet another object of the present invention is to provide a cap in which the crown part and the headband are joined using rubber thread and nylon thread.
[0011] In accordance with these and other objects, the present invention is directedFto headwear having a crown portion and a headband attached to and extending around the lowerFinside edge of the crown portion. A visor part may also be attached to the underside of the crown portion. The sewing thread used on the headband includes rubber thread and nylon stretch thread sewn together in a chain-like pattern to provide expandability and thereby increase the number of different wearer head sizes that may be accommodated by the headband. With this construction, a wide range of automatic size adjustment is obtained without imposing undue elastic pressure on the wearer.
[0012] These together with other objects and advantages which will become subsequently apparent reside in the details of construction and operation as more fully hereinafter described and claimed, reference being had to the accompanying drawings forming a part hereof, wherein like numerals refer to like parts throughout.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] [0013]FIG. 1 is a partially sectioned view of a baseball-style cap with a headband according to the present invention;
[0014] [0014]FIG. 2 is a top view of a visor cap with the headband according to the present invention;
[0015] [0015]FIG. 3 is a top view of another hat style with the headband according to the present invention;
[0016] [0016]FIG. 4 is an outer perspective view of the headband sewn with rubber and nylon stretch threads according to the present invention;
[0017] [0017]FIG. 5 is an inner perspective view of the headband shown in FIG. 4;
[0018] [0018]FIG. 6 is a cross-sectional view of a conventional stitching pattern; and
[0019] [0019]FIG. 7 is a cross-sectional view of the chain-like stitching pattern according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] In describing preferred embodiments of the invention illustrated in the drawings, it is to be understood that these embodiments are given by way of illustration only. It is not intended that the invention be limited in its scope to the details of construction and arrangement of components set forth in the following description or illustrated in the drawings. Also, in describing the preferred embodiments, specific terminology will be resorted to for the sake of clarity. It is to be understood that each specific term includes all technical equivalents which operate in a similar manner to accomplish a similar purpose.
[0021] The present invention is directed to headwear of various types, each having a headband sewn with rubber thread and nylon stretch thread in a chain-like pattern to provide automatic size adjustment to accommodate a wider range of head sizes and with greater comfort than is possible using prior art headwear structures and sewing methods.
[0022] According to a first embodiment as illustrated in FIG. 1, the present invention is directed to a baseball-style cap including a crown main body, generally designated by the reference numeral 1 , a visor portion, generally designated by the reference numeral 2 , and a headband, generally designated by the reference numeral 3 . The crown part 1 is generally made of more than one piece of fabric. The visor portion 2 is secured to the forward edge of the crown main body 1 , and the headband 3 is secured to the lower peripheral edge of the interior of the crown 1 . The visor 2 may include a stiffening member 4 covered with the visor fabric. The headband 3 is folded to have a tunnel-like shape and is secured using a plurality of stitching lines 5 , each of which is composed of rubber thread and nylon stretch thread.
[0023] In addition, the joint between the crown main body 1 and the headband 3 (not shown) is sewn using rubber thread and nylon thread, further enhancing the stretchability of the cap. The stitching of such joint may be sewn so as to be visible on the outer surface of the crown main body 1 , or may be sewn so as to be visible only from the inside of the cap such that the consistency of the outer appearance of the cap is not disturbed.
[0024] A second embodiment of the headwear in accordance with the present invention, namely that of a visor, is shown in FIG. 2 . The visor includes a crown part, generally designated by the reference numeral 6 , a visor part 2 attached to the front side of the crown part 6 , and a headband, generally designated by the reference numeral 8 . The headband 8 is attached to the lower peripheral edge of the interior of the crown part 6 . The headband 8 is folded to have a tunnel-like shape and is secured using a plurality of stitching lines 9 , each of which is composed of rubber thread and nylon stretch thread. The elastic thread may be readily stretched in the direction of the periphery of the crown part 6 to accommodate various head sizes. As with the cap, the joint between the crown part 6 and the headband 8 is sewn using rubber thread and nylon thread.
[0025] A third embodiment of the headwear in accordance with the present invention, namely that of a brimmed hat, is shown in FIG. 3. The brimmed hat includes a crown part, generally designated by the reference numeral 10 , a brim part, generally designated by the reference numeral 11 , and a headband, generally designated by the reference numeral 12 . The crown part 10 is generally made of more than one piece of fabric. The headband 12 and the brim part 11 are each attached to the lower peripheral edge of the interior of the crown part 10 . The headband 12 is folded to have a tunnel-like shape and is secured using a plurality of stitching lines 13 , each of which is composed of rubber thread and nylon stretch thread. As with the baseball-style cap and the visor, the elastic thread used to stitch the headband of the brimmed hat may be readily stretched in the direction of the periphery of the crown part 10 to accommodate various head sizes, and the joint between the crown part 10 and the headband 12 is sewn using rubber thread and nylon thread.
[0026] As shown in each of FIGS. 1 - 3 , the respective headwear is constructed without a separate size controlling element so that, upon wearing thereof, the fabric of the headband and the stitching thereon are stretched as necessary to fit the wearer's head. The headband may be made of a textile containing no spandex yarn to limit the stretchability of such band or may, alternatively, be made of a textile which includes spandex yarn for increased size adjustability.
[0027] [0027]FIG. 4 illustrates the headband according to the present invention, generally designated by the reference numeral 14 , as sewn with rubber thread and nylon stretch thread, shown from the outer side 18 , with “outer” referring to that side of the headband which directly contacts the wearer's head when the headwear bearing the headband is worn. Conversely, FIG. 5 illustrates a view of the inner side 19 of the headband 14 , with “inner” referring to that side of the headband opposite the outer side 18 and contacting the inner surface of the lower edge of the crown part of the headwear bearing the headband. The headband 14 shown in FIGS. 4 and 5 is representative of each of the headbands 3 , 8 , 12 depicted in the various embodiments of FIGS. 1 - 3 .
[0028] As shown in FIGS. 4 and 5, the headband 14 preferably includes four lines of stitching, generally designated by the reference numeral 15 . Each line of stitching 15 is formulated using at least two threads, which may be made of different materials, with only one of the threads being visible on one of the sides of the headband. Particularly, as shown in FIG. 4, the outer portion of the lines of stitching 15 a , namely that portion visible on the outer side 18 of the headband 14 , represents only an outer thread 20 and has an appearance like that of conventional stitching; an example of conventional stitching is shown in FIG. 6. However, according to the present invention, the inner portion of the lines of stitching 15 b , namely that portion visible on the inner side 19 of the headband 14 , shown in FIG. 5, includes both the outer thread 20 and an inner thread 21 which, as shown in greater detail in FIG. 7, are sewn together in a chain-like pattern.
[0029] According to the conventional stitching method as shown in FIG. 6, an upper thread 16 and a lower thread 17 are interwoven in a tongue-and-groove type relationship to each other through the space between the outer fabric 18 and the inner fabric 19 . The resulting lines of stitching look the same on both the outer fabric 18 and inner fabric 19 , with a single one of the threads 16 , 17 being visible on each fabric, respectively.
[0030] According to the method of sewing with rubber thread according to the present invention, shown in FIG. 7, the outer thread 20 and the inner thread 21 are interwoven in a chain-like pattern. Starting at the outer fabric 18 (for purposes of description), the outer thread 20 goes through both the outer fabric 18 and the inner fabric 19 , and then weaves down and up through a double loop of the inner thread 21 , as shown, to form a chain-like pattern on the inner portion 15 b of the lines of stitching. The outer thread 20 then goes back through the inner fabric 19 and the outer fabric 18 to form a generally linear pattern on the outer portion 15 a of the lines of stitching 15 . As shown, only the outer thread passes through the outer and inner fabric layers 18 , 19 of the headband, and the outer thread 20 goes through a double loop of said inner thread 21 in between each pass through such headband fabric layers 18 , 19 .
[0031] According to a preferred embodiment, the outer thread 20 is rubber thread and the inner thread 21 is nylon stretch thread. It is also possible to use rubber thread for both the outer thread 20 and the inner thread 21 , or to use nylon stretch thread for both threads, but best results are obtained with the rubber outer thread and the nylon stretch inner thread in accordance with the preferred embodiment.
[0032] Through the use of elastic thread elements and the chain-like pattern as described and illustrated herein, the headband according to the present invention achieves good expandability, accommodating a wide range of head sizes with a high degree of comfort for the wearer.
[0033] The foregoing descriptions and drawings should be considered as illustrative only of the principles of the invention. The invention may be configured in a variety of shapes and sizes and is not limited by the dimensions of the preferred embodiment. Numerous applications of the present invention will readily occur to those skilled in the art. For example, the headband may be incorporated into hats, caps and visors of other styles. Therefore, it is not desired to limit the invention to the specific examples disclosed or the exact construction and operation shown and described. Rather, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention.
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Headwear having a crown portion and a headband attached to and extending around the lower inside edge of the crown portion. The sewing thread used on the headband includes rubber thread and nylon stretch thread sewn together in a chain-like pattern to provide expandability and thereby increase the number of different wearer head sizes that may be accommodated by the headband. With this construction, a wide range of automatic size adjustment is obtained without imposing undue elastic pressure on the wearer.
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CROSS REFERENCE TO RELATED PATENT APPLICATIONS
[0001] This application is a continuation of U.S. patent application Ser. No. 13/721,171 filed Dec. 20, 2012, which is a continuation of U.S. patent application Ser. No. 12/764,226 filed Apr. 21, 2010, now U.S. Pat. No. 8,357,171, which is a divisional of U.S. patent application Ser. No. 11/245,493 filed Oct. 7, 2005, now U.S. Pat. No. 7,717,926, which claims benefit of and priority to U.S. Provisional Application No. 60/617,016 filed Oct. 8, 2004, and the disclosures of each of the above-identified applications are hereby incorporated by reference in their entirety.
TECHNICAL FIELD
[0002] The technical field relates to surgical clip appliers and more particularly to an endoscopic surgical clip applier having a mechanism for stabilizing the jaw structure during the insertion of a surgical clip.
DESCRIPTION OF THE RELATED ART
[0003] Endoscopic staplers and clip appliers are known in the art and are used for a number of distinct and useful surgical procedures. In the case of a laparoscopic surgical procedure, access to the interior of an abdomen is achieved through narrow tubes or cannulas inserted through a small entrance incision in the skin. Minimally invasive procedures performed elsewhere in the body are often generally referred to as endoscopic procedures. Typically, a tube or cannula device is extended into the patient's body through the entrance incision to provide an access port. The port allows the surgeon to insert a number of different surgical instruments therethrough using a trocar and for performing surgical procedures far removed from the incision.
[0004] During a majority of these procedures, the surgeon must often terminate the flow of blood or another fluid through one or more vessels. The surgeon will often apply a surgical clip to a blood vessel or another duct to prevent the flow of body fluids therethrough during the procedure. An endoscopic clip applier is known in the art for applying a single clip during an entry to the body cavity. Such single clip appliers are typically fabricated from a biocompatible material and are usually compressed over a vessel. Once applied to the vessel, the compressed clip terminates the flow of fluid therethrough.
[0005] One significant design goal is that the surgical clip be loaded between the jaws without any compression of the clip from the loading procedure. Such bending or torque of the clip during loading is disfavored and care is exercised to prevent any damage to the jaws and/or the clip or compression to the clip by a force during loading. This compression could slightly alter the alignment of the clip between the jaws, or damage the clip causing the surgeon to remove the clip from between the jaws for discarding the clip. Additionally such preloading compression may slight compress parts of the clip and change the geometry of the clip. This will cause the surgeon to remove the compressed clip from between the jaws for discarding the clip. Accordingly, there is a need for an apparatus that eliminates one or more of the aforementioned drawbacks and deficiencies of the art.
SUMMARY
[0006] According to a first aspect of the present disclosure, there is provided an apparatus for application of surgical clips to body tissue. The apparatus has a handle portion with a body extending distally from the handle portion defining a longitudinal axis and a plurality of surgical clips disposed within the body. The apparatus also has a jaw assembly mounted adjacent a distal end portion of the body with the jaw assembly including first and second jaw portions movable between a spaced-apart and an approximated position. The apparatus further has a wedge plate longitudinally movable between the first and the second jaw portions, and a clip pusher configured to individually distally advance a surgical clip to the jaw assembly while the jaw portions are in the spaced apart position with an actuator. The actuator is at least partially disposed within the body and longitudinally movable in response to actuation of the handle portion and has a cam link. The apparatus also has a jaw closure member positioned adjacent the first and second jaw portions to move the jaw portions to the approximated position. The cam link longitudinally moves wedge plate between the first and the second jaw portions.
[0007] According to another aspect of the present disclosure, the apparatus has the wedge plate biasing the first and the second jaw portions when said wedge plate is longitudinally moved between the first and the second jaw portions and the wedge plate maintains the first and the second jaw portions in a fixed predetermined relationship during loading of the clip. The fixed predetermined relationship prevents flexing of the first and the second jaw members during clip loading.
[0008] According to another aspect of the present disclosure, the apparatus has the wedge plate with a rounded distal tip.
[0009] According to another aspect of the present disclosure, the apparatus has the wedge plate with a first proximal window. The first proximal window is adapted to be engaged by a member disposed in the body with the member being configured to hold the wedge plate in a distal most position. The distal most position being between the first and the second jaw members.
[0010] According to another aspect of the present disclosure, the apparatus has the wedge plate with a second proximal window. The second proximal window is adapted to be engaged by the member and the second proximal window is configured to hold the wedge plate in a proximal most position retracted from the first and the second jaw members. The proximal most position of the wedge plate is configured to allow the first and the second jaw members to be moved to the approximated position to compress the clip.
[0011] According to another aspect of the present disclosure, the apparatus has the first proximal window connected to the second proximal window by a longitudinal slot.
[0012] According to another aspect of the present disclosure, the apparatus has the member movable from the second proximal window to first proximal window by moving the wedge plate distally.
[0013] According to still another aspect of the present disclosure, the apparatus has the cam link engageable with a cam slot in the wedge plate. The cam slot has a driving edge.
[0014] According to another aspect of the present disclosure, the member is a flexible leg.
[0015] According to another aspect of the present disclosure, the apparatus has the cam slot with a proximal side and a distal side. At the distal side, the cam link traverses past the driving edge at a demarcation line. At the demarcation line, the cam link terminates distal movement of the wedge plate.
[0016] According to another aspect of the present disclosure, the apparatus has the wedge plate further comprising a biasing device. At the demarcation line, the disengagement between the cam link and the driving edge permits the biasing device to retract the wedge plate.
[0017] According to another aspect of the present disclosure, the cam link disengages the wedge plate at the demarcation line, and the disengagement of the cam link permits retraction of the rounded distal end from between the first and the second jaw members.
[0018] According to another aspect of the present disclosure, there is provided an apparatus for application of surgical clips to body tissue. The apparatus has a handle portion and a body extending distally from the handle portion and defining a longitudinal axis with a plurality of surgical clips disposed within the body and a jaw assembly mounted adjacent a distal end portion of the body. The jaw assembly has first and second jaw portions movable between a spaced-apart and an approximated position. The apparatus also has a clip pusher configured to individually distally advance a surgical clip to the jaw assembly while the jaw portions are in the spaced apart position and an actuator at least partially disposed within the body and longitudinally movable in response to actuation of the handle portion. The actuator is biased to longitudinally move proximally. The apparatus also has a jaw closure member positioned adjacent the first and second jaw portions to move the jaw portions to the approximated position and a rack having a plurality of ratchet teeth being connected to the actuator with a pawl biased to the handle portion. The pawl has at least one tooth configured to engage the ratchet teeth. As the actuator is moved longitudinally, the plurality of ratchet teeth are passed over the pawl and the pawl is configured to prevent inadvertent return of the actuator before full actuation of the apparatus.
[0019] According to another aspect of the present disclosure, the pawl is biased by a spring and the spring is connected to the handle portion to bias the pawl into engagement with the rack.
[0020] According to another aspect of the present disclosure, the apparatus has the pawl is pivotally mounted in the handle portion.
[0021] According to another aspect of the present disclosure, when actuation of the handle portion is terminated in mid stroke, the ratchet teeth restrain the pawl against proximal motion, and any inadvertent partial actuation of the jaw assembly is prevented.
[0022] According to another aspect of the present disclosure, the apparatus has the first jaw and second portions moved to the approximated position and the ratchet teeth are advanced a predetermined distance past the pawl to permit retraction of the actuator.
[0023] According to another aspect of the present disclosure, there is provided an apparatus for application of surgical clips to body tissue. The apparatus has a handle assembly with a handle and a trigger movable relative to the handle, and a body extending distally from the handle portion and defining a longitudinal axis. The apparatus also has a plurality of surgical clips disposed within the body and a jaw assembly mounted adjacent a distal end portion of the body with the jaw assembly including first and second jaw portions movable between a spaced-apart and an approximated position. The apparatus further has a clip pusher configured to individually distally advance a surgical clip to the jaw assembly while the jaw portions are in the spaced-apart position and an actuator at least partially disposed within the body and longitudinally movable in response to actuation of the handle portion. The apparatus also has a link connected at a first end to the actuator and connected at a second end to the trigger with a jaw closure member positioned adjacent the first and second jaw portions to move the jaw portions to the approximated position.
[0024] According to another aspect of the present disclosure, the link is connected to a rack having a plurality of ratchet teeth and the ratchet teeth are connected to a pawl and are configured to prevent inadvertent return of the actuator before full actuation of the apparatus.
[0025] According to another aspect of the present disclosure, the apparatus has the pawl biased to the handle. As the trigger is actuated the link is advanced distally and the link advances the rack distally. The pawl ratchet teeth slide along the pawl.
[0026] According to another aspect of the present disclosure, the apparatus has the pawl is pivotally connected to the handle.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] A particular embodiment of a surgical clip applier is disclosed herein with reference to the drawings wherein;
[0028] FIG. 1 is a perspective view of a surgical clip applier;
[0029] FIG. 2 is another perspective view of the surgical clip applier of FIG. 1 ;
[0030] FIG. 3 is an enlarged perspective view of the jaw structure of the surgical clip applier;
[0031] FIG. 4 is a top view of the surgical clip applier;
[0032] FIG. 5 is a side view of the surgical clip applier;
[0033] FIG. 6 is a side view, with half of the body removed, of the handle assembly of the surgical clip applier;
[0034] FIG. 7 is an exploded perspective view of the handle of the clip applier, with shaft assembly;
[0035] FIG. 8 is a perspective view of a pawl;
[0036] FIG. 9 is a perspective view of a yoke;
[0037] FIG. 10 is an exploded perspective view of the shaft assembly of the surgical clip applier;
[0038] FIG. 10A is a perspective view of a feed bar;
[0039] FIG. 10B is a perspective view of a follower and surgical clips;
[0040] FIGS. 10C and 10D are opposite perspective views of a trip block;
[0041] FIG. 10E is a perspective view of a spindle;
[0042] FIG. 10G is an enlarged area of detail of FIG. 10E ;
[0043] FIG. 10F is an enlarged area of detail of FIG. 10E ;
[0044] FIG. 11 is a perspective view of the distal end of the spindle and a driver;
[0045] FIG. 12 is a perspective view of a trip lever mechanism on the spindle;
[0046] FIG. 13 is a perspective view of a wedge plate and biasing spring;
[0047] FIGS. 14 and 15 are opposite perspective views of a filler component;
[0048] FIG. 16 is a perspective view of the rotation knob and shaft assembly;
[0049] FIG. 17 is a perspective view of the overpressure assembly;
[0050] FIG. 18 is a perspective view of the spindle and jaw assembly;
[0051] FIG. 19 is an enlarged area of detail of the spindle and jaw assembly of FIG. 18 ;
[0052] FIG. 20 is an enlarged area of detail of the spindle and trip lever of FIG. 18 ;
[0053] FIG. 21 is an enlarged view of the distal end of the surgical clip applier with outer tube removed;
[0054] FIG. 22 is a perspective view of the surgical clip applier shaft assembly with parts removed;
[0055] FIG. 23 is an enlarged area at detail of FIG. 22 ;
[0056] FIG. 24 is an enlarged area of detail of FIG. 22 ;
[0057] FIG. 25 is an enlarged area of detail of FIG. 22 ;
[0058] FIG. 26 is a perspective view of the spindle, driver and jaw assembly;
[0059] FIG. 27 is an enlarged area of detail of FIG. 26 ;
[0060] FIG. 27A is a cross-sectional view taken along line 27 A- 27 A of FIG. 27 .
[0061] FIG. 28 is a perspective view of the cam link and wedge plate assembly;
[0062] FIG. 29 is an enlarged area of detail of FIG. 28 ;
[0063] FIG. 30 is an enlarged area of detail of FIG. 29 ;
[0064] FIG. 31 is a perspective view of the filler component and jaw assembly;
[0065] FIG. 32 is an enlarged perspective view of the jaw assembly of FIG. 31 ;
[0066] FIGS. 33 and 34 are perspective views of the distal end of the spindle including wedge plate and driver;
[0067] FIG. 35 is a side view, partially shown in section, of the surgical clip applier in a pre-fired condition;
[0068] FIG. 36 is in enlarged area of detail of FIG. 35 ;
[0069] FIG. 37 is an enlarged area of detail of FIG. 35 ;
[0070] FIG. 38 is in enlarged area of detail of FIG. 37 showing the trip lever;
[0071] FIG. 39 is an enlarged area of detail of FIG. 37 showing the follower;
[0072] FIG. 40 is an enlarged the area of detail of FIG. 37 ;
[0073] FIG. 41 is enlarged area of detail of FIG. 40 ;
[0074] FIG. 42 is a side view, shown in section, of the distal end of the surgical clip applier of FIG. 37 ;
[0075] FIG. 43 is a perspective view of the wedge plate and jaw assembly;
[0076] FIG. 44 is an enlarged area of detail of FIG. 43 showing the wedge plate and jaw members;
[0077] FIG. 45 is a top view of FIG. 43 taken along line 45 - 45 ;
[0078] FIG. 46 is an enlarged area of detail of FIG. 45 showing the jaw and the wedge plate;
[0079] FIG. 47 is an enlarged area of detail of FIG. 45 showing the wedge plate and cam link;
[0080] FIG. 48 is a side view, shown in section, of the handle housing at the beginning of an initial stroke;
[0081] FIG. 49 is an enlarged area of detail of FIG. 48 showing the rack and pawl;
[0082] FIG. 50 is an enlarged area of detail of FIG. 48 similar to FIG. 49 ;
[0083] FIG. 51 is a side view, shown in section, of the feed bar and trip lever;
[0084] FIG. 52 is a side view, shown in section, of the follower;
[0085] FIG. 53 is a side view, shown in section, of the endoscopic portion of the surgical clip applier;
[0086] FIG. 54 is an enlarged area of detail of FIG. 53 illustrating the spindle movement;
[0087] FIG. 55 is a top view of the wedge plate and filler component illustrating the movement of the cam link;
[0088] FIG. 56 is a side view, shown in section, illustrating the feed bar advancing a clip;
[0089] FIG. 57 is a top view of the wedge plate and cam link moving distally;
[0090] FIG. 58 is a side view, shown in section, showing the movement of the flexible leg cammed out of a wedge plate window;
[0091] FIG. 59 is a side view, shown in section, illustrating a clip entering the jaws;
[0092] FIG. 60 is a further top view of the cam link and wedge plate movement;
[0093] FIG. 61 is a side view, shown in section, of the flexible leg and wedge plate disengagement;
[0094] FIG. 62 is a top view of the wedge plate entering the jaw structure;
[0095] FIG. 63 is a perspective view illustrating the wedge plate camming open the jaw structure;
[0096] FIG. 64 is a top view illustrating further advancement of the cam link in the wedge plate;
[0097] FIG. 65 is a side view, shown in section, illustrating the trip lever engaged with the feed bar;
[0098] FIG. 66 is a side view, shown in section, illustrating the spindle camming the flexible leg out of engagement with the wedge plate;
[0099] FIG. 67 is a side view, shown in section, illustrating the feed bar loading a clip into the jaw structure;
[0100] FIG. 68 is a side view, shown in section, illustrating the trip lever being cammed out of engagement with the feed bar by means of a trip block;
[0101] FIG. 69 is a side view, shown in section, illustrating the retraction of the wedge plate and feed bar;
[0102] FIG. 70 is a side view, shown in section, illustrating further advancement of the spindle;
[0103] FIG. 71 is a side view, shown in section, illustrating the retraction of the wedge plate and further advancement of the spindle;
[0104] FIG. 72 is a perspective view of the wedge plate retracting from the jaw structure;
[0105] FIG. 73 is a side view, shown in section, with the spindle engaging the driver and a latch retractor engaging the spindle;
[0106] FIG. 74 is a side view of the handle housing with the trigger at full stroke;
[0107] FIG. 75 is an enlarged area of detail of FIG. 74 with the pawl clearing the ratchet rack;
[0108] FIG. 76 is a side view, shown in section, of the driver camming the jaws closed about a surgical clip;
[0109] FIGS. 77 to 79 are sequential views of the driver camming the jaws closed about a surgical clip;
[0110] FIG. 80 is a view, shown in section, of the overpressure mechanism including the impact spring;
[0111] FIG. 81 is a perspective view of a surgical clip formed on a vessel;
[0112] FIG. 82 is an enlarged area of detail of the ratchet mechanism resetting;
[0113] FIG. 83 is a side view, shown in section, illustrating the latch retractor resetting;
[0114] FIG. 84 is a side view, shown in section, illustrating the spindle retracting; and
[0115] FIGS. 85 and 86 are top views illustrating the cam link resetting within the wedge plate.
DETAILED DESCRIPTION
[0116] There is disclosed a novel endoscopic surgical clip applier having a jaw control mechanism configured to maintain jaws of the surgical clip applier in a spaced apart and stable position during insertion of a surgical clip. It should be noted that, while the disclosed jaw control mechanism is shown and described in an endoscopic surgical clip applier, the disclosed jaw control mechanism is applicable to any surgical clip applier or other instrument having a pair of compressible jaws.
[0117] Referring now to FIGS. 1-5 , surgical clip applier 10 generally includes a handle assembly 12 and an endoscopic portion including an elongated tubular member 14 extending distally from handle assembly 12 . Handle assembly 12 is formed of a plastic material while elongated tubular member 14 is formed of a biocompatible material such as stainless steel. A pair of jaws 16 are mounted on the distal end of elongated tubular member 14 and are actuated by a trigger 18 movably mounted in handle assembly 12 . Jaws 16 are also formed of a biocompatible material such as stainless steel or titanium. A knob 20 is rotatably mounted on a distal end of handle assembly 12 and affixed to elongated tubular member 14 to provide 360 degree rotation of elongated tubular member 14 and jaws 16 about its longitudinal axis. Referring for the moment to FIG. 3 , jaws 16 define a channel 22 for receipt of a surgical clip therein.
[0118] Referring now to FIGS. 6 and 7 , handle assembly 12 of clip applier 10 is shown. Handle assembly 12 includes a longitudinally movable yoke 24 connected to trigger 18 by a link 26 . Handle assembly 12 includes housing channels 28 to guide yoke wings 30 of yoke 24 within handle assembly 12 during actuation of clip applier 10 . Yoke 24 is connected to the drive mechanisms and is biased to a proximal position by a return spring 32 . Knob 20 includes a flange 34 which is rotatably mounted in a journal 36 in housing 12 .
[0119] Referring to FIGS. 6-9 , in order to prevent inadvertent return of trigger 18 and yoke 24 before full actuation of surgical instrument 10 , yoke 24 includes a rack 38 having rack teeth 40 . A pawl 42 is pivotally mounted in handle assembly 12 and includes pawl teeth 44 engageable with rack teeth 40 . Pawl 42 is biased into engagement with rack 38 by a spring 46 . Rack 38 and pawl 42 prevent release of trigger 18 before full actuation in a manner described in more detail hereinbelow.
[0120] Combinations of the various elements and mechanisms associated with clip applier 10 will now be described.
[0121] Referring to FIG. 10 , a bushing 48 , including retention pins 50 , is provided to secure the bushing 48 to the knob 20 . A drive link 52 is connected, typically with a snap type connection, to yoke 24 such that a proximal end of drive link 52 engages yoke 24 . An over pressure mechanism including an impact spring 56 is provided about outer tube 14 , between bushing 48 and housed in a bore of knob 20 to prevent over compression of jaws 16 during actuation of the instrument in a manner described in more detail hereinbelow. Drive link 52 extends through a bore 58 in knob 20 .
[0122] A flange located at a proximal end of elongated tube member 14 abuts a proximal end of bushing 48 .
[0123] In order to actuate the various components there is provided an actuation mechanism or spindle 60 mounted for longitudinal movement through elongated tubular member 14 . Spindle 60 includes a boss 62 at its proximal end which is engageable with a recess 64 on the distal end of drive link 52 . A camming mechanism including a driver 66 and a slider joint 68 extend from a distal end of spindle 60 to cam closed jaws 16 about a surgical clip.
[0124] Clip applier 10 is configured to retain a plurality of surgical clips for application to tissue. Clip applier 10 includes an elongated channel member 70 configured to retain a plurality of surgical clips 72 and convey surgical clips 72 to jaws 16 . It should be noted that channel member 70 and jaws 16 do not move longitudinally relative to elongated tubular member 14 . A follower 74 is biased by a spring 76 to urge surgical clips 72 distally within channel member 70 . A channel cover 78 overlies channel 70 to retain and guide spring 76 and surgical clips 72 therein. A nose 80 is provided at a distal end of channel cover 78 to assist in directing surgical clips 72 into jaws 16 .
[0125] A feeder mechanism including a feed bar 82 is provided for longitudinal movement relative to channel cover 78 in order to advance individual clips 72 into jaws 16 . A trip block 84 having a guide pin 86 and a feed bar spring 88 are provided adjacent the proximal end of channel cover 78 to bias feed bar 82 in a proximal direction. Specifically, a proximal end 90 of guide pin 86 is interconnected with a hook 92 on an underside of feed bar 82 ( FIGS. 38A & B) and through slot 94 in trip block 84 . (See also FIGS. 10 A, C, & D) In order for spindle 60 to move feed bar 82 , spindle 60 is provided with a trip lever 96 and a biasing spring 98 . Trip lever 96 is engageable with a proximal end of feed bar 82 in a manner described in more detail herein below.
[0126] A notable advantage of presently disclosed clip applier 10 is that it is provided with a wedge plate 100 which is configured to advance into jaws 16 during actuation of surgical clip applier 10 and maintain jaws 16 in a spaced apart condition while receiving a surgical clip 72 . Cam slot 136 ( FIG. 13 ), described in detail hereinbelow, formed through wedge plate 100 and a filler component 102 mounted within elongated tubular member 14 , cooperate in connection with a cam link 104 , provided on spindle 60 , to move wedge plate 100 relative to filler component 102 and jaws 16 . Filler component 102 is positioned directly behind jaws 16 and does not move relative to elongated tubular member 14 .
[0127] Turning to FIG. 10A , and as noted above, feed bar 82 is provided to move surgical clips 72 into jaws 16 . Feed bar 82 is driven by trip lever 96 on spindle 60 . (See FIG. 10 .) Specifically, feed bar 82 is provided with an elongated window 106 which is configured to be engaged by trip lever 96 as spindle 60 is driven distally. To facilitate insertion of the clip into jaws 16 , feed bar 82 is provided with a pusher 108 at its distal end which is configured to advance an individual clip 72 out of the line of clips 72 and into jaws 16 . As shown in FIG. 10B , follower 74 is positioned behind the line of clips to advance clips 72 through surgical clip applier 10 .
[0128] Referring to FIG. 10C , as noted above, trip block 84 includes a slot 94 to receive hook 92 of feed bar 82 . In order to disengage trip lever 96 from window 106 and thus feed bar 82 , trip block 84 is provided with an angled surfaces 110 which is configured to engage trip lever 96 and disengage it from window 106 of feed bar 82 as best shown in FIG. 10D .
[0129] Referring now to FIGS. 10E-10G , various features of spindle 60 will now be described. A perspective view of spindle 60 , isolated from other components is shown in FIG. 10E . With specific reference to FIG. 10F , at a proximal end, spindle 60 includes a pivot point 112 for attachment of trip lever 96 at its proximal end. Additionally, a boss 114 is provided in spindle 60 for attachment of biasing spring 98 to bias trip lever 96 into engagement with window 106 of feed bar 82 . Similarly, with respect to FIG. 10G , at a distal end, spindle 60 is provided with a boss 116 for mounting cam link 104 . Spindle 60 is additionally provided with a raised feature 118 which functions to disengage filler component 102 from wedge plate 100 in a manner described in hereinbelow.
[0130] Referring to FIG. 11 , spindle 60 is provided to advance driver 66 into engagement with jaws 16 to close jaws 16 about a surgical clip after the surgical clip has been positioned within jaws 16 . A distal end 120 of slider joint 68 resides in a recess 122 in driver 66 . A proximal projection 124 of slider joint 68 rides within a longitudinal slot 126 in the distal end of spindle 60 . The length of longitudinal slot 126 allows spindle 60 to move a predetermined longitudinal distance before engaging and moving driver 66 longitudinally to close jaws 16 about a clip 72 . A latch retractor 128 is provided within a slot 130 in slider joint 68 so as to allow driver 66 to be driven distally after wedge plate 100 has been allowed to retract proximally in a manner described in more detail hereinbelow. A spindle guard 132 is provided between latch retractor 128 and the surface of spindle 60 to prevent damage to the plastic surface of spindle 60 by the surface of latch retractor 128 .
[0131] Referring now to FIG. 13 , wedge plate 100 will be described in more detail. As noted above, wedge plate 100 is provided to maintain jaws 16 in a spaced apart condition during loading of a surgical clip 72 within jaws 16 . Additionally, the presence of wedge plate 100 provides stability to jaws 16 to prevent them from flexing during loading of surgical clip 72 . As shown, wedge plate 100 includes a distal tip 134 which is configured to engage and cam jaws 16 open and maintain them in a spaced condition. Additionally, wedge plate 100 includes a cam slot 136 which is configured to cooperate with cam link 104 mounted on spindle 60 to control the motions of wedge plate 100 as discussed in more detail below. Further, distal and proximal windows 138 and 140 , respectively, are provided to engage flexible structure on the filler component 102 . A biasing spring 142 is provided on a mount 144 to bias wedge plate 100 generally proximally within elongated tubular member 14 . Finally, a stop 146 is configured to engage corresponding structure on filler component 102 .
[0132] Referring now to FIGS. 14 and 15 , various aspects of filler component 102 will now be described. Filler component 102 includes a flexible leg 152 which is configured to engage distal and proximal windows 138 and 140 in wedge plate 100 . Filler component 102 also includes an elongated cam slot 148 configured to receive part of cam link 104 . A disengaging edge 150 is provided within cam slot 148 to facilitate disengaging cam link 104 from within cam slot 136 in wedge plate 100 . Filler component 102 additionally includes a recess 154 for engagement with stop 146 on wedge plate 100 ( FIG. 13 ), to limit the proximal retraction of wedge plate 100 , as well as a longitudinal recess 156 to accommodate the length of return spring 142 of wedge plate 100 .
[0133] FIGS. 16 and 17 illustrate the position of impact spring 56 relative to rotation knob 20 . As noted above, impact spring 56 is provided as an over pressure mechanism to prevent over compression of jaws 16 during the crimping of a surgical clip 72 as described in more detail below with respect to the operation of surgical clip applier 10 . The over pressure mechanism is designed to prevent overstroke of trigger 18 applied by the surgeon and ultimately prevent damage to jaws 16 .
[0134] Referring to FIGS. 18-20 , spindle 60 and related drive components are shown with elongated tubular member 14 removed. Specifically, with regard to FIG. 19 , pusher 108 of feed bar 82 extends through a slot 158 in nose 80 to engage a surgical clip 72 . Similarly, as shown in FIG. 20 , at a proximal end of spindle 60 , trip lever 96 extends through window 106 in feed bar 82 . In this position, trip lever 96 can engage an edge of slot 106 to drive feed bar 82 distally along with spindle 60 through elongated tubular member 14 .
[0135] Referring to FIG. 21 , there is a view similar to FIG. 19 , however, nose 80 has been removed to illustrate pusher 108 engaging a surgical clip 72 located in channel 70 .
[0136] Referring now to FIG. 22 , spindle 60 and associated components are shown with feed bar 82 removed.
[0137] Referring to FIG. 23 , there are illustrated multiple clips 72 positioned within channel 70 for supply to jaws 16 at a distal end of spindle 60 . Clips 72 are arranged in longitudinal alignment within channel 70 . Retention fingers 71 are provided at a distal end of channel 70 to restrain a stack of clips 72 within channel 70 until advanced into jaws 16 by feed bar 82 .
[0138] Referring to FIG. 24 , there is illustrated an intermediate section of spindle 60 assembled with follower 74 and follower spring 76 . As noted, spring 76 biases follower 74 distally relative to spindle 60 .
[0139] With reference to FIG. 25 , there is illustrated spindle 60 assembled with trip lever 96 and biasing spring 98 , with trip lever 96 being biased into a upward most position by biasing spring 98 .
[0140] Referring to FIGS. 26 and 27 , an opposed side of spindle 60 assembled with driver 66 about jaws 16 is illustrated. As noted above, driver 66 is configured to cam jaws 16 closed about a surgical clip. Thus, jaws 16 include angled camming surfaces 160 for receipt of corresponding camming surfaces 184 ( FIG. 34 ) of driver 66 . A pocket 187 ( FIG. 31 ) in the proximal end of jaws 16 limits the retraction of driver 66 . Specifically, protrusion 186 of slider joint 68 engages pocket 187 of jaws 16 . (See FIGS. 31 & 34 ).
[0141] Referring for the moment to FIG. 27A , camming surfaces 160 on jaws 16 and corresponding camming surfaces 184 of driver 66 are smoothly rounded, curved or radiused. By forming these camming surfaces in this manner, the friction between camming surfaces 160 and 184 is greatly reduced providing an improved smooth closure of jaws 16 about clip 72 .
[0142] Referring to FIGS. 28-30 , the relative assembled positions of channel 70 , trip lock 84 , wedge plate 100 and filler component 102 will now be described. Referring initially to FIGS. 29 and 30 , filler component 102 is positioned on channel 70 . Proximal end of filler component 102 abuts a stop 162 positioned on channel 70 . The.wedge plate 100 lies over filler component 102 in the manner shown. As best shown in FIG. 30 , filler component 102 includes a cam slot 148 having a disengaging edge 150 formed within cam slot 148 . Similarly, wedge plate 100 includes a cam slot 136 . As noted above, a cam link 104 is provided attached to spindle 60 (not shown) in order to drive wedge plate 100 distally. To facilitate driving wedge plate 100 , cam link 104 is provided with a cam link boss 164 which rides in cam slots 136 and 148 of wedge plate 100 and filler component 102 respectively. As cam link 104 is advanced distally relative to wedge plate 100 cam link boss 164 engages a driving edge 166 of wedge plate 100 to drive wedge plate 100 distally. In the manner described hereinafter, once cam link 104 , and in particular cam link boss 164 , engages disengaging edge 150 of filler component 102 cam link boss 164 is cammed out of engagement of driving edge 166 .
[0143] Referring to FIG. 30 , filler component 102 is provided with a flexible leg 152 which is movable between distal and proximal windows 138 , 140 , respectively, of wedge plate 100 . In order to cam flexible leg 152 out of one of the proximal or distal windows, there is provided a cam surface 168 on flexible leg 152 which cams flexible leg 152 out of the windows in response to relative movement of wedge plate 100 relative to filler component 102 .
[0144] As noted hereinabove, jaws 16 are provided to receive and crimp surgical clips 72 positioned therein. Referring to FIGS. 31 and 32 , jaws 16 generally include a pair of flexible legs 170 fixed to a base 172 . Jaw members 16 A and 16 B are located at a distal end of flexible legs 170 . A pair of locking arms 174 extend distally from base 172 and terminate in tabs 176 . Tabs 176 are configured to engage corresponding holes 177 on elongated tube 14 ( FIG. 10 ) to secure jaws 16 to elongated tube 14 . Jaws 16 include channel 22 for receipt of surgical clips 72 . As shown, filler component 102 is positioned directly behind jaws 16 and, as with jaws 16 , does not move longitudinally relative to outer tubular member 14 .
[0145] Referring for the moment to FIG. 32 , jaws 16 are configured to receive wedge plate 100 such that the distal tip 134 of wedge plate 100 is used to initially separate jaws section 16 a and 16 b and maintain them in a separated and aligned configuration during insertion of a surgical clip into jaws 16 . As noted, this prevents any torquing or flexing of jaw 16 a relative to jaw 16 b while a surgical clip 72 is being loaded therein. Each of flexible legs 170 includes a cam edge 178 (see FIGS. 44 & 63 ) to guide distal tip 134 of wedge plate 100 within jaws 16 .
[0146] Referring to FIG. 33 , wedge plate 100 is illustrated positioned on spindle 60 such that latch retractor 128 extends through a slot 182 in wedge plate 100 . As best shown in FIG. 34 , with wedge plate 100 removed, it can be seen that a distal end of driver 60 is provided with camming surfaces 184 . Camming surfaces 184 cooperate with cam surfaces 160 on jaws 16 , (see FIG. 27 ), to cam jaws 16 together in response to longitudinal movement of driver 60 relative to jaws 16 . Protrusion 186 on slider joint 68 extends through a slot 188 in wedge plate 100 to limit retraction of slider joint 68 relative to jaws 16 .
[0147] The operation of surgical clip applier 10 to crimp a surgical clip around a target tissue, such as, for example, a vessel, will now be described. With reference to FIGS. 35 and 36 , trigger 18 is in a generally uncompressed state with yoke 24 biased to a proximal-most position by return spring 32 . As best shown in FIGS. 37-42 , and with initial reference to FIG. 38 , in an unfired state, trip lever 96 carried by spindle 60 , biased upwardly by biasing spring 98 , is positioned adjacent to, and in contact with, a slot in feed bar 82 . Trip block 84 is in a distal position relative to trip lever 96 .
[0148] Referring to FIG. 39 , follower 74 is biased distally by a spring 76 such that clips 72 are biased in a distal direction.
[0149] Referring to FIG. 40 , spindle 60 and feed bar 82 are stationery with latch retractor 128 biased to an upward position.
[0150] Referring to FIG. 41 , flexible leg 152 of filler component 102 is in the distal window 138 of wedge plate 100 . Raised feature 118 on spindle 60 is proximal of flexible leg 152 .
[0151] As best shown in FIG. 42 , at the distal end of surgical clip applier 10 , when at rest in an unfired state, wedge plate 100 and feed bar 82 are in a proximal-most position relative to jaws 16 .
[0152] FIGS. 43-47 illustrate the initial at rest position of the wedge plate 100 , jaws 16 and filler component 102 .
[0153] Referring initially to FIGS. 43 and 44 , as shown, wedge plate 100 is in a proximal-most position relative to jaws 16 . As shown in FIG. 43 , flexible leg 152 is in distal window 138 of wedge plate 100 , while cam link 104 is in a proximal-most position relative to cam slot 136 in wedge plate 100 .
[0154] As best shown in FIGS. 45 and 46 , wedge plate 100 is in a proximal most position relative to jaws 16 with distal tip 134 proximal of cam edges 178 of jaws 16 .
[0155] Referring to FIG. 47 , wedge plate 100 is in a proximal-most position relative to filler component 102 , such that driving edge 166 of wedge plate 100 is proximal of disengaging edge 150 of filler component 102 .
[0156] Referring to FIG. 48 , to initiate actuation of clip applier 10 , trigger 18 is moved through an initial swing as shown by arrow A such that link 26 drives yoke 24 distally as shown by arrow B. As best shown in FIG. 49 , as yoke 24 is driven distally in the direction of arrow C, rack teeth 40 on rack 38 slide over pawl teeth 44 on pawl 42 . With reference for the moment to FIG. 50 , if the trigger 18 is released at this point, rack teeth 40 would restrain pawl teeth 44 against proximal motion, preventing release of trigger 18 and partial or inadvertent partial actuation of surgical clip applier 10 .
[0157] During the initial stroke, spindle 60 moves a predetermined distance. With regard to FIG. 51 , as spindle 60 is driven an initial distal distance, trip lever 96 engages elongated window 106 feed bar 82 and moves feed bar 82 distally a similar distance. As shown in FIGS. 42 & 51 , as feed bar 82 is driven distally and a clip 72 is driven into jaws 16 , follower 74 moves distally ( FIG. 52 ) due to the bias of spring 76 to urge the stack of surgical clips 72 distally.
[0158] Referring to FIGS. 53 and 54 , as spindle 60 and feed bar 82 move distally, spindle 60 drives cam link 104 distally an initial distance such that cam link boss 164 on cam link 104 engages wedge plate 100 . As shown, flexible leg 152 of filler component 102 is positioned in distal-most window 138 of wedge plate 100 .
[0159] As shown in FIG. 55 , as cam link 104 moves distally with spindle 60 , cam link boss 164 engages driving edge 166 on wedge plate 100 to urge wedge plate 100 distally relative to filler component 102 .
[0160] Referring to FIG. 56 , as feed bar 82 moves distally, pusher 108 at the distal end of feed bar 82 engages a clip 72 and begins to urge clip 72 into jaws 16 . Notably, at this point, spindle 60 has not yet contacted driver 66 , thereby preventing compression of jaws 16 prior to full insertion of surgical clip 72 .
[0161] Turning again to FIG. 55 , as surgical clip applier 10 is actuated through a further second predetermined distance, cam boss 164 on cam link 104 continues to drive wedge plate 100 distally and flexible leg 152 is cammed out of distal window 138 and into proximal window 140 by cam surface 168 to engage wedge plate 100 with filler component 102 . As shown in FIGS. 57 & 58 , at this point, feed bar 82 , wedge plate 100 , spindle 60 , clips 72 and follower 74 ( FIG. 52 ) are all moving in a distal-most direction.
[0162] Referring to FIG. 59 , feed bar 82 continues to urge pusher 108 at the distal end of feed bar 82 against a surgical clip 72 to urge clip 72 into channel 22 in jaws 16 . Surgical clips 72 contained in channel 70 are biased in a distal direction by follower 74 ( FIG. 52 ) and wedge plate 100 ( FIG. 54 ) continues to move distally while driver 66 remains stationery relative to elongated tubular member 14 .
[0163] Referring to FIG. 60 , as spindle 60 is moved further, cam boss 164 of cam link 104 is cammed out of engagement with driving edge 166 of wedge plate 100 by means of disengaging edge 150 formed in filler component 102 as best shown by the arrows in FIG. 60 . During this further stroke of a predetermined distance, flexible leg 152 of filler component 102 snaps into proximal window 140 of wedge plate 100 , thereby preventing retraction of wedge plate 100 from its distal-most position.
[0164] As shown in FIG. 61 , flexible leg 152 is positioned within proximal window 140 of wedge plate 100 , thereby restraining wedge plate 100 against retraction, while feed bar 82 and spindle 60 continue to move in a distal direction as shown by the arrows.
[0165] As shown in FIGS. 62-63 , distal tip 134 of wedge plate 100 urges jaw members 16 a and 16 b apart by engaging cam surfaces 178 in jaw members 16 a and 16 b . As noted above, by positioning wedge plate 100 in cam surfaces 178 of jaw members 16 a and 16 b , wedge plate 100 not only spreads the jaws 16 apart to properly receive surgical slip 72 , but additionally restrains each individual jaw member 16 a and 16 b from flexing with respect to each other, thereby preventing any torque of clip 72 as it is being inserted into jaws 16 .
[0166] Referring to FIG. 64 , as noted above, flexible leg 152 restrains wedge plate 100 from proximal retraction while cam link 104 continues to advance through slots 148 and 136 in filler component 102 ( FIG. 64 ) and wedge plate 100 .
[0167] As best shown in FIG. 65 , as spindle 60 continues to move distally through the stroke, trip lever 96 is urged distally with spindle 60 until trip lever 96 engages camming surface 110 (See FIG. 10D ) of trip block 84 . As camming surface 110 of trip block 84 is urged against trip lever 96 , trip lever 96 will be cammed out of engagement with elongated window 106 of feed bar 82 allowing feed bar 82 to return to a proximal position due to the bias of feed bar spring 88 (see FIG. 10 ).
[0168] Referring for the moment to FIG. 66 , as spindle 60 continues to move through its stroke, raised feature 118 on spindle 60 begins to cam flexible leg 152 out of proximal window 140 of wedge plate 100 , so that the wedge plate 100 will be able to retract prior to, and so that, surgical clip 72 is crimped between jaws 16 . This is best illustrated in FIG. 67 where feed bar 82 has fully inserted clip 72 within jaws 16 and wedge plate 100 has retracted to a proximal-most position.
[0169] FIG. 68 illustrates trip lever 96 being cammed out of engagement with feed bar 82 by camming surface 110 of trip block 84 and against the bias of biasing spring 98 such that feed bar 82 is disengaged from trip lever 96 and feed bar 82 can start to retract proximally. As shown, in FIG. 69 , pusher 108 of feed bar 82 is retracted to a proximal position behind the next distal most clip 72 as wedge plate 100 retracts leaving clip 72 inserted into jaws 16 .
[0170] Referring to FIG. 70 , trip lever 96 is completely cammed down by cam surface 110 on trip block 84 and spindle 60 continues to move distally through a further predetermined stroke.
[0171] Referring for the moment to FIG. 71 , as wedge plate 100 retracts proximally while spindle 60 continues to move distally, flexible leg 152 on filler component 102 snaps into distal window 138 of wedge plate 100 . As shown in FIG. 72 , wedge plate 100 is retracted to a proximal position relative to jaws 16 .
[0172] Referring to FIG. 73 , when latch retractor 128 is cammed downwardly relative to spindle 60 , spindle 60 has moved distally to a predetermined distance. The action of spindle 60 , now engaging driver 66 , pushes driver 66 distally. Driver 66 draws slider joint 68 and simultaneously slider joint 68 drags latch retractor 128 distally mechanically forcing cam surface no. of latch retractor 128 downward to underside of jaw pad 172 and engaging latch retractor 128 with slot 126 of spindle 60 .
[0173] Referring to FIGS. 74-75 , as trigger 18 is fully compressed to drive spindle 60 to a distal-most position, rack 38 clears pawl 42 so that the entire drive assembly can retract when the trigger is released. Notably, a full stroke of the spindle 60 is required to take a clip 72 from an initial position to a fully inserted position in the jaws 16 . As spindle 60 moves through its distal-most position, it moves driver 66 in the manner described hereinabove to crimp a surgical clip 72 . For example, referring to FIGS. 76-79 , driver 66 advances distally relative to camming surfaces 160 on jaws 16 a and 16 b , such that camming surfaces 184 on driver 66 cam jaws 16 a and 16 b closed thereby closing surgical clip 72 contained therebetween.
[0174] Referring for the moment to FIG. 80 , a security mechanism is provided to prevent an overstroke condition and thereby excessive compression of clip 72 from damaging tissue, jaws 16 or driver 66 . If trigger 18 is continued to be squeezed past a stroke required for a full forming of clip 72 impact spring 56 compresses within the space defined between knob 20 and bushing 48 thereby preventing any further distal movement of spindle 60 .
[0175] A fully formed clip formed about vessel V is illustrated in FIG. 81 .
[0176] Referring to FIG. 82 , as trigger 18 is released (not shown), pawl 42 rotates against the bias of pawl spring 46 such that pawl teeth 44 ride along rack teeth 40 to reset the handle assembly. As shown in FIG. 83 , when driver 66 retracts, latch retractor 128 is again biased up into its upper-most position, thereby, resetting the drive mechanism.
[0177] Referring to FIGS. 84-86 , as spindle 60 retracts, raised feature 118 of spindle 60 moves past flexible leg 152 in filler component 102 . It should be noted that wedge plate 100 does not move as it has already fully retracted. As spindle 60 retracts, it draws cam link 104 proximally within slots 136 and 148 of wedge plate 100 and filler component 102 to its initial position. As best seen in FIG. 86 , in this position, clip applier 10 is again in an initial position to be refired and thus to attach another clip to a vessel.
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An apparatus for application of surgical clips to body tissue includes a jaw assembly mounted adjacent a distal end portion of a body, the jaw assembly including first and second jaw portions movable between a spaced-apart and an approximated position; a yoke slidably supported at least partially in a handle portion and being connected to at least one trigger; a drive link slidably supported at least partially in the handle portion and the body, the drive link having a proximal end connected to the yoke; a spindle supported in the body and rotatably connected to the drive link; and a jaw closure member connected to a distal end of the spindle and being positioned adjacent the first and second jaw portions to move the jaw portions to the approximated position upon a squeezing of the at least one trigger which results in distal advancement of the jaw closure member.
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FIELD OF THE INVENTION
[0001] This invention generally relates to heat treatment, and more particularly to induction hardening.
BACKGROUND OF THE INVENTION
[0002] Induction hardening is a non-contact heat treatment process which utilizes the phenomena of inductive heating to harden all or a portion of a surface layer of a workpiece. During this process, the conductive workpiece is placed into a strong alternating magnetic current, thereby creating electrical currents on the surface of the workpiece. These electrical currents flow predominantly into the surface layer of the workpiece causing this layer to rapidly increase in temperature.
[0003] In the context of a steel workpiece, ideally the same is heated until the surface layer is at a temperature that is at or above the transformation range temperature. Thereafter, the workpiece is immediately quenched thereby forming a martensitic structure in the surface layer that is harder than the base material. Generally, the hardened surface layer functions as a protective “skin” for the workpiece, with reduced wear vulnerability. The aforementioned process is used in various applications, including tool tip hardening, pin and shaft hardening, blade edge hardening, etc.
[0004] There are generally two principal methods for induction edge hardening. The first is referred to as “single shot” hardening, wherein a workpiece is held statically in the alternating magnetic field so that the entire area that will be heat treated is heated simultaneously. The second method is referred to as “traverse” hardening, wherein the workpiece moves through the alternating magnetic field progressively, so that the area that will be heat treated is incrementally heated as it passes through the field.
[0005] In either case, both single shot and traverse edge hardening processes are known to produce substantial deformations in the workpiece. As a result, a post-hardening straightening operation is required to remove the dimensional anomalies that result from these deformations to ensure that the workpiece meets its required dimensional specifications.
[0006] Unfortunately, such a post-hardening straightening process is very undesirable. From a cost perspective, this additional process increases the cost of manufacturing per part. From a lead time perspective, this additional process increases the overall processing time from order to delivery. Furthermore, the depth of the surface layer that is hardened must be deep enough to accommodate subsequent material removal during straightening. As such, the heat treated surface layer is often times much deeper than necessary simply to ensure that a sufficient amount of the hardened surface layer will remain. To achieve this overshoot in hardened depth, higher frequency and power requirements are necessary during the induction edge hardening process to generate a sufficient amount of electrical current that will achieve the desired hardened surface layer depth.
[0007] Therefore, there is a need in the art for an edge hardening apparatus and method that will substantially reduce or entirely eliminate the need for any post-hardening straightening operations. The invention provides such an apparatus and method. These and other advantages of the invention, as well as additional inventive features, will be apparent from the description of the invention provided herein.
BRIEF SUMMARY OF THE INVENTION
[0008] In one aspect, embodiments of the present provide a method for traverse induction hardening. One embodiment of such a method may include aligning a pair of parts such that the parts are in a side-by-side relationship with one another along their entire length such that one part does not extend beyond the other part. The parts are aligned in a pair such that an interior surface of one of the pair of parts is in contact with an interior surface of the other one of the pair of parts. The method further includes loading the aligned pair of parts into a linear track and feeding the aligned pair of parts along a linear track along a feed direction. The method further includes passing the aligned pair of parts through a coil assembly, such that at least a portion of each part of the pair of parts is simultaneously subjected to induction heating. The method also includes simultaneously quenching each one of the pair of parts as they exit the coil assembly.
[0009] In certain embodiments, the method also includes aligning subsequent pairs of parts sequentially and in an abutted end-to-end relationship such that each one of the aligned subsequent pairs of parts is aligned in an identical manner to each other one of the aligned subsequent pairs of parts.
[0010] In certain embodiments, the step of loading includes sequentially loading each one of the pairs of parts into the linear track. The step of feeding includes sequentially and continuously feeding each one of the aligned pairs of parts along the feed direction. The step of passing includes sequentially and continuously passing each one of the aligned pairs of parts through the coil assembly. The step of simultaneously quenching includes simultaneously quenching each one of each pair of parts sequentially and continuously.
[0011] In certain embodiments, the step of loading includes positioning the aligned pair of parts into a channel of the linear track. The channel is defined between two upstanding guides in an opposed space relation. The step of feeding the aligned pair of parts includes gripping the aligned pair of parts between at least one pair of rollers arranged adjacent to the track. The step of feeding may also include gripping the aligned pair of parts between the at least one pair of rollers such that the inter surface of one part is held tightly against the interior surface of the other part. The step of feeding may also include gripping the aligned pair of parts successively by a plurality of pairs of rollers arranged sequentially adjacent to the track. The step of feeding may also include gripping the aligned pair of parts before it enters the coil assembly, and after the aligned pair of parts exits the coil assembly.
[0012] In certain embodiments, the step of passing the aligned pair of parts through a coil assembly includes passing an uppermost edge of each one of the pair of parts through the coil assembly simultaneously to edge harden each one of the pair of parts.
[0013] The step of quenching may include passing the aligned pair of parts under a quench head which directs a shower of coolant towards the aligned pair of parts. The step of quenching may also include separating the aligned pair of parts such that their respective interior surfaces are no longer in contact as the aligned pair of parts pass under the quench head. In certain embodiments, the method may also include a step of passing the aligned pair of parts down a chute and into a quench bath after passing the pair of parts under the quench head. In another aspect, embodiments of the present invention provide a method for traverse induction hardening. An embodiment of a method according to this aspect includes the steps of sequentially aligning pairs of parts such that for each pair of parts, an interior surface of one part is in contact with an interior surface of the other part. The method also includes sequentially loading each pair of aligned parts into a track such that each one of the aligned pairs of parts are arranged in an abutted end-to-end relationship along the track to form a linear row of aligned pairs of parts. The method also includes continuously feeding the linear row of aligned pairs of parts through a coil assembly such that each pair of parts is sequentially subjected to induction heating. The method also includes separating the two parts of each pair of parts as they exit the coil assembly such that the interior surface of one part of the pair of parts is no longer in contact with the other part of the pair of parts. The method also includes quenching each separated pair of parts in a quenching station positioned adjacent the track such that coolant flows on the interior surface of both parts of the separated pair of parts, as well as an exterior opposed surface of both parts of the pair of parts.
[0014] In certain embodiments, the step of sequentially aligning includes aligning each pair of parts such that for each pair, the parts are in a side-by-side relationship and with one another along their entire length.
[0015] In certain embodiments, the step of sequentially loading includes loading the pairs of parts into a channel of the track defined between two upright opposed guides which extend generally perpendicular to a base surface.
[0016] In certain embodiments, the step of continuously feeding includes feeding the linear row of pairs of parts through a plurality of sequentially arranged rollers which are arranged in spaced-apart pairs.
[0017] In yet another aspect, embodiments of the present invention provide an induction hardening apparatus. The apparatus according to this aspect includes a track including a base surface and a pair of opposed guides extending upwardly from the base surface to define a channel. A coil assembly for edge hardening parts via induction heating is also provided. The coil assembly is positioned adjacent and above the track. The coil assembly is spaced from the track such that a portion of each one of a pair of side-by-side parts may simultaneously pass through the coil assembly. The apparatus also includes a feed arrangement configured for feeding a linear row of pairs of side-by-side parts along the track in a feed direction through the coil assembly. The apparatus also includes a quenching station downstream from the coil assembly relative to the feed direction. The quenching station is positioned adjacent to and above the track and operable to quench the linear row of pairs of side-by-side parts as they sequentially exit the coil assembly.
[0018] In certain embodiments, the opposed guides are spaced apart a first distance upstream of the coil assembly and spaced apart a second distance downstream of the coil assembly. The second distance is greater than the first distance. The feed arrangement may also include a plurality of rollers arranged sequentially in pairs such that the track is interposed between the rollers of each pair of rollers. The spacing of the quenching station from an exit of the coil assembly may be adjustable to govern a delay of time from part heat-up to part quenching at the quenching station.
[0019] Other aspects, objectives and advantages of the invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] The accompanying drawings incorporated in and forming a part of the specification illustrate several aspects of the present invention and, together with the description, serve to explain the principles of the invention. In the drawings:
[0021] FIG. 1 is a side view of one embodiment of an induction hardening apparatus according to the teachings of the present invention;
[0022] FIG. 2 is a partial perspective view of a track of the induction hardening apparatus of FIG. 1 ;
[0023] FIG. 3 is a side perspective view of a coil assembly of the induction hardening apparatus of FIG. 1 ;
[0024] FIG. 4 is a partial perspective view of the coil assembly of FIG. 3 ;
[0025] FIG. 5 is a partial front cross section of parts exiting the coil assembly of FIG. 3 ; and
[0026] FIG. 6 is a partial perspective view of a quenching station of the induction hardening apparatus of FIG. 1 .
[0027] While the invention will be described in connection with certain preferred embodiments, there is no intent to limit it to those embodiments. On the contrary, the intent is to cover all alternatives, modifications and equivalents as included within the spirit and scope of the invention as defined by the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
[0028] Turning now to FIG. 1 , an exemplary embodiment of an induction hardening apparatus 20 is illustrated. As will be explained in greater detail below, induction hardening apparatus 20 advantageously reduces or entirely eliminates the additional straightening step otherwise required by conventional transverse induction hardening apparatuses. Indeed, induction hardening apparatus 20 is operable to edge harden parts 22 such that under typical dimensional specifications, no additional straightening step is required. Put differently, induction hardening apparatus 20 substantially reduces or entirely eliminates part deformations otherwise present after conventional induction edge hardening.
[0029] Induction hardening apparatus 20 feeds parts 22 along feed direction 24 such that they pass through a coil assembly 26 . While passing through coil assembly 26 parts 22 are edge hardened under the phenomena of induction edge hardening. Parts 22 are arranged in a side-by-side relationship such that two parts 22 simultaneously pass through coil assembly 26 . Further, pairs of parts 22 are arranged end-to-end as illustrated so that any given side-by-side pair of parts 22 begin and end the edge hardening process at the same time. Put differently, parts 22 are arranged in identical pairs consisting of two side-by-side parts, with successive pairs arranged in an end-to-end relationship such that a leading edge of each one of a pair of parts 22 enters coil assembly 26 at the same time, while a trailing edge of each of the parts 22 leaves coil assembly 26 at the same time.
[0030] To facilitate such an arrangement, induction hardening apparatus 20 includes a track 34 for feeding pairs of parts 22 along feed direction 24 . Track 34 includes a pair of opposed guides 36 which support parts 22 in a generally upright position. Track 34 is supported by a base stand 38 . A feed arrangement in the form of a plurality of feed rollers 46 are disposed on either side of coil assembly 26 and are operable to feed the aforementioned pairs of parts 22 through coil assembly 26 . Once through coil assembly 26 , feed rollers 46 are also operable to feed pairs of parts 22 along feed direction 24 such that parts 22 pass underneath a quench station 40 which exposes the heated parts 22 to a coolant quench. After passing through quench station 40 , parts 22 fall along a chute 42 and into a quench bath 44 .
[0031] Induction hardening apparatus 20 is illustrated as schematically connected to a power supply 48 for providing the required electrical power for coil assembly 26 , rollers 46 , and other various sensors of induction hardening apparatus 20 . It will be recognized that the particular characteristics of power supply 48 will vary depending upon application, however one exemplary embodiment of a power supply 48 can be an incoming electrical supply of 480 volt three phase electric power at 60 Hz.
[0032] Induction hardening apparatus 20 is also illustrated as schematically connected to a coolant supply 50 . Coolant supply 50 is operable to provide the quenching coolant to quench station 40 , as well as replenish quench bath 44 as needed. Coolant supply 50 includes means for circulating coolant throughout induction hardening apparatus 20 . The coolant utilized may be organic or inorganic, and/or oil or water based.
[0033] Turning now to FIG. 2 , a perspective view of track 34 is illustrated. As illustrated, guides 36 depend upwardly from a base surface 50 of track 34 and are generally perpendicular relative thereto. Guides 36 are arranged in an opposed space relationship such that a channel 52 is formed therebetween. Feed rollers 46 are disposed adjacent guides 36 and function in two respects.
[0034] First, feed rollers 46 feed adjacent parts 22 along feed direction 24 (See FIG. 1 ) so that the parts 22 simultaneously pass through coil assembly 26 at an exemplary rate of about 30 ft./min. to about 60 ft./min. Second, feed rollers 46 maintain tight contact between adjacent ones of a pair of parts 22 so that good surface contact is maintained on the interior sides of each part 22 of the pair of parts 22 . As illustrated, feed rollers 46 are disposed on either side of parts 22 . Feed rollers 46 may be identical to one another, or alternatively, the feed rollers 46 on one side of the pair of parts 22 may be of a greater or lesser hardness than the feed rollers 46 on the other side of the pair of parts 22 . Further, belts, conveyors, etc. may be used in place of or in addition to feed rollers 46 to feed the linear row of pairs of parts 22 along feed direction 24 . Yet further, feed rollers 46 on one side of coil assembly 26 may be the same as, or a different size than feed rollers 46 on the other side of coil assembly 26 . For example, feed rollers 46 upstream from coil assembly 26 may have a smaller diameter than feed rollers 46 downstream from coil assembly 26 .
[0035] Turning now to FIG. 3 , quench station 40 is disposed a predetermined distance W from the exit of coil assembly 26 . The predetermined distance W may be varied to allow for greater or lesser “soak” times, i.e. the amount of time that the parts remain at an elevated temperature prior to rapid cooling at quench station 40 . Furthermore, the size of channel 52 increases to a distance D as illustrated adjacent quench station 40 to allow for a finished pair of parts 22 to separate so that coolant from quench station 40 will pass on both the exterior and interior sides of each part 22 of the pair of parts 22 . Such an arrangement insures that each one of the pair of parts 22 is properly quenched and the desired hardness is achieved on all intended surfaces.
[0036] Turning now to FIG. 4 , as stated above, each one of a pair of parts 22 enter coil assembly 26 at the same time. Parts 22 are fed by feed rollers 46 through a coil 54 of coil assembly 26 . As illustrated, only a portion of parts 22 are exposed to coil 54 such that only a portion of the overall height of each upright part 22 is rapidly elevated in temperature by way of induction heating. In an exemplary embodiment, the temperature of parts 22 is elevated from ambient to about 1700° F. Those skilled in the art will recognize that this configuration is an edge hardening application.
[0037] Turning now to FIG. 5 , the portions of each part 22 which are elevated in temperature are generally shown at regions 56 . It will be recognized that regions 56 are simply a schematic representation that generally illustrate the heated area of each part 22 under typical specifications and operation, parts 22 are hardened to an exemplary case depth of about 0.100″ to about 0.125″, and about 45 minimum RL. As indicated previously, and illustrated throughout the various figures herein, parts 22 are held tightly together in a side-by-side relationship as illustrated in FIG. 5 . This side-by-side relationship allows for each part 22 to support the other part 22 such that deformations along the thickness of parts 22 are substantially reduced or entirely eliminated. Furthermore, because each pair of parts 22 is positioned end-to-end along track 34 (See FIG. 1 ), the energy imparted to each part 22 as it passes through coil assembly 26 may propagate to the other parts 22 in sequential contact with the pair of parts 22 currently positioned in coil assembly 26 . This alternative path of energy dissipation allows for a substantial reduction if not an elimination of part 22 deformation.
[0038] Turning now to FIG. 6 , quench station 40 is shown in greater detail. As indicated above, guides 36 in the region of quench station 40 are spaced apart at a distance D which is generally greater than the spacing of guides 36 prior to encountering quench station 40 . This allows parts 22 to separate as they pass under quench station 40 to insure that coolant passes over the interior and exterior sides of each part 22 . Such a result may be achieved by angling guides 36 in the region of quench station 40 as illustrated, or simply providing a separate set of guides 36 which are spaced apart at distance D. Further, a dividing feature 60 may be provided within channel 52 to aid in separating each pair of parts 22 as they pass under quench station 40 .
[0039] Having described the structural attributes of edge hardening apparatus 20 , a description will now be provided of the methods of operating the same. Referring back to FIG. 1 , a pair of similar parts 22 are arranged such that their leading and trailing edges are adjacent one another. The pair of parts 22 are then positioned approximate the left most roller 46 in FIG. 1 . Thereafter, other pairs of parts 22 are sequentially arranged behind the leading pair of parts 22 . The induction hardening apparatus 20 is then powered on allowing feed rollers 46 to pull the first pair of parts 22 along feed direction 24 . Simultaneously as this occurs, an operator continues to feed pairs of parts 22 into track 34 at the left most end thereof by pushing the pair of parts into contact with the sequentially arranged pairs of parts 22 positioned on track 34 . This pushing by the operator insures that each of the pairs of parts 22 maintain an end-to-end contact with one another as they pass through coil assembly 26 .
[0040] Each pair of parts 22 then sequentially passes through coil assembly 26 and is heated to a desired heat treating temperature. Upon exiting coil assembly 26 each pair of parts 22 is then exposed to a soak process, i.e. where the pairs of parts 22 continue to travel along feed direction 24 in the ambient air after exiting coil assembly 26 . These pairs of parts 22 are at an elevated temperature until they reach quench station 40 and are quenched. As the parts enter quench station 40 , the parts are allowed to break the surface contact previously maintained between the interior surfaces of each of the pair of parts 22 to allow coolant to flow over the exterior and interior surfaces of each part 22 . After passing through the quench station 40 , the parts 22 travel along chute 42 and are introduced to a quench bath 44 . After resting in the quench bath 44 , parts 22 may be removed and are ready for storage and/or shipment.
[0041] As described herein, the induction hardening apparatus 20 advantageously provides a system and method which substantially reduces or eliminates entirely the need to conduct a post-hardening straightening operation which is otherwise required by conventional induction hardening apparatuses. It has been observed that by the elimination of the aforementioned step part output per day has increased from a typical 2,000 parts per day to 6,000 parts per day. As will be readily appreciated, such a tripling of part output has led to significant reduction in part lead time. Further, the cost of manufacture of each part is substantially reduced given the elimination of the aforementioned post-hardening straightening step.
[0042] All references, including publications, patent applications, and patents cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
[0043] The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) is to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
[0044] Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.
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An induction hardening apparatus and methods are provided. The induction hardening apparatus includes a feed line having first and second ends. A coil assembly is positioned between the first and second ends. The feed line includes a support arrangement for supporting two workpieces against one another and transferring the workpieces simultaneously through the coil assembly along a feed axis defined by the feed line.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation application based upon and claims the benefit of the prior PCT International Patent Application No. PCT/JP2004/015058 filed on Oct. 13, 2004, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a combined valve for controlling the flow of fluid, integrally including a manual valve to be operated as a safety device and a pilot valve.
BACKGROUND ART
[0004] 2. Description of Related Art
[0005] In conventional facilities having piping for flowing various kinds of gasses or the like, typically in a semiconductor manufacturing process, a safety device is required to prevent gas leakage resulting from malfunction of a pilot valve during various works needing demounting of the piping. As such conventional technique, Japanese unexamined patent application publication No. 11(1999)-51226 is explained below with reference to FIG. 14 .
[0006] FIG. 14 shows a structure of a process gas unit 200 in a first prior art to be used in a semiconductor manufacturing process. The process gas unit 200 includes a manual valve 201 , input air-operated valve 205 , mass flow controller 208 , output air-operated valve 210 , manual valve 211 , and others, which are connected in series. In this unit, process gas flows in along a left arrow GI and out along a right arrow GO toward a vacuum chamber or the like (not shown).
[0007] During normal use, the manual valves 201 and 211 are held in a valve opening position, and the input air-operated valve 205 and the output air-operated valve 210 are operated by remote control to open and close for supply and stop of the process gas.
[0008] During repair or maintenance of the process gas unit 200 by for example demounting of the mass flow controller 208 , the manual valves 201 and 211 are held in a valve closed state to stop gas supply regardless of the open/closed state of the air-operated valves 205 and 210 . Accordingly, gas supply can be started/stopped as needed while the manual valves 201 and 211 are open, whereas gas supply can surely be stopped while the manual valves 201 and 211 are closed.
[0009] In case of emergency, even in supplying gas, gas supply can be stopped when the manual valves 201 and 211 are switched from the opening position to the closing position. In this piping arrangement that the manual valves and the air-operated valves are connected in series, the manual valves 201 and 211 serve as a safety device.
[0010] For the semiconductor manufacturing line, the reduction in size and cost of devices has always been further demanded. Hence, it is conceivable that a manual valve and an air-operated valve are integrally arranged in one unit, forming a combined valve, as a measure of saving space of a process gas unit. Such combined valve is disclosed in for example Japanese unexamined patent application publication No. 2003-130249 relating to an air-operated valve combined with a manual operating lever valve into one unit. As one example of the air-operated valve with operating lever valve, a second prior art disclosed in the publication '249 is explained below.
[0011] FIG. 15 shows the air-operated valve with operating lever valve in the second prior art. This valve is arranged to control the flow of fluid by driving a valve element by means of a driving device provided in a valve casing and to inhibit the flow of fluid with the operating lever attached to the valve casing regardless of operation of the driving device.
[0012] The structure shown in FIG. 15 is described below. A main operation valve 101 includes a valve casing 103 provided therein with a flow passage 102 formed between an inlet and an outlet for process liquid. A valve seat 104 is formed near the center of the flow passage 102 . A valve element 105 is connected to an end of a valve rod 106 . The valve casing 103 is also provided with a holding part 107 in which the valve rod 106 is held movably toward and away from the valve seat 104 . This holding part 107 contains a piston 108 that is connected to the other end of the valve rod 106 and slidable within the holding part 107 . The piston 108 is normally urged by a compression coil spring 109 to bring the valve element 105 into contact with the valve seat 104 . When an electromagnetic valve not shown is activated, the piston 108 is caused to slide in a cylinder 116 by air pressure supplied through a through hole 115 against the urging force of the coil spring 109 . A pin-shaped pressing member 110 is urged by an extension spring not shown in an opposite direction to the piston 108 . The pressing member 110 has a round base end 110 a. An operating lever 111 is disposed in contact with the base end 110 a of the pressing member 110 . This lever 111 is provided with a handle 113 at one end and a contact end 114 abutting against the base end 110 a at the other end with respect to an eccentric shaft 112 .
[0013] When the handle 113 of the operating lever 111 is rotated up (in a direction indicated by an arrow A in FIG. 15 ), the contact end 114 is rotated about the eccentric shaft 112 , pushing the pressing member 110 toward the piston 108 to bring the valve element 105 into contact with the valve seat 104 . In other words, the operating lever 111 may be switched between a first position for forcibly bringing the valve element 105 into contact with the valve seat 104 and a second position for bringing the valve element 105 out of contact with the valve seat 104 . As above, the valve element 105 is driven by the holding part 107 provided in the valve casing 103 to control the flow of process liquid and the pressing member 110 and the operating lever 111 provided in the valve casing 103 are operated to forcibly inhibit the flow of fluid regardless of the operating condition of the holding part 107 .
[0014] The above conventional techniques involve the following problems.
[0015] (1) In the first prior art, according to the piping arrangement in FIG. 14 , the manual valves 201 and 211 function as a safety device. However, two types of valves, namely, the air-operated valves 205 and 210 and the manual valves 201 and 211 are needed, so that space for mounting the valves could not be saved.
[0016] (2) The second prior art has the following disadvantages.
[0017] As the action of toggle, it is possible to readily control the flow condition of process liquid by a toggle from the outside of the device. In the second prior art shown in FIG. 15 , the operating lever 111 is adopted as the toggle and the air-operated valve with the operating lever valve is arranged.
[0018] This arrangement may achieve an integral unit of the operating lever valve and the air-operated valve; however, this unit only could be closed manually and has no function to fixedly hold the operating lever 111 at a predetermined position. Thus, the valve closed state could not be ensured and it has no function as the safety device.
[0019] In other words, the second prior art is merely arranged to manually perform temporal valve-closing. In case the piping is demounted for maintenance or the like, therefore, liquid may leak out due to malfunction of the air-operated valve.
[0020] In the above publication '249, it is disclosed that “this can combine two functions of a conventional toggle valve ( 13 ) and a safety valve ( 17 ), thus achieving a main operation valve ( 21 ) with reduced space for mounting”. However, this device has no function to reliably maintain the valve closed state and does not function as an original safety valve.
[0021] (3) In case of a chemical liquid valve, chemical liquid to be used in the semiconductor manufacturing process is allowed to flow through the valve. Accordingly, a valve element has to be made of fluorocarbon resin having resistance to corrosion. The fluorocarbon resin is likely to creep. A long-term normal use as a pilot valve may therefore lead to plastic deformation of the valve seat, which shrinks in a loading direction.
[0022] As such plastic deformation progresses, a sealing strength between the valve element and the valve seat will be decreased, causing leakage.
[0023] (4) There is no mechanism to fixedly hold the operating lever 111 at the predetermined valve-opening position. Thus, the valve closed state could not be ensured and there is no function to maintain normal use as the pilot valve. Specifically, the second prior art is merely arranged to manually perform valve-opening. For example, when the piston 108 makes contact with a stopper (not shown) restricting a piston stroke, vibration is transmitted to the operating lever 111 , which may shift to the valve-closing position. Consequently, the pilot valve is closed irrespective of the intension of an operator, thus stopping the flow of liquid.
[0024] (5) Further, when the operating lever 111 is to be operated to forcibly bring the valve element 105 into contact with the valve seat 104 if the cylinder 116 is supplied with air through the through hole 115 , a larger force than the air pressure on the piston 108 in the cylinder 116 is required to operate the operating lever 111 .
SUMMARY OF THE INVENTION
[0025] The present invention has been made to solve the above problems and has a purpose to provide a combined valve integrally including a manual valve to be operated as a safety mechanism and a pilot valve.
[0026] To be more concrete, to solve the above problems (1) to (3) of the prior arts mentioned above, an object of the present invention is to provide a combined valve which may be used as a chemical liquid valve arranged such that a pilot valve is allowed to open/close only when a manual valve operating as a safety mechanism is in a release position, the manual valve is switched to a valve closing position to shut off the flow of fluid even where the pilot valve is open, and the manual valve can be held in such position.
[0027] To solve the above problem (4), another object of the present invention is to provide a combined valve allowing continuous normal use as a pilot valve by a mechanism for holding a manual valve in a valve opening position.
[0028] To solve the above problem (5), further, another object of the present invention is to provide a combined valve including a manual valve easy for an operator to operate without applying large force.
[0029] To achieve the above purpose, there is provided a combined valve comprising: a valve mechanism including a diaphragm valve element and a valve seat with which the diaphragm valve element is brought into and out of contact to control a flow of fluid; a pilot mechanism including an urging device that presses the diaphragm valve element against the valve seat, the pilot mechanism being operated to bring the diaphragm valve element out of contact with the valve seat by air pressure; and a manual mechanism arranged to act on operations of the pilot mechanism; wherein when the manual mechanism is operated to interrupt a supply passage of air to the pilot valve, the diaphragm valve element is axially moved from a valve open position to a valve closed position by means of the urging device, and the combined valve further comprises a manual-mechanism holding device for holding the manual mechanism in a predetermined position to hold the diaphragm valve element in the valve closed position.
[0030] Accordingly, even in case of emergency where the valve operating mechanism has to be switched from a valve open state allowing air supply to a pilot mechanism to a valve closed state, an operator may react appropriately with the manual operating mechanism.
[0031] Further, irrespective of air supply to the pilot mechanism, the valve operating mechanism is switched to the valve closed state by the manual operating mechanism. Even in the case where the air supply to the pilot mechanism is erroneously caused during maintenance, for example, the valve operating mechanism will not be switched to the valve open state. Accordingly, the operator may perform the maintenance work safely.
[0032] According to another aspect of the present invention, there is provided a combined valve comprising: a valve mechanism including a diaphragm valve element and a valve seat with which the diaphragm valve element is brought into and out of contact to control a flow of fluid; a pilot mechanism including and an urging device that presses the diaphragm valve element against the valve seat, the pilot mechanism being operated to bring the diaphragm valve element out of contact with the valve seat by air pressure; and a manual mechanism arranged to act on operations of the pilot mechanism; wherein the manual mechanism is operated to axially move the diaphragm valve element from a valve open position to a valve closed position, and the manual mechanism is directly provided with a first manual-mechanism holding device for holding the diaphragm valve element in the valve closed position.
[0033] According to the present invention, as described above, valve mounting space can be saved and further the pilot valve is allowed to open/close only when the manual valve is in a release state. Even where the pilot valve is in the open state, the flow of fluid can be stopped by switching the manual valve to a valve-closing position and the manual valve can be held in such position. Thus the manual valve has a function as a safety device and also can function as a safety valve.
BRIEF DESCRIPTION OF DRAWINGS
[0034] FIG. 1 is a sectional view of a combined valve held in a valve closed state by a manual operating mechanism in a first preferred embodiment;
[0035] FIG. 2 is a sectional view of the combined valve in a valve closed state;
[0036] FIG. 3 is a sectional view of the combined valve in the valve open state;
[0037] FIG. 4 is a partial view of the combined valve held in the valve closed state by the manual operating mechanism locked with a padlock;
[0038] FIG. 5 is a sectional view of the combined valve used as a chemical liquid valve, showing a state of a valve seat plastic-deformed;
[0039] FIG. 6 is a sectional view of the combined valve operated to cause a diaphragm valve element to follow the valve seat plastic-deformed shown in FIG. 5 ;
[0040] FIG. 7 is a sectional view of a combined valve held in a valve closed state by a manual operating mechanism in a second preferred embodiment;
[0041] FIG. 8 is a sectional view of the combined valve in the valve closed state in the second embodiment;
[0042] FIG. 9 is a sectional view of the combined valve in a valve open state in the second embodiment;
[0043] FIG. 10 is a view of the combined valve in the second embodiment, in which the manual operating mechanism is rotated until a knob comes into contact with an adjusting rod at a curvature-changing point of the outer periphery of the knob to change the combined valve from the valve open state to the valve closed state by the manual operating mechanism,;
[0044] FIG. 11 is a sectional view of a combined valve held in a valve closed state by a manual operating mechanism in a third preferred embodiment;
[0045] FIG. 12 is a sectional view of the combined valve in the valve closed state in the third embodiment;
[0046] FIG. 13 is a sectional view of the combined valve in the valve open state in the third embodiment;
[0047] FIG. 14 is a view showing a structure of a process gas unit in a prior art;
[0048] FIG. 15 is a view showing an air-operated valve with an operating lever valve in the prior art;
[0049] FIG. 16 is a sectional view of a combined valve held in a valve closed state by a manual operating mechanism in a fourth preferred embodiment;
[0050] FIG. 17 is a sectional view of the combined valve in the valve closed state in the fourth embodiment;
[0051] FIG. 18 is a sectional view of the combined valve in a valve open state in the fourth embodiment;
[0052] FIG. 19 is a view showing the position of a keyhole in a bracket and rotational play of a handle of the knob;
[0053] FIG. 20 is a view showing a positional relation between the knob and the bracket;
[0054] FIG. 21 is a sectional view of a combined valve in a valve open state in a fifth preferred embodiment;
[0055] FIG. 22 is a top view of the combined valve in the fifth embodiment;
[0056] FIG. 23 is an external view of an upper part of the combined valve in the fifth embodiment;
[0057] FIG. 24 is a sectional view of a rod taken along a line A-A;
[0058] FIG. 25 is a sectional view of the combined valve in a valve closed state in the fifth embodiment;
[0059] FIG. 26 is a view of a packing in the fifth embodiment;
[0060] FIG. 27 is an external view of the knob part;
[0061] FIG. 28 is a view showing the relation between the knob, rod, and pin;
[0062] FIG. 29 is a general view showing a technique to automatically slide by use of a return spring;
[0063] FIG. 30 is a general view showing another technique to automatically slide by use of a return spring;
[0064] FIG. 31 is a view showing another form of locking; and
[0065] FIG. 32 is a view showing the shape of an end of a rod opposite to an end having the knob.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0066] A detailed description of preferred embodiments of a combined valve embodying the present invention will now be given referring to FIGS. 1 to 13 and 16 to 32 .
First Embodiment
[0067] A combined valve 1 in a first embodiment will be described with reference to FIGS. 1 to 6 .
[0068] FIGS. 1 to 3 are sectional views of the combined valve 1 in the first embodiment of the present invention. As shown in FIG. 3 , a body section of the combined valve 1 integrally includes a valve body 11 , cylinder 12 , and cover 13 . The combined valve 1 is structured of a pilot valve, a manual valve, and a valve-seat following mechanism. As for the combined valve 1 , “Upper” indicates a manual valve side and “Lower” indicates a pilot valve side.
[0069] Firstly, the pilot valve of the combined valve 1 is explained. The pilot valve is further divided into a pilot mechanism and a valve operating mechanism. Here, the pilot mechanism includes the cylinder 12 , the cover 13 , a piston rod 21 , a spring 22 , and a spring 52 . These cylinder 12 and cover 13 constitute an airtight container, in which the piston rod 21 is slidably mounted. This piston rod 21 partitions the space defined by the cylinder 12 and the cover 13 into two chambers, upper and lower. The lower chamber is a pressure chamber 23 . This pressure chamber 23 is communicated with an operation port 24 . On the piston rod 21 , the springs 22 and 52 which urge the piston rod 21 downwards are mounted.
[0070] The valve operating mechanism includes the valve body 11 , a valve seat 31 , a diaphragm valve element 32 , and ports 33 and 34 . In the valve body 11 , the ports 33 and 34 are communicated with each other through the valve seat 31 and a communicating area 35 . The diaphragm valve element 32 which will be brought into/out of contact with the valve seat 31 is partially sandwiched between the valve body 11 and the cylinder 12 . Accordingly, the valve body 11 and the cylinder 12 are airtightly partitioned by the diaphragm valve element 32 , preventing the fluid flowing in the communicating area 35 from leaking out to the cylinder 12 side. Slidably mounted in the cylinder 12 is the piston rod 21 coupled to the diaphragm valve element 32 . The diaphragm valve element 32 is arranged to come apart from the valve seat 31 when the piston rod 21 is not urged downwards, but come into contact with the valve seat 31 when the diaphragm valve element 32 is pressed downwards by the piston rod 21 .
[0071] The manual valve of the combined valve 1 is explained below. The manual valve includes a rod 51 , a spring 52 , and a knob 53 . Above the rod 51 , the knob 53 is attached to be rotatable about an eccentric shaft 54 . The knob 53 is provided with a handle 55 and a keyhole 56 .
[0072] The valve-seat following mechanism is described below. The valve-seat following mechanism includes a feed screw 71 formed with external threads, a holder 72 formed with internal threads which engage with the external threads of the feed screw 71 , an adjusting knob 73 , a setscrew 74 , and a lock nut 75 . The feed screw 71 is located in rotatable engagement with the holder 72 of the cover 13 . A rotation-locking pin 20 is provided between the feed screw 71 and the piston rod 21 . The lock nut 75 is placed on the holder 72 . The adjusting knob 73 and the setscrew 74 are arranged on the outer periphery of the holder 72 .
[0073] The combined valve 1 having the above structure is operated as follows.
[0074] A normal operation of the pilot valve will be described first. FIG. 3 shows the combined valve 1 with the manual valve held in a valve opening position and the pilot valve opened to allow the flow of fluid. FIG. 2 shows the combined valve 1 with the manual valve held in the valve opening position but the pilot valve closed to prevent the flow of fluid.
[0075] FIG. 3 is first explained. FIG. 3 shows the combined valve 1 with the pilot valve opened by supply of air pressure thereto by an electromagnetic valve not shown. Specifically, when air is supplied to the pressure chamber 23 through the operation port 24 , the air pressure in the pressure chamber 23 is increased. Under upward pressure, the piston rod 21 slides upwards in the cylinder 12 against the downward urging force of the springs 22 and 52 . In association with the upward sliding of the piston rod 21 , the diaphragm valve element 32 , which is not urged downwards, comes apart from the valve seat 31 . Accordingly, a passage space is generated between the valve seat 31 and the diaphragm valve element 32 , providing communication between the ports 33 and 34 through the communicating area 35 . The fluid supplied through the port 33 is thus allowed to flow out through the port 34 .
[0076] Next, FIG. 2 shows the combined valve 1 with the pilot valve brought into a closed state. Specifically, when air supply into the pressure chamber through the operation port 24 is stopped and the air pressure forcing the piston rod 21 upwards in the pressure chamber 23 is reduced, the piston rod 21 is pushed down by the urging force of the springs 22 and 52 mounted on the piton rod 21 . Accordingly, the piston rod 21 is urged downwards, bringing the diaphragm valve element 32 into contact with the valve seat 31 , thus closing the flow passage space between the valve seat 31 and the diaphragm valve element 32 . This interrupts the communication between the port 33 , the communicating area 35 , and the port 34 and thus the fluid supplied through the port 33 is not allowed to flow out through the port 34 .
[0077] When the manual valve is located in the valve opening position, opening/closing operation of the pilot valve can be performed by the electromagnetic valve.
[0078] An operation of the manual valve when used by an operator for example as a safety mechanism during maintenance or the like is explained referring to FIG. 1 . FIG. 1 shows the combined valve 1 with the manual valve in the valve closing position, which is switched from the valve opening position shown in FIG. 2 or 3 .
[0079] Firstly, explanation is made on the manual valve switched from the valve opening position shown in FIG. 3 to the valve closing position.
[0080] To be concrete, the operator rotates the handle 55 of the knob 53 , 180 degrees counterclockwise in front view, about the eccentric shaft 54 from the valve opening position (hereinafter, referred to as a safety mechanism release position R) to a position (hereinafter, referred to as a safety mechanism set position S). Then, the rod 51 comes into contact with the piston rod 21 which also receives the downward urging force of the springs 22 and 52 . The piston rod 21 is therefore urged downwards, bringing the diaphragm valve element 32 integral with the piston rod 21 into contact with the valve seat 31 . As a result, the fluid flowing in the port 33 is prevented from passing through the communicating area 35 closed by the diaphragm valve element 32 and flowing toward the port 34 .
[0081] Secondly, explanation is made on the manual valve switched from the valve opening position shown in FIG. 2 to the valve closing position.
[0082] To be concrete, the operator rotates the manual valve from the safety mechanism release position R to the safety mechanism set position S. Then, the rod 51 comes into contact with the piston rod 21 which also receives the downward urging force of the springs 22 and 52 . The piston rod 21 is therefore urged downwards, holding the diaphragm valve element 32 integral with the piston rod 21 in contact with the valve seat 31 . As a result, the fluid flowing in the port 33 is prevented from passing through the communicating area 35 closed by the diaphragm valve element 32 and flowing toward the port 34 .
[0083] As above, when the manual valve is rotated from the valve opening position in FIGS. 2 and 3 to the valve closing position, the flow passage space between the diaphragm valve element 32 and the valve seat 31 is closed, thus interrupting the communication between the port 33 , the communicating area 35 , and the port 34 . Consequently, the fluid flowing in the port 33 is prevented from flowing out through the port 34 .
[0084] In other words, even where the pilot valve is in a valve open state as shown in FIG. 3 , the operator may rotate the handle 55 from the safety mechanism release position R to the safety mechanism set position S to forcibly switch the pilot valve from the valve open state to the valve closed state. Accordingly, in case of emergency where fluid discharge should be stopped immediately, the operator can react to the emergency case appropriately.
[0085] Further, for example a padlock 57 may be inserted in the keyhole 56 of the knob 53 in the state of FIG. 1 by the operator. In this case, the handle 55 is prevented from rotating from the safety mechanism set position S ( FIG. 4 ) even where air is supplied to the operation port 24 . The rod 51 and the piston rod 21 are thus held in contact relation, so that the rod 21 will not slide upwards. Thus, the pilot valve can be maintained in the valve closed state even if air is supplied through the operation port 24 .
[0086] In other words, when the operator locks the manual valve in the valve closing position, the fluid will not flow out even if air is supplied through the operation port 24 due to malfunction. The operator is therefore allowed to safely work for maintenance or the like.
[0087] Next, FIGS. 5 and 6 are explained. Here, FIGS. 5 and 6 are sectional views of the combined valve with the valve-seat following mechanism to prevent a decrease in the sealing strength of the valve operating mechanism when the combined valve 1 of the present invention is used as the chemical liquid valve.
[0088] For use of the combined valve 1 as the chemical liquid valve, it is assumed that the valve seat 31 is made of a material having resistance to corrosion, such as fluorocarbon resin. At this time, when the valve is continuously used as the normal pilot valve shown in FIGS. 2 and 3 for a long term, the valve seat 31 repeatedly receives stress from the diaphragm valve element 32 for the long term. Conceivably, the valve seat 31 may shrink downwards by plastic-deformation called a creep phenomenon. This may cause a clearance between the rod 51 and the piston rod 21 when the manual valve is placed in the safety mechanism set position S. Hence, if air is supplied through the operation port 24 , the piston rod 21 is caused to slide upwards by the clearance against the downward urging force of the springs 22 and 52 , leading to a decrease in downward urging force exerted on the diaphragm valve element 32 integral with the piston rod 21 . Consequently, the sealing strength between the diaphragm valve element 32 and the valve seat 31 may become insufficient.
[0089] Even when air is not supplied through the operation port 24 , the diaphragm valve element 32 and the piston rod 21 may be moved to slide upwards by the pressure of chemical liquid flowing into the port 33 . This may leads to insufficient sealing strength between the diaphragm valve element 32 and the valve seat 31 .
[0090] In other words, when the valve seat 31 shrinks downwards by plastic deformation, the sealing strength between the diaphragm valve element 32 and the valve seat 31 becomes insufficient, so that the port 33 , the communicating area 35 , and the port 34 are communicated with each other. Thus, the chemical liquid supplied to the port 33 might flow out through the port 34 .
[0091] In FIG. 6 , an operating state of the valve-seat following mechanism is illustrated. Specifically, when turned, the feed screw 71 is moved up/down, and the rod 51 inserted in the feed screw 71 is also moved up/down. Here, when the feed screw 71 is turned to move downwards, allowing the rod 51 to move down, thereby moving the piston rod 21 held in contact with the rod 51 downwards. Accordingly, the downward urging force on the diaphragm valve element 32 integral with the piston rod 21 is increased, thus providing sufficient sealing strength between the diaphragm valve element 32 and the valve seat 31 .
[0092] In other words, by moving the feed screw 71 downwards, the sealing strength is enhanced between the diaphragm valve element 32 and the valve seat 31 to prevent the communication between the port 33 , the communicating area 35 , and the port 34 . It is therefore possible to prevent the chemical liquid supplied to the port 33 from flowing out through the port 34 .
Second Embodiment
[0093] A combined valve 2 in a second embodiment will be explained with reference to FIGS. 7 and 10 . As shown in FIG. 9 , a body section of the combined valve 2 includes a valve body 311 , cylinder 312 , piston cylinder 314 , and cover 313 , which are integrally formed in one unit. The combined valve 2 is structured of a pilot valve and a manual valve. As for the combined valve 2 , “Upper” indicates a manual valve side and “Lower” indicates a pilot valve side.
[0094] Firstly, the pilot valve of the combined valve 2 is explained. The pilot valve is further divided into a pilot mechanism and a valve operating mechanism. Here, the pilot mechanism includes the cylinder 312 , the cover 313 , a piston rod 321 , springs 322 and 352 , a piston 326 , and springs 327 and 328 .
[0095] These cylinder 312 , cover 313 , and piston cylinder 314 constitute an airtight container. Mounted in the piston cylinder 314 are the piston 326 slidable therein, the spring 327 which urges the piston 326 upwards, and the spring 328 which urges the piston 326 downwards. The piston 326 partitions the space defined by the piston cylinder 314 and cover 313 into two chambers, upper and lower. The lower chamber is a pressure chamber 323 which is communicated with an operation port 324 .
[0096] The shaft 325 is inserted in the piston 326 and integrally coupled to the rod 321 . Here, the spring 322 is located between the shaft 325 and the piston cylinder 314 to urge the shaft 325 downwards.
[0097] The valve operating mechanism includes the valve body 311 , a diaphragm valve element 332 , and ports 333 and 334 . In the valve body 311 , the ports 333 and 334 are communicated with each other through a communicating area 335 . The diaphragm valve element 332 which will be brought into/out of contact with the valve body 311 is partially sandwiched between the valve body 311 and the cylinder 312 . Accordingly, the valve body 311 and the cylinder 312 are airtightly partitioned by the diaphragm valve element 32 , preventing the fluid flowing in the communicating area 335 from leaking out to the cylinder 312 side. The diaphragm valve element 332 , integrally coupled to the rod 321 , is arranged to be separated from the valve body 311 when the rod 321 is not urged downwards and to be brought into contact with the valve body 311 when the rod 332 is urged downwards.
[0098] The manual valve of the combined valve 2 is explained below. The manual valve includes an adjusting rod 351 , the spring 328 , and a knob 353 . Above the adjusting rod 351 , the knob 353 is attached to be rotatable about an eccentric shaft 354 . The knob 353 is provided with a handle 355 , a keyhole 356 , and a notch 360 .
[0099] The combined valve 2 having the above structure is operated as follows.
[0100] A normal operation of the pilot valve will be described first. FIG. 9 shows the combined valve 2 with the manual valve held in a valve opening position and the pilot valve opened to allow the flow of fluid. FIG. 8 shows the combined valve 2 with the manual valve held in the valve opening position but the pilot valve closed to prevent the flow of fluid.
[0101] FIG. 9 is first explained. FIG. 9 shows the pilot valve opened by supply of air pressure thereto by an electromagnetic valve not shown. Specifically, when air is supplied to the pilot valve through the operation port 324 , the air is fed into the pressure chamber 323 via the air supply passage 315 of the piston cylinder 314 . Then, the air pressure in the pressure chamber 323 is increased. Under upward pressure in association with the increase in air pressure in the pressure chamber 323 , the piston 326 slides upwards in the piston cylinder 314 against the downward urging force of the spring 328 . In association with the upward sliding of the piston 326 , the shaft 325 whose flange portion bears on the piston 326 is simultaneously moved upwards against the downward urging force of the spring 322 . The rod 321 integral with the shaft 325 is also moved upwards. Accordingly, the diaphragm valve element 332 coupled to the rod 321 is not pressed downwards and is brought out of contact with the valve body 311 . Thus, a passage space is generated between the diaphragm valve element 332 and the valve body 311 , providing communication between the ports 333 and 334 through the communicating area 335 . The fluid supplied into the valve body 311 through the port 333 is then discharged out through the port 334 .
[0102] Next, FIG. 8 shows the pilot valve in the closed state. Specifically, when air supply into the pressure chamber 323 through the operation port 24 is stopped and the air pressure forcing the piston 326 upwards is reduced, the piston 326 is moved down by the urging force of the springs 327 and 328 . Then, the shaft 325 held in contact with the piston 326 is urged downwards by the spring 322 and then the diaphragm valve element 332 integral with the shaft 325 and the rod 321 is brought into contact with the valve body 311 .
[0103] Accordingly, the flow passage space between the diaphragm valve element 332 and the valve body 311 is closed. This interrupts the communication between the ports 333 and 334 through the communicating area 335 and thus the fluid supplied through port 333 is not allowed to flow out through the port 334 .
[0104] When the manual valve is located in the valve opening position, opening/closing operation of the pilot valve can be performed by the electromagnetic valve.
[0105] Further, when the adjusting rod 351 is engaged in the notch 360 of the knob 353 , the manual valve is prevented from shifting to the valve closing position. This makes it possible to ensure the opening/closing operation of the pilot valve by the electromagnetic valve.
[0106] Next, an operation of the manual valve when used by an operator for example as a safety mechanism during maintenance or the like is explained referring to FIGS. 7 and 10 . FIG. 7 shows the combined valve 2 with the manual valve in the valve closing position, which is switched from the valve opening position shown in FIG. 8 or 9 .
[0107] Firstly, explanation is made on the manual valve switched from the valve opening position shown in FIG. 9 to the valve closing position. To be concrete, the operator rotates the handle 355 of the knob 353 , 180 degrees counterclockwise in front view, about the eccentric shaft 354 from the valve opening position (hereinafter, referred to as a safety mechanism release position R) to a predetermined position (hereinafter, referred to as a safety mechanism set position S). Here, the predetermined position represents the position where the outer tapered periphery of the knob 353 is in contact with the adjusting rod 351 . Then, as the rotating operation is started, the adjusting rod 351 receiving the downward load resulting from the rotation of the handle 355 of the knob 353 is moved down into contact with the piston 326 which is then slid downwards. Accordingly, the piston 326 is brought out of contact with the flange portion of the shaft 325 . The shaft 325 becomes movable up and down separately from the piston 326 . The shaft 325 is therefore urged downwards by the spring 322 . The shaft 325 and the diaphragm valve element 332 integral with the rod 321 are brought into contact with the valve body 311 .
[0108] On the other hand, explanation is made on the manual valve switched from the valve opening position shown in FIG. 8 to the valve closing position. To be concrete, the operator rotates the handle 355 of the knob 353 from the safety mechanism release position R to the safety mechanism set position S. Then, as the rotating operation is started, the adjusting rod 351 receiving the downward load resulting from the rotation of the handle 355 of the knob 353 is moved down into contact with the piston 326 which is then slid downwards. Accordingly, the piston 326 is brought out of contact with the flange portion of the shaft 325 . The shaft 325 becomes movable up and down separately from the piston 326 . However, the shaft 325 is urged downwards by the spring 322 . The shaft 325 and the diaphragm valve element 332 integral with the rod 321 are thus held in contact with the valve body 311 .
[0109] As above, when the manual valve is rotated form the valve opening position shown in FIGS. 8 and 9 to the valve closing position, the flow passage space between the diaphragm valve element 332 and the valve body 311 is closed, interrupting the communication between the ports 333 and 334 through the communicating area 335 . Thus, the fluid flowing in the port 333 is prevented from flowing out through the port 334 .
[0110] In other words, even where the pilot valve is in a valve open state as shown in FIG. 9 , the operator may rotate the handle 355 from the safety mechanism release position R to the safety mechanism set position S to forcibly switch the pilot valve from the valve open state to the valve closed state. Accordingly, in case of emergency where fluid discharge should be stopped immediately, the operator can react to the emergency case appropriately.
[0111] Further, when the knob 353 is rotated to the position ( FIG. 7 ) where the outer tapered periphery of the knob 353 makes contact with the adjusting rod 351 , the handle 355 of the knob 353 can be locked in the safety mechanism set position S.
[0112] Here, the reason why the handle 355 of the knob 353 can be locked in the safety mechanism set position S is as described below. Specifically, the distance (hereinafter, referred to as a “distance R 1 ”) from the center point of the eccentric shaft 354 of the knob 353 to an inflection point of the outer periphery of the knob 353 in FIG. 10 is longer than the distance (hereinafter, referred to as a “distance R 2 ”) from the center point of the eccentric shaft 354 of the knob 353 to the outer tapered periphery of the knob 353 . Therefore the handle 355 of the knob 353 is held against rotation unless it receives a force pressing the adjusting rod 351 downwards by a distance corresponding to the difference between the distances R 1 and R 2 against the urging force of the spring 328 . The handle 355 can thus be locked in the state shown in FIG. 7 .
[0113] The pilot valve can be maintained in the valve open state even if air is supplied thereto through the operation port 324 .
[0114] In other words, when the manual valve is placed in the valve closing position by the operator as shown in FIG. 7 , the fluid is prevented from flowing out even when air is supplied through the operation port 324 due to malfunction. Accordingly, the operator is allowed to safely perform maintenance or the like.
[0115] In addition, for example a padlock 357 may be inserted in the keyhole 356 of the knob 353 in the state of FIG. 7 by the operator. This case is the same as in the combined valve 1 in the first embodiment and therefore the details are not repeated here.
[0116] Further, when the handle 355 of the knob 353 in FIG. 9 is rotated from the safety mechanism release position R to the safety mechanism set position S, as the rotating operation is started, the adjusting rod 351 receives the downward load resulting from the rotation of the handle 355 of the knob 353 and then is brought into contact with the piston 326 even where air is supplied to the operation port 324 by the electromagnetic valve not shown. The piston 326 is slid downwards, separating from the flange portion of the shaft 325 . Then, the air supplied through the operation port 324 and the air in the pressure chamber 323 are released through a gap generated between the piston 326 and the flange portion of the shaft 325 separated therefrom. Consequently, the air pressure in the enclosed space formed by the cover 313 placed above the piston 326 , the piston cylinder 314 , and the adjusting rod 351 becomes equal to the air pressure in the pressure chamber 323 under the piston 326 . As for the adjusting rod 351 , accordingly, upward thrust to the piston 326 resulting from the air pressure in the pressure chamber 323 is reduced. As a result, the upward thrust to the piston 326 resulting from the air pressure in the pressure chamber 323 is reduced. The handle 355 of the knob 353 can therefore be rotated when applied enough load against the upward urging force of the spring 327 .
[0117] The operator is allowed to close the manual valve without applying a large force to counterbalance the air pressure.
Third Embodiment
[0118] A combined valve 3 in a third embodiment is explained referring to FIGS. 11 to 13 .
[0119] As shown in FIG. 13 , a body section of the combined valve 3 includes a valve body 411 , cylinder 412 , piston cylinder 414 , and cover 413 , which are integrally formed in one unit. The combined valve 3 is structured of a pilot valve and a manual valve. As for the combined valve 3 , “Upper” indicates a manual valve side and “Lower” indicates a pilot valve side.
[0120] Firstly, the pilot valve of the combined valve 3 is explained. The pilot valve is further divided into a pilot mechanism and a valve operating mechanism. Here, the pilot mechanism includes the cylinder 412 , the piston cylinder 414 , a rod 421 , a spring 422 , a shaft 425 , a piston 426 , and a spring 428 .
[0121] The piston cylinder 414 and the adjusting rod 451 constitute an airtight container in which the piston 426 is slidably mounted. The spring 428 is placed to urge the adjusting rod 451 upwards and the piston 426 downwards. The piston 426 partitions the space defined by the piston cylinder 414 and the adjusting rod 451 into two chambers, upper and lower. The lower chamber is a pressure chamber 423 which is communicated with an operation port 429 through an air supply passage 415 of the piston cylinder 414 and an air supply passage 459 formed in the outer periphery of the adjusting rod 451 .
[0122] Further, the shaft 425 is inserted in the piston 426 and coupled to the rod 421 . Here, the spring 422 is placed in contact with the shaft 425 to urge the shaft 425 and the rod 421 downwards.
[0123] On the other hand, the valve operating mechanism includes the valve body 411 , a diaphragm valve element 432 , ports 433 and 434 . This structure is the same as in the combined valve 2 in the second embodiment and therefore the details thereof are not repeated here.
[0124] Next, the manual valve of the combined valve 3 is explained. The manual valve includes the adjusting rod 451 , spring 428 , and knob 453 . The basic structure of the combined valve 3 except for the shape of the adjusting rod 451 is similar to that of the combined valve 2 in the second embodiment and its explanation is omitted here.
[0125] The combined valve 3 having the above structure is operated as follows.
[0126] A normal operation of the pilot valve will be described first. FIG. 13 shows the combined valve 3 with the manual valve held in the valve opening position and the pilot valve opened to allow the flow of fluid. FIG. 12 shows the combined valve 3 with the manual valve held in the valve opening position but the pilot valve closed to prevent the flow of fluid.
[0127] FIG. 13 is first explained. FIG. 13 shows the pilot valve opened by supply of air pressure thereto through an electromagnetic valve not shown. Specifically, when air is supplied to the pilot valve through the operation port 429 , the air is fed into the pressure chamber 423 via the air supply passage 459 formed on the outer periphery of the adjusting rod 451 and the air supply passage 415 of the cylinder 414 . Then, the air pressure in the pressure chamber 423 is increased. Under upward pressure in association with the increase in air pressure in the pressure chamber 423 , the piston 426 is allowed to slide upwards in the piston cylinder 414 against the downward urging force of the spring 428 . In association with the upward sliding of the piston 426 , the shaft 425 whose flange portion bears on the piston 426 is simultaneously moved upwards against the downward urging force of the spring 422 . The rod 421 coupled to the shaft 425 is also moved upwards. Accordingly, the diaphragm valve element 432 coupled to the rod 421 is not pressed downwards and is brought out of contact with the valve body 411 . Thus, a passage space is generated between the diaphragm valve element 432 and the valve body 411 , providing communication between the ports 433 and 434 through the communicating area 435 . The fluid supplied into the valve body 41 through the port 433 is then discharged out through the port 434 .
[0128] Next, FIG. 12 shows the pilot valve in a closed state. Specifically, air supply into the pressure chamber 423 through the operation port 429 is stopped and the air pressure forcing the piston 426 upwards is reduced. The subsequent operations are similar to those in the combined valve 2 in the second embodiment and therefore the details are not repeated here.
[0129] Next, an operation of the manual valve when used by an operator for example as a safety mechanism during maintenance or the like is explained referring to FIG. 11 . FIG. 11 shows the combined valve 2 with the manual valve in the valve closing position, which is switched from the valve opening position shown in FIG. 12 or 13 . This operation is similar to in the combined valve 2 in the second embodiment and therefore the details of switching of the manual valve from the valve opening position to the valve closing position are omitted here.
[0130] Further, when the knob 453 is rotated to the position where the outer tapered portion of the knob 453 comes into contact with the adjusting rod 451 , as shown in FIG. 11 , the handle 455 of the knob 453 can be locked in the safety mechanism set position S. The subsequent operations are similar to those in the combined valve 2 in the second embodiment and therefore the details thereof are not repeated here.
[0131] In addition, for example a padlock 457 may be inserted in a keyhole 456 of the knob 453 in the state of FIG. 11 by the operator. This case is the same as in the combined valve 1 in the first embodiment and the combined valve 2 in the second embodiment and therefore the details thereof are omitted here.
[0132] Further, when the handle 455 of the knob 453 in FIG. 13 is rotated from the safety mechanism release position R to the safety mechanism set position S, as the rotating operation is started, the communication between the air supply passage 459 of the adjusting rod 451 and the air supply passage 415 of the piston cylinder 414 is interrupted even where air is supplied to the operation port 429 by the electromagnetic valve not shown. The air is not supplied through the operation port 429 . Consequently, the handle 455 of the knob 453 is allowed to be rotated under no air pressure thereon.
[0133] In other words, the operator is allowed to rotate the manual valve to the valve closing position without applying a large force to the manual valve.
Fourth Embodiment
[0134] A combined valve 4 in a fourth embodiment is explained referring to FIGS. 16 to 20 .
[0135] As shown in FIG. 18 , a body section of the combination 4 includes a valve body 511 , piston cylinder 512 , spool cylinder 514 , and cover 513 , which are integrally formed in one unit. The combined valve 4 is structured of a pilot valve and a manual valve. As for the combined valve 4 , “Upper” indicates a manual valve side and “Lower” indicates a pilot valve side.
[0136] Firstly, the pilot valve of the combined valve 4 is explained. The pilot valve is further divided into a pilot mechanism and a valve operating mechanism. Here, the pilot mechanism includes the cylinder 512 , the spool cylinder 514 , a spring 522 , and a piston 526 .
[0137] The piston cylinder 512 and the spool cylinder 514 constitute an airtight container in which the piston 526 is slidably mounted. The spring 522 is located to urge the spool cylinder 514 upwards and the piston 526 downwards.
[0138] The piston 526 partitions the space defined by the piston cylinder 512 and the spool cylinder 514 into two chambers, upper and lower. The lower chamber is a pressure chamber 523 which is communicated with an operation port 529 through an air supply passage 515 formed in the piston 526 and an air supply passage 559 formed in an adjusting rod 551 mentioned later. Alternatively, the pressure chamber 523 is communicated with an exhaust port 529 through the air supply passage 515 of the piston 526 .
[0139] On the other hand, the valve operating mechanism includes the valve body 511 , a diaphragm valve element 532 , and ports 533 and 534 . This structure is the same as in the combined valve 2 in the second embodiment and the combined valve 3 in the third embodiment and therefore the details thereof are not repeated here.
[0140] Next, the manual valve of the combined valve 4 is explained. The manual valve includes the adjusting rod 551 , the spring 528 , the knob 553 , and a bracket 558 . Attached above the adjusting rod 551 is a knob 553 rotatable about an eccentric shaft 554 . This knob 553 includes a handle 555 and a notch 560 . An air supply passage 559 is formed in the adjusting rod 551 , providing a simple passage structure easy to make. As shown in FIG. 20 , furthermore, the bracket 558 is interposed between two arms of the forked handle of the knob 553 . The bracket 558 is formed with a keyhole 556 .
[0141] The combined valve 4 having the above structure is operated as follows.
[0142] A normal operation of the pilot valve will be described first. FIG. 18 shows the combined valve 4 with the manual valve held in a valve opening position and the pilot valve opened to allow the flow of fluid. FIG. 19 shows the combined valve 4 with the manual valve held in the valve opening position but the pilot valve closed to prevent the flow of fluid.
[0143] FIG. 18 is first explained. FIG. 18 shows the pilot valve opened by supply of air pressure thereto through an electromagnetic valve not shown. Specifically, when air is supplied to the pilot valve through the operation port 529 , the air is fed into the pressure chamber 523 via the air supply passage formed in the adjusting rod 551 and the air supply passage 515 of the piston 526 . Then, the air pressure in the pressure chamber 523 is increased. Under upward pressure in association with the increase in air pressure in the pressure chamber 523 , the piston 526 is allowed to slide upwards in the piston cylinder 512 against the downward urging force of the spring 522 . Accordingly, the diaphragm valve element 532 integral with the piston 526 is not pressed downwards and then is brought out of contact with the valve body 511 . Thus, a passage space is generated between the diaphragm valve element 532 and the valve body 511 , providing communication between the ports 533 and 534 through the communicating area 535 . The fluid supplied into the valve body 511 through the port 533 is then discharged out through the port 534 .
[0144] Next, FIG. 17 shows the pilot valve in a closed state. Specifically, air supply into the pressure chamber 523 through the operation port 529 is stopped and the air pressure forcing the piston 526 upwards is reduced. The subsequent operations are simply the reverse of the above mentioned operations for opening the pilot valve by supply of air pressure, and the details thereof are not repeated here.
[0145] Next, an operation of the manual valve when used by an operator for example as a safety mechanism during maintenance or the like is explained referring to FIG. 16 . FIG. 16 shows the combined valve 4 with the manual valve in the valve closing position, which is switched from the valve opening position shown in FIG. 17 or 18 .
[0146] Firstly, explanation is made on the manual valve switched from the valve opening position shown in FIG. 18 to the valve closing position. To be concrete, the operator rotates the handle 555 of the knob 553 clockwise in front view about the eccentric shaft 554 from the valve opening position (hereinafter, referred to as a safety mechanism release position R) to a predetermined position (hereinafter, referred to as a safety mechanism set position S). Then, a pressing force of the handle 555 of the knob 553 is decreased as the rotation thereof is started, thereby allowing the adjusting rod 551 to move upwards. In this state, the communication between the operation port 529 and the air supply passage 559 of the adjusting rod 551 is closed, whereas the pressure chamber 523 is brought into communication with the exhaust port 530 . Accordingly, the air in the pressure chamber 523 is exhausted through the exhaust port 530 , causing the downward sliding of the piston 526 by the urging force of the spring 522 . Then, the diaphragm valve element 532 integral with the piston 526 is moved downwards into contact with the valve body 511 . The combined valve 4 is thus placed in the valve closed state as shown in FIG. 16 .
[0147] In the above operation, only the adjusting rod 551 is moved by the knob 553 and the piston 526 is not pressed. Accordingly, the piston 526 receives no force resulting from the rotation of the knob 553 , and the valve body 511 receives only the urging force of the spring 522 through the piston 526 and the diaphragm valve element 532 . No creep will therefore be caused, so that the sealing strength of the valve operating mechanism can be ensured.
[0148] Further, for example a padlock 557 may be inserted in the keyhole 556 of the bracket 558 in the state of FIG. 16 by the operator. In this case, the handle 555 is prevented from rotating even where air is supplied to the operation port 529 , so that the pilot valve can be maintained in the valve closed state ( FIG. 20 ). Referring to FIG. 19 , the keyhole 556 of the bracket 558 is designed to have sufficient play or clearance to hold the adjusting rod 551 against movement even if the handle 555 wobbles when the padlock 557 is inserted in the keyhole 556 . In other words, the keyhole 556 has play enough to prevent the knob 553 from making contact with the adjusting rod 551 even when the knob 553 is rotated and the handle 555 touches a shackle of the padlock 557 . The adjusting rod 551 is therefore held against movement even when the operator erroneously touches the handle 555 . Thus, no air will be supplied into the pressure chamber 523 through the operation port 529 . In FIG. 19 , an arrow X indicates a moving range of the handle 555 where the adjusting rod 51 is held against movement. As an alternative, the bracket 558 may be formed to have a reduced thickness. In this case, a padlock 557 with a shackle having a curved end smaller in radius may be used as shown in FIG. 20 .
[0149] Further, when the handle 555 of the knob 553 in FIG. 18 is rotated from the safety mechanism release position R to the safety mechanism set position S, as the rotation of the handle 555 is started, the communication between the air supply passage 559 of the adjusting rod 551 and the operation port 529 is interrupted even where air is supplied to the operation port 529 by an electromagnetic valve not shown. Consequently, no air is supplied through the operation port 529 and the handle 555 of the knob 553 is thus allowed to be rotated without the air pressure thereon. In the combined valve 4 in the fourth embodiment, particularly, the diameter of the adjusting rod 551 is small and therefore the upward air pressure exerted on the adjusting rod 551 is low. Even at the beginning of rotation of the handle 555 of the knob 553 , the operator does not have to apply strong force to rotate the handle 555 .
[0150] In other words, the above structure enables the operator to readily rotate the manual valve to the valve closing position.
[0151] In the combined valve 4 , moreover, the air supply passage 515 is formed in the piston 526 and the spring 528 is located inside the spring 522 in a height direction as shown in FIGS. 16 to 18 . Accordingly, the combined valve 4 is of a smaller height as compared with the combined valves in the above embodiments. Here, a component urging the adjusting rod 551 , namely, the spring 528 in the present embodiment corresponds to the springs 328 and 428 in the combined valves 2 and 3 in the second and third embodiment respectively. If particularly paying attention to the positional relation of those springs, it is to be understood that the combined valve 4 is shorter in height than the combined valves 2 and 3 in the second and third embodiments.
Fifth Embodiment
[0152] A combined valve 5 in a fifth embodiment is explained referring to FIGS. 21 to 32 .
[0153] FIG. 21 is a sectional view of the combined valve 5 in a valve open state. FIG. 22 is a top view of the combined valve 5 . FIG. 23 is an external view of an upper part of the combined valve 5 .
[0154] As shown in FIG. 21 , a body section of the combined valve 5 includes a valve body 611 , cylinder 612 , and housing 613 . The combined valve 5 is also structured of a pilot valve and a manual valve. As for the combined valve 3 , “Upper” indicates a manual valve side and “Lower” indicates a pilot valve side.
[0155] Firstly, the pilot valve of the combined valve 5 is explained. The pilot valve is further divided into a pilot mechanism and a valve operating mechanism. Here, the pilot mechanism includes the cylinder 612 , the housing 613 , a spring 622 , and a piston 626 .
[0156] The cylinder 612 and the housing 613 constitute an airtight container in which the piston 626 is slidably mounted. The spring 622 is located on the piston 626 to urge the housing 613 upwards and the piston 626 downwards.
[0157] The piston 626 partitions the space defined by the cylinder 612 and the housing 613 into two chambers, upper and lower. The lower chamber is a pressure chamber 623 which is communicated with an air supply port 659 mentioned later through an air supply passage 615 formed in the piston 626 .
[0158] As shown in FIGS. 21 to 23 , the housing 613 is formed with an operation port 629 , exhaust port 630 , and air supply port 659 , which constitute a 3-port valve shown in FIGS. 24A to 24 C in combination with a rod 651 mentioned later. FIGS. 24A to 24 C are sectional views of a part of the combined valve 5 taken along a line A-A of FIG. 25 . FIG. 24A shows the manual valve placed in a valve opening position; FIG. 24C shows the manual valve in a valve closed position; and FIG. 24B shows the manual valve in an intermediate position between those in FIG. 24A and 24 .
[0159] On the other hand, the valve operating mechanism includes the valve body 611 , a diaphragm valve element 632 , and ports 633 and 634 . This structure is the same as in the combined valves 2 to 4 in the second to fourth embodiments and therefore the details thereof are not repeated here.
[0160] Next, the manual valve of the combined valve 5 is explained. The manual valve includes a rod 651 , knob 653 , gaskets 661 , 662 , and 663 , and slide plate 665 . The rod 651 is fit in a through hole 667 formed in the housing 613 . The knob 653 is rotatably attached to one end of the rod 651 . The knob 653 is provided with a handle 655 . The rod 651 is formed with a pin 664 placed in a hole of the knob 653 . The gasket 661 having the shape shown in FIG. 26 is located on the outer periphery of the rod 651 at its center area in an axial direction. The gaskets 662 and 663 are located surrounding the rod 651 at both sides of the gasket 61 in the axial direction. The slide plate 665 is placed above the rod 651 . FIG. 26A is a top view of the gasket 661 and FIG. 26B is a sectional view of the gasket 661 taken along a line A-A of FIG. 26A .
[0161] The combined valve 5 having the above structure is operated as follows.
[0162] A normal operation of the pilot valve will be described first. FIG. 21 shows the combined valve 5 with the manual valve held in the valve opening position and the pilot valve opened to allow the flow of fluid. FIG. 25 shows the combined valve 5 with the manual valve held in the valve opening position but the pilot valve closed to prevent the flow of fluid.
[0163] FIG. 21 is first explained. FIG. 21 shows the pilot valve opened by supply of air pressure thereto through an electromagnetic valve not shown. Specifically, when air is supplied to the pilot valve through the operation port 629 , the air passes through the space formed between the outer periphery of the rod 651 and the through nole 667 and the air supply passage 659 and then the air is fed into the pressure chamber 623 through the air supply passage 615 in the piston 626 . Accordingly, the air pressure in the pressure chamber 623 is increased. Under upward pressure in association with the increase in air pressure in the pressure chamber 623 , the piston 626 is allowed to slide upwards in the cylinder 612 against the downward urging force of the spring 622 . Then, the diaphragm valve element 632 integral with the piston 626 is not pressed downwards and is brought out of contact with the valve body 611 . A passage space is accordingly generated between the diaphragm valve element 632 and the valve body 611 , providing communication between the ports 633 and 634 through the communicating area 635 . The fluid supplied into the valve body 611 through the port 633 is then discharged out through the port 634 .
[0164] Next, FIG. 25 shows the pilot valve in the closed state. Specifically, air supply into the pressure chamber 623 through the operation port 629 is stopped and the air pressure forcing the piston 626 upwards is reduced. The subsequent operations are simply the reverse of the above mentioned operations and the details thereof are not repeated here.
[0165] Next, an operation of the manual valve when used by an operator for example as a safety mechanism during maintenance or the like is explained referring to FIGS. 27 and 28 . FIG. 27 is a sectional view of the knob 653 taken along a line B-B of FIG. 25 . FIGS. 28A to 28 C are explanatory views showing a relation between the knob 653 , rod 651 , and pin 664 .
[0166] Explanation is made on the manual valve switched from the valve opening position to the valve closing position. To be concrete, the operator rotates the handle 655 of the knob 653 couterclockwise in front view in FIG. 27 from the valve opening position (hereinafter, referred to as a safety mechanism release position R) to a predetermined position (hereinafter, referred to as a safety mechanism set position S). When the handle 655 is rotated by a predetermined angle from a state of FIG. 28A to a different state of FIG. 28B , the rotation of the knob 653 is transmitted to the rod 651 through the pin 664 , causing the rod 651 to rotate. When the handle 655 has completely been rotated to the safety mechanism set position S, the knob 653 is positioned as shown in FIG. 28C .
[0167] The knob 653 is provided as shown in FIG. 28 with a predetermined amount of play to provide a delay until the rotating of the knob 653 is transmitted to the rod 651 through the pin 664 . In other words, backlash is provided for the rotating amount of the rod 651 with respect to the rotating amount of the knob 653 . The rotating amount with backlash is set in a range from 90 degrees to 110 degrees. Accordingly, the rotating amount of the knob 653 is 180 degrees, whereas the actual rotating amount of the rod 651 is in a range from 70 degrees to 90 degrees.
[0168] When the manual valve is rotated to the safety mechanism set position S, the communication between the operation port 629 and the air supply port 659 is interrupted with the gasket 661 , while the exhaust port 630 is communicated with the air supply port 659 and hence with the pressure chamber 623 . Accordingly, air is exhausted through the exhaust port 630 , reducing the air pressure in the pressure chamber 623 . The piston 626 is slid downwards by the urging force of the spring 622 . The diaphragm valve element 632 coupled to the piston 626 is also then moved downwards into contact with the valve body 611 , bringing the combined valve 5 to the valve closed state.
[0169] Further, the slide plate 665 is slid from the above position toward the knob 653 until an end of the slide plate 665 protrudes as shown in FIGS. 21 and 23 . A padlock 657 for example is inserted and locked in a key hole 665 a formed in the end of the slide plate 665 . In this state, the knob 653 is prevented from rotating and therefore the combined valve 5 can be held in the valve closed state.
[0170] The slide plate 665 may be slid by;
[0171] (1) Pushing a lug 665 b of the slide plate 665 with fingers; or
[0172] (2) Utilizing a return spring placed between the slide plate 665 and the housing 613 for automatic sliding.
[0173] To be concrete, the above manner (2) that utilizes the return spring for automatic sliding may include the following techniques A and B.
[0174] FIGS. 29A to 29 D are schematic views of the manual valve to explain the technique A; specifically, FIG. 29A is a side view of the manual valve in the valve opening position, FIG. 29B is a sectional view of the same, FIG. 29C is a side view of the manual valve in the valve closing position, and FIG. 29D is a sectional view of the same.
[0175] In the technique A, the slide plate 665 is provided with the lug 665 b and a hook 665 c as shown FIGS. 29A to 29 D, and a return spring 666 is located between the slide plate 665 and the housing 613 . While the manual valve is in the valve opening position, the hook 665 c is engaged with a flange 651 a of the rod 651 as shown in FIG. 29A and 29B , thereby holding the slide plate 665 against sliding. In this state, tension is exerted on the return spring 666 .
[0176] The flange 651 a of the rod 651 includes a notch formed along the periphery thereof. When the knob 653 is rotated to bring the manual valve to the valve closing position, the notch will be adjusted to face to the hook 665 c of the slide plate 665 as shown in FIGS. 29C and 29D . The hook 665 c of the slide plate 665 is then disengaged from the flange 651 a of the rod 651 . Accordingly, the tension exerted on the return spring 666 is eliminated, allowing automatic sliding the slide plate 665 .
[0177] FIGS. 30A and 30B are schematic views of the manual valve to explain the technique B; specifically, FIG. 30A is a sectional view of the manual valve in the valve opening position and FIG. 30B is a sectional view of the same in the valve closing position.
[0178] In the technique B, the slide plate 665 is similarly provided with the lug 665 b and a return spring 666 is located between the slide plate 665 and the housing 613 . This technique B adopts the reverse operation of the return spring 666 to that in the technique A. To be concrete, while the lug 665 b of the slide plate 665 is not pressed with fingers, the return spring 666 is held in a natural length, generating no spring force. The slide plate 665 is therefore held in a non-sliding state. To slide the slide plate 665 , the lug 665 b is pushed with fingers, thereby compressing the return spring 666 .
[0179] Another configuration using a padlock 657 may be adopted as shown in FIGS. 31 and 32 . In this combined valve 5 , the rod 651 is provided with a flange 651 a at an end opposite to the knob 653 side. This flange 651 a has a shape shown in FIG. 32 . In particular, the flange 651 a is oriented as shown by a solid line in FIG. 32 when the manual valve is in the valve opening position. On the other hand, the flange 651 a is oriented as shown by a double-dashed line in FIG. 32 when the manual valve is in the valve closing position. When the manual valve is in the valve closing position, accordingly, the keyhole 651 b is placed vertically above the housing 613 . In this position, the padlock 657 or the like is engaged for locking.
[0180] In the above operation, only the rod 651 is moved by the knob 653 and the piston 626 is not pressed. Accordingly, the piston 626 receives no force resulting from the rotation of the knob 653 , and the valve body 611 receives only the urging force of the spring 622 through the diaphragm valve element 632 . No creep will therefore be caused, so that the sealing strength of the valve operating mechanism can continuously be ensured.
[0181] Further, when the handle 655 of the knob 653 in FIG. 21 is rotated from the safety mechanism release position R to the safety mechanism set position S, as the rotation of the handle 655 is started, the communication between the air supply passage 659 and the operation port 629 is interrupted by the gasket 661 of the rod 651 even when air is supplied to the operation port 629 by an electromagnetic valve not shown. Consequently, no air is supplied through the operation port 629 and the handle 655 of the knob 653 is thus allowed to be rotated under no air pressure thereon.
[0182] The above structure enables the operator to readily rotate the manual valve to the valve closing position without applying a large force to the manual valve.
[0183] In the combined valve 5 , moreover, the rod 651 is placed in a lateral direction perpendicular to a vertical (height) direction of the combined valve 5 and also the knob 653 is provided on the side of the combined valve 5 . Accordingly, the combined valve 5 is shorter in height than the combined valves 1 to 4 in the first to fourth embodiment where the valve mechanisms are arranged vertically and coaxially.
[0184] According to the above embodiments of the present invention, the above combined valves include a mechanism for preventing or covering a decrease in sealing strength of the valve operating function due to creep phenomenon which may occur in the valve seats. If the valve seats are made of fluorocarbon resin having resistance to corrosion, therefore, those combined valves may also be applied to a chemical liquid valve used in a semiconductor manufacturing process.
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A combined valve is constructed by integrating a manual valve operating as a safety mechanism and a pilot valve. When a handle of a knob of the manual valve is in a safety mechanism release position, a valve mechanism can be opened and closed depending on whether or not there is air supply to an operation port. When the handle is in the safety mechanism release position and the valve mechanism is even in a valve open state, the valve mechanism can be forcibly brought to a valve closed state by rotating the handle to a safety mechanism set position. Further, when the handle is in the safety mechanism set position, the valve mechanism can always be kept in the valve closed state irrespective of air supply to the operation port.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an apparatus and method for continuously producing filled dough pieces from a continuously fed filled cylindrical dough body, and particularly to an apparatus and method for continuously producing separate filled dough pieces of a desired shape without exposing the filler by cutting the continuously fed filled cylindrical dough body into pieces.
2. Description of Prior Art
Japanese Patent Publication No. 1169/69 discloses a confectionery molder where oppositely positioned toothed plates, each having two converging faces to form a tooth, cut a bar-shaped filled dough body conveyed on a conveyor belt, and then the upper toothed plates sway laterally to roll divided dough pieces in the space surrounded by the adjacent teeth to form spherical filler-containing dough pieces. Although this apparatus can make ball-shaped filled dough pieces, it requires a complex mechanism and the filler is liable to be exposed when the toothed plates cut the bar-shaped filler-containing dough body.
In this invention, dividers, each having a cutting edge, constrict the filled cylindrical dough body cooperatively with a pair of rotary disc cutters which cut the narrowed dough portion containing no filler, so that perfectly incrusted spherical dough pieces are produced without exposing the filler.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an apparatus and method for continuously producing filled dough pieces.
It is another object of the present invention to provide an apparatus and method for continuously cutting a filled cylindrical dough body, which is continuously conveyed, to make spherical or variously shaped dough pieces, the filler of which is completely incrusted by the outer material.
It is a further object of the present invention to provide an apparatus and method for continuously cutting a filled cylindrical dough body, which is continuously conveyed, by which the filled cylindrical dough body is cut in a simple and reliable process to form separate spherical or variously shaped dough pieces consisting of a filler incrusted by the outer material.
In one aspect of the present invention, an apparatus for continuously producing filled dough pieces from a filled cylindrical dough body is provided, comprising a conveyor belt; a pair of rotary disc cutters oppositely and horizontally arranged on the conveyor belt and synchronously driven in opposite directions, each of the rotary disc cutters being formed with a plurality of teeth at predetermined intervals at its periphery, each of the teeth of a rotary disc cutter arranged to periodically contact the corresponding tooth of the other rotary disc cutter in operation; and a plurality of dividers, which are positioned between and above the pair of cutters, and disposed at predetermined intervals on the periphery of a circle arranged to rotate about a horizontal shaft perpendicular to the direction of movement of the conveyor, each divider being adapted to engage a tooth of each of the rotary disc cutters for a distance sufficient to form a filled dough piece.
In another aspect of the present invention, a method of continuously producing filled dough pieces from a filled cylindrical dough body is provided, comprising constricting at every interval a portion of the filled cylindrical dough body, while being fed on a conveyor belt, to make a flattened portion which is almost exclusively composed of an outer layer, and, while maintaining the height of the flattened portion, laterally narrowing the length thereof to cut the filled cylindrical dough body into separate filled dough pieces of a desired shape.
The apparatus of the invention has a conveyor belt, a pair of rotary disc cutters disposed on the belt, and a plurality of dividers which are positioned between and above the cutters.
The divider constricts and flattens a poriton of the filled cylindrical dough body. The cutting edge of the divider may preferably be blunt and it presses the cylindrical dough body to flatten it until the outer layer is flattened and the filler is removed from the area. The dough body is then narrowed and cut from both sides by a pair of disc cutters disposed beneath the dividers.
The dividers may be radially mounted on the periphery of a wheel. They periodically cut the cylindrical dough body. By changing the space between the dividers at the periphery of the wheel, for example, filled dough pieces of a different length can be produced.
Furthermore, flattening the dough body by the divider and narrowing the flattened dough portion by a pair of rotary disc cutters are carried out in synchronism in such a manner that, when a certain divider presses the cylindrical dough body to a predetermined height, the cutters can compress, narrow, and cut the flattened dough portion which is composed almost exclusively of the outer material, thereby cutting the cylindrical dough body into separate spherical or variously shaped or dimensioned incrusted dough pieces.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevational view of an embodiment of the present invention.
FIG. 2 is a side elevational view, partly in cross-section, of an embodiment of the present invention.
FIG. 3 is a perspective view of a divider of an embodiment of the present invention.
FIG. 4(A) is a side elevational view of the dividers in cross-section and the cutter of an embodiment of the present invention showing the function of the dividers.
FIG. 4(B) illustrates cross-sectional views of the cylindrical dough body at points corresponding to points (1), (2), (3), and (4) of FIG. 4(A).
FIG. 4(C) is a plan view of a pair of rotary disc cutters of an embodiment of the present invention showing the function of the cutters.
DESCRIPTION OF THE PREFERRED EMBODIMENT
An embodiment of the present invention will now be described with reference to the drawings.
In FIG. 1, a pair of rotary disc cutters 2 and 2' are disposed slidably on a conveyor belt 4.
The cutters have a plurality of teeth 1 and 1',as seen in FIG. 4(C), to compress, narrow, and cut the dough and are located opposite to each other and adapted to be synchronously driven in opposite directions. The rotation of the cutters is carried out through rotary shafts 3 and 3', bevel gears 7, 8, and 7',8' and by rotary shafts 6 and 6'.
The teeth are provided at predetermined intervals circumferentially of the rotary disc cutters and adapted periodically to be in contact with each other to cut the dough at the middle of the belt 4.
Each of cutters 2 and 2' has upper and lower flat surfaces and a predetermined thickness, preferably slightly less than double the thickness of the outer layer 17 of the dough body 18. The cutters rotate at the same angular velocity to cut the dough and produce incrusted filled dough pieces in cooperation with the dividers 5.
FIG. 2 shows a plurality of dividers 5 and a wheel 11 to support the same and shows the positional relationship between the upper flat surfaces of the rotary disc cutters 2 and 2' and the flat faces 9 of the dividers 5. A perspective view of the divider 5 is shown in FIG. 3. The divider consists of a rectangular body. The outermost end surface 9 is flat and slidably engages the teeth 1 and 1' of the cutters 2 and 2' when they come into contact with each other. The opposite end of the divider 5 is provided with a rod 10, circular in cross-section, with a protruding ring 14. A recess 21 is provided straddling the outermost end surface 9 and the leading surface, and another recess 21 is formed straddling the outermost end surface and the trailing surface of the divider 5, in such a manner that the middle portion of the outermost end surface is the narrowest.
An example of the recess 21 is shown in FIG. 3. It forms a triangular indent on each of the adjoining outermost end and the leading or trailing end surfaces, and constitutes two faces of an imaginary tetrahedron. The edge between the two faces is indicated by a line 20. This recess is designed to accomodate the portion of the dough body protruding above the cutters 2 and 2' when the dough is fed to the cutting area. The shape of the recess can be changed to respond to the configuration of the desired filled dough pieces.
The rod 10 is adapted to be loosely fitted in one of the holes 12 radially bored in the periphery of the wheel 11 at predetermined intervals. The hole 12 may be circular in cross-section and has a circular shoulder near the inward end. The diameter of the hole inside the shoulder is smaller than the remainder. A coil spring 13 is provided between the rod 10 and the hole l2 and is held between the shoulder of the hole 12 and the ring 14 of the rod 10. A stopper 15 is provided at the outer end of the hole 12 and engages the ring 14 positioned within the hole so that the rod 10 may not leave the hole 12 by the rotation of the wheel or by the pressure of the spring member 13. Therefore, the dividers 5 can be pressed in the radial direction of the wheel 11 or restored to its original position depending on the pressure externally applied.
The position of the wheel 11 is so arranged that the flat face 9 of the divider 5 is in contact with the teeth 1 and 1' of the cutters 2 and 2' for a distance l (shown in FIG. 4(B); also see FIG. 2), while the dividers 5 rotate around the axis of the wheel 11 in the clockwise direction in FIG. 2, as shown by a curved arrow. For the distance l the devider 5 moves in the horizontal direction. The bottom of the recess 20 is shown by broken lines in FIG. 2.
The filled cylindrical dough body 18 is conveyed on the belt 4 in the direction shown by an arrow under the belt 4 in FIG. 2 and enters between the divider and the belt and simultaneously enters between the cutters. The rotation of the divider is so synchronized with the rotation of the cutters that when the flat face 9 of the divider 5 approaches its lowest position, the flat face 9 of the divider 5 contacts the teeth 1 and 1' of the cutters 2 and 2'. When the wheel 11 further rotates, the divider 5 is pushed in the direction of the center of the wheel 11 against the spring 13. When the divider 5 reaches the bottom of the wheel 11, the spring 13 is compressed to the greatest degree. At that time, the teeth 1 and 1' also contact each other.
Turning now to the operation of the invention, the filled cylindrical dough body 18 conveyed on the belt 4 enters between thc dividers 5 and the belt 4 and between the cutters 2 and 2'. Along with the progress of the dough body 18, a divider 5 gradually compresses the dough from above, while the cutters 2 and 2' squeeze the dough from both sides. The relationships of the movements of the dough, the cutters and the divider are illustrated in FIG. 4. The point at which the divider 5 comes into contact with the dough 18 is shown by the reference number (1) in FIG. 4(A). At this point, the cross-section of the dough is as shown in FIG. 4(B) by the reference number (1). when the divider moves to point (2), the teeth 1 and 1' of the cutters 2 and 2' touch the dough. At this point, an edge of the divider 5 comes into contact with the upper surface of the teeth 1 and 1', and the shape of the dough in cross-section is as shown in FIG. 4(B) by the reference number (2). The filler is almost completely excluded from the area. When the divider 5 moves a little further, the middle portion of the flat surface 9 comes into contact with the teeth 1 and ' and the dough is pressed to the height of the teeth. At this stage, the dough has a cross-section as shown in FIG. 4(B) by the reference number (3), where no filler is present and is composed only of the outer material 17. Since the portion of the dough that is compressed by the divider 5 is free of the filler, the teeth 1 and 1' can cut the dough without causing the filler to spill. When the flat face 9 of the divider 5 comes to the bottom of the whee1 11, the teeth 1 and 1' engage each other, and the divider is most strongly pressed against the teeth by the force of the spring 13. These positional relationships are shown by the reference number (4) in FIG. 4(A) as viewed from a side and in FIG. 4(C) as viewed from above. At this time, a portion of the cylindrical dough body is separated at its foremost end, and both the trailing half of the separated portion and the leading end of the remaining cylindrical dough body are completely covered with the outer material 17. It is evident from the above that by the next cutting cycle a second dough piece completely covered with the outer material is produced. A filled dough piece 19 as produced is shown in FIG. 4(A) and 4(C).
The separation of dough pieces from the cylindrical dough body without exposing the filler is facilitated by the mechanism where the flat face 9 of the divider 5, while rotating around the axis of the wheel 11 and in contact with the teeth 1 and 1' of the cutters 2 and 2', compresses the portion of the cylindrical dough body where it is cut for a certain distance. The number of the divider or the tooth, their dimensions and intervals, and the speed of rotation may be changed to respond to the required dimensions of the filled dough pieces desired, the production rate, and so forth. The tensility of the outer material of the cylindrical dough body to be cut should be taken into consideration in working the invention. If the outer material is very tensile so that it can readily stretch and shrink, such as rice-cake dough or bread dough, the divider can compress it more than the other types of dough, so that the height of the cutters 2 and 2' can be minimal.
According to the present invention, a continuously fed filled cylindrical dough body is compressed from above at the portion where it is cut to the extent that the filler is almost completely excluded from the compressed area, and then cut by oppositely arranged teeth of the cutters, thereby to cut the dough into perfectly incrusted filled dough pieces of a desired shape.
Also, no exposure of the filler is observed when constricting, flattening, and splitting the cylindrical dough body, and spherical or variously shaped filled dough pieces can be successively produced without requiring a complex mechanism.
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An apparatus and method for continuously producing filled dough pieces is provided. A pair of toothed rotary disc cutters are arranged on a conveyor belt feeding a filled cylindrical dough body. A plurality of dividers mounted on the periphery of a wheel are disposed between and above the teeth. The dividers and the teeth rotate about their own axes to flatten the cylindrical dough body and to split it by their cooperatively synchronized movement whereby completely incrusted spherical or variously shaped filled dough pieces are produced.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to monitoring damper position. More particularly, this invention relates to monitoring and calibrating damper position of a damper in a heating system.
2. Description of the Prior Art
In a heating system, fuel and combustion air are generally provided to a combustion chamber where they are ignited and burned. Fuel and air supplies are controlled by a modulation motor which rotates air damper and fuel valve shafts between a closed position (a low fire position) and an open position (a high fire position). Modulation of the rate that an air and fuel mixture is supplied to the combustion chamber (the firing rate) is accomplished by operating the air damper and fuel valve shafts between the low fire and high fire positions.
In the past, the firing rate has been controlled by crude, electromechanical devices. High fire and low fire position information was provided to a heating system controller by limit switches which were activated by cams mounted on the modulation motor shaft. However, the cams were mounted on the motor shaft at operating angles which were adjustable and could, therefore, be misadjusted. A misadjusted operating angle could lead to a false indication of a high fire or low fire position to the heating system controller. This, in turn, could lead to insufficient purging of the combustion chamber at start-up or to ignition at a high gas flow-rate. Both of these situations are undesirable. In addition to safety concerns, position accuracy is poor in this type of damper control.
Therefore, there is a need for a damper control system which is both safe and which maintains position accuracy.
SUMMARY OF THE INVENTION
With the present invention, damper position of damper means which control flow of combustion air or fuel in a heating system is monitored and calibrated on an automatic basis. The damper means is movable between end positions in response to movement of a motor shaft. The motor shaft, in turn, moves in response to a movement request signal. A shaft position signal is received by position detector means and has a value representative of position of the motor shaft. When the damper means reaches an end position, it is determined whether the value of the shaft position signal is within a predetermined tolerance.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of a portion of a heating system.
FIG. 2 is a flow diagram of the process of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is a schematic diagram of monitoring system 10. Monitoring system 10 comprises burner controller 12. motor drive 14, transformer T1, motor -6 and damper/fuel valves 18. Burner controller 12 receives various inputs such as operator inputs and sensor inputs and determines a firing rate. Based on that firing rate, it commands motor drive 14 to operate motor 16 so that damper/fuel valves 18 are opened or closed in a manner consistent with the firing rate determined by burner controller 12.
Line voltage L1 is stepped down by transformer T1 and supplied, in this preferred embodiment as 24 volts AC, to monitoring system 10 at a common terminal at motor drive 14 and an energized terminal at motor 16. An "Open" terminal and a "Close" terminal are energized by motor drive 14 based on the commands of burner controller 12. When burner controller 12 commands motor drive 14 to operate motor 16 so that damper/fuel valves 18 are open, motor drive 14 energizes the Open terminal and completes a line voltage circuit through high fire end switch 20 and open coil 22. When the line voltage circuit is completed through open coil 22, a motor shaft in motor 16 rotates opening a selected damper or fuel valve in damper/fuel valves 18. Cams are mounted on the motor shaft of motor 16 to actuate high fire end switch 20 when the motor shaft is in a predetermined high fire position. When high fire end switch 20 opened, the line voltage circuit is broken and the motor shaft is stopped.
Similarly, when burner controller 12 commands motor drive 14 to operate motor 16 so that a selected damper or fuel valve and damper/fuel valves 18 closes, the "close" terminal in motor drive 14 is energized completing a line voltage circuit across low fire switch 24 and close coil 26. This causes the motor shaft in motor 16 to rotate so that the selected damper or fuel valve in damper/fuel valves 18 closes. When the selected damper or fuel valve reaches the low fire position, a cam, mounted on the motor shaft in motor 16 opens low fire end switch 24 stopping the motor shaft. Potentiometer 28 is also coupled to the motor shaft of motor 16 and is connected to feedback circuit 30. Its wiper voltage, which varies with the motor shaft position of motor 16 and which corresponds to the position of the selected damper or fuel valve at damper/fuel valves 18, is provided to amplifier 32. Amplifier 32, in turn, provides a shaft position feedback signal to burner controller 12 at feedback terminal 34. Also, a reference voltage is provided to feedback circuit 30 at reference voltage nodes 36 and 38. FIG. 2 is a flow diagram of the monitoring system of the present invention. Burner controller 12 determines whether to command motor drive 14 for a high fire request or a low fire request or neither. If a high fire request is generated, then open coil 22 is energized. The feedback voltage at feedback node 24 is monitored to determine if it is still changing. If it is, then the motor shaft (as well as the damper or fuel valve) is still moving and burner controller 12 exits to wait until it is no longer moving. This is shown by blocks 40, 42, 44, and 46. However, if the feedback voltage at feedback node 34 is no longer changing, then high fire end switch 20 has opened causing the motor shaft in motor 16 (and the corresponding damper or fuel valve) to stop. In that case, burner controller 12 reads the feedback voltage at feedback node 34 and compares it with an expected high fire calibration voltage. A reasonable tolerance is allowed when preforming this comparison, to avoid nuisance shutdowns. However, if the feedback voltage at node 34 is not within the tolerance, then either the motor stopped at an incorrect position which would indicate that the mechanical endstops are not properly adjusted, or feedback circuit 30 has failed. In either case, burner controller 12 will shutdown the heating system and activate an alarm. This is indicated in blocks 48, 50 and 52.
If, at block 40, burner controller 12 does not issue a high fire request, it may either issue a low fire request or a modulation request which does not require the damper or fuel valve to go to either the high fire or the low fire position. In that case, the damper or fuel valve is simply modulated. This is indicated in blocks 54 and 56.
If, on the other hand, a low fire request is issued, operation is similar to that when a high fire request is issued. Close coil 26 is energized and the feedback voltage at feedback node 34 is monitored to determined when it stops changing. When it does, that indicates that the motor shaft has rotated to the low fire position and the feedback voltage at feedback node 34 is read by burner controller 12. The feedback voltage is then compared with an expected low fire calibration voltage to determine whether it is within an allowed tolerance. If not, as in the case of a high fire request, either the mechanical endstop or feedback circuit 30 has malfunctioned and a safety shutdown state is entered. This is indicated in blocks 58, 60, 62 and 64.
Total tolerance can build up in monitoring system 10 which can lead to the selected damper or fuel valve travelling an unacceptably short or long distance. Therefore, a total travel test is imposed on monitoring system 10. In this preferred embodiment, the total travel test is designed to ensure that the selected damper or fuel valve travels a minimum of 75° between the low fire and high fire positions and a maximum of 105°.
There are a predetermined number of steps which correspond to damper positions between these low fire and high fire positions. Each step corresponds to a feedback voltage from feedback terminal 34. Controller 12 subtracts the feedback voltage read from feedback terminal 34 during the most recent low fire positioning from the feedback voltage read at feedback terminal 34 during the most recent high fire positioning. Based upon this difference and upon an initial default unit step size, burner controller 12 determines the total number of degrees which the selected damper or fuel valve must travel in order to move from the low fire position to the high fire position. If it does not meet the minimum travel distance, a safety shutdown state is entered. This is indicated in block 66 and block 68. However, if the minimum travel distance is met, burner controller 12 runs a recalibration routine. Tolerance buildup and wear over time can cause a wide swing in the relationship between the feedback voltage seen at feedback node 34 and the angle of the motor shaft in motor -6. In this preferred embodiment, position accuracy is maintained by recalibrating a position equation used by burner controller 12 in positioning the motor shaft. Each time the motor shaft travels either to the high fire or to the low fire position (assuming the feedback voltage is within the tolerance window and satisfies the total travel test), a high fire and low fire voltage are set to equal the feedback voltage monitored at node 34 during the corresponding high or low fire position. The volts per unit step used to position the motor shaft in motor 16 is then calculated as follows: ##EQU1##
This active calibration assures position accuracy until either the feedback voltages read during the high fire or low fire positions fall outside of the tolerance window at which time the system is determined to be unreliable and is shutdown or, until the damper fails to meet the total travel test.
It should be noted that feedback circuit 30 need not be a potentiometer but could be another position detection means. For example, an optical encoder could be used instead of a feedback potentiometer. Voltage at feedback node 34 would then be replaced with counts. However, the concept remains unchanged.
CONCLUSION
This method of position control provides a cross check between mechanical endstops and electrical feedback position detection. This enhances system safety with respect to motor positioning errors.
Additionally, active calibration is used to assure position accuracy of the damper or fuel valve. Also a total travel test is used to assure that the damper travelled more than a minimum threshold distance between low fire and high fire positions but less than a maximum threshold distance. This ensures a sufficient amount of air flow to the combustion chamber in the heating system for safe operation.
Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention.
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Damper position of a damper in a heating system is monitored. The damper is movable between end positions in response to movement of a motor shaft. The motor shaft moves in response to a movement request signal. A shaft position signal is received by a position detector and has a value representative of position of the motor shaft. When the damper reaches an end position, it is determined whether the value of the shaft position signal is within a predetermined tolerance. If it is outside of the tolerance, then the system is shut down as unreliable; otherwise, the shaft position signal is recalibrated to maintain accuracy.
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[0001] The present invention provides novel compounds, novel compositions, method of their use and methods of their manufacture, such compounds generally useful pharmacologically as agents in those disease states alleviated by the alteration of mitogen activated signalling pathways in general, and in particular in the inhibition or antagonism of protein kinases, which pathologically involve aberrant cellular proliferation, such disease states including tumor growth, restenosis, atherosclerosis, and thrombosis. In particular, the present invention relates to a series of substituted oxindole compounds, which exhibit protein tyrosine kinase and protein serinelthreonine kinase inhibition, and which are useful in protecting a patient undergoing chemotherapy from chemotherapy-induced alopecia.
BACKGROUND OF THE INVENTION
[0002] Cell growth, differentiation, metabolism and function are extremely tightly controlled in higher eukaryotes. The ability of a cell to rapidly and appropriately respond to the array of external and internal signals it continually receives is of critical importance in maintaining a balance between these processes (Rozengurt, Current Opinion in Cell Biology 1992, 4, 161-5; Wilks, Progress in Growth Factor Research 1990, 2, 97-111). The loss of control over cellular regulation can often lead to aberrant cell function or death, often resulting in a disease state in the parent organism.
[0003] The protein kinases represent a large family of proteins which play a central role in the regulation of a wide variety of cellular processes and maintaining control over cellular function (Hanks, et al., Science 1988, 241, 42-52). A partial list of such kinases includes ab1, ATK, bcr-ab1, Blk, Brk, Btk, c-kit, c-met, c-src, CDK1, CDK2, CDK4, CDK6, cRaf1, CSF1R, CSK, EGFR, ErbB2, ErbB3, ErbB4, ERK, Fak, fes, FGFR1, FGFR2, FGFR3, FGFR4, FGFR5, Fgr, FLK4, fit-1, Fps, Frk, Fyn, Hck, IGF-1R, INS-R, Jak, KDR, Lck, Lyn, MEK, p38, PDGFR, PIK, PKC, PYK2, ros, tie 1 , tie 2 , TRK, Yes, and Zap70.
[0004] One of the most commonly studied pathways involving kinase regulation is cellular signalling from receptors at the cell surface to the nucleus (Crews and Erikson, Cell 1993, 74, 21′,-7). One example of this pathway includes a cascade of kinases in which members of the Growth Factor receptor Tyrosine Kinases (such as EGF-R, PDGF-R, VEGF-R, IGF1-R, the Insulin receptor), deliver signals through phosphorylation to other kinases such as Src Tyrosine kinase, and the Raf, Mek and Erk serine/threonine kinase families (Crews and Erikson, Cell 1993, 74, 215-7; IhIe, et al., Trends in Biochemical Sciences 1994, 19, 222-7). Each of these kinases is represented by several family members (Pelech and Sanghera, Trends in Biochemical Sciences 1992, 17, 233-8) which play related, but functionally distinct roles. The loss of regulation of the growth factor signalling pathway is a frequent occurence in cancer as well as other disease states.
[0005] The signals mediated by k,inases have also been shown to control growth, death and differentiation in the cell by regulating the processes of the cell cycle (Massague and Roberts, Current Opinion in Cell Biology 1995, 7, 769-72). Progression through the eukaryotic cell cycle is controlled by a family of kinases called cyclin dependent kinasies (CDKs) (Myerson, et al., EMBO Journal 1992, 11, 2909-17). The regulation of CDK activation is complex, but requires the association of the CDK with a member of the cyclin family of regulatory subunits (Draetta, Trends in Cell Biology 1993, 3, 287-9; Murray and Kirschner, Nature 1989, 339, 275-80; Solomon, et al., Molecular Biology of the Cell. 1992, 3, 13-27). A further level of regulation occurs through both activating and inactivating phosphorylations of the CDK subunit (Draetta, Trends in Cell Biology 1993, 3, 287-9; Murray and Kirschner, Nature 1989, 339, 275480; Solomon, et al., Molecular Biology of the Cell 1992, 3, 13-27; Ducommun, et al., EMBO Journal 1991, 10, 3311-9; Gautier, et al., Nature 1989, 339, 626-9; Gould and Nurse, Nature 1989, 342, 39-45; Krek and Nigg, EMBO Journal 1991, 10, 333141; Solomon, et al., Cell 1990, 63, 1013-24). The coordinate activation and inactivation of different cyclin/CDK complexes is necessary for normal progression through the cell cycle (Pines, Trends in Biochemical Sciences 1993, 18, 195-7; Sherr, Cell 1993, 73, 1059-65). Both the critical G1-S and G2-M transitions are controlled by the activation of different cyclin/CDK activities. In G1, both cyclin D/CDK4 and cyclin E/CDK2 are thought to mediate the onset of S-phase (Matsushime, et al., Molecular & Cellular Biology 1994, 14, 2066-76; Ohtsubo and Roberts, Science 1993, 259, 1908-12; Quelle, et al., Genes & Development 1993, 7, 15591-71; Resnitzky, et al., Molecular & Cellular Biology 1994, 14, 1669-79). Progression through S-phase requires the activity of cyclin A/CDK2 (Girard, et al., Cell 1991, 67, 1169-79; Pagano, et al., EMBO Journal 1992, 11, 961-71; Rosenblatt, et al., Proceedings of the National Academy of Science USA 1992, 89, 2824-8; Walker and Mailer, Nature 1991, 354, 314-7; Zindy, et al., Biochemical & Biophysical Research Communications 1992, 182, 1144-54) whereas the activation of cyclin A/cdc2 (CDK1) and cyclin B/cdc2 are required for the onset of metaphase (Draetta, Trends in Cell Biology 1993, 3, 287-9; Murray and Kirschner, Nature 1989, 339, 275-80; Solomon, et al., Molecular Biology of the Cell. 1992, 3, 13-27; Girard, et al., Cell 1991, 67, 1169-79; Pagano, et al., EMBO Journal 1992, 11, 961-71; Rosenblatt, et al., Proceedings of the National Academy of Science USA 1992, 89, 2824-8; Walker and Mailer, Nature 1991, 354, 314-7; Zindy, et al., Biochemical & Biophysical Research Communications 1992, 182, 1144-54). It is not surprising, therefore, that the loss of control of CDK regulation is a frequent event in hyperproliferative diseases and cancer. (Pines, Current Opinion in Cell Biology 1992, 4, 144-8; Lees, Current Opinion in Cell Biology 1995, 7, 773-80; Hunter and Pines, Cell 1994, 79, 573-82). The selective inhibition of CDKs is therefore an object of the present invention.
[0006] The compounds of the present invention are additionally useful in the treatment of one or more diseases afflicting mammals which are characterized by cellular proliferation in the areas of blood vessel proliferative disorders, fibrotic disorders, mesangial cell proliferative disorders and metabolic diseases. Blood vessel proliferative disorders include arthritis and restenosis. Fibrotic disorders include hepatic cirrhosis and atherosclerosis. Mesangial cell proliferative disorders incilude glomerulonephritis, diabetic nephropathy, malignant nephrosclerosis, thrombotic microangiopathy syndromes, organ transplant rejection and glomerulopathies. Metabolic disorders include psoriasis, diabetes mellitus, chronic wound healing, inflammation, neurodegenerative diseases, macular degeneration, and diabetic retinopathy.
[0007] Inhibitors of kinases involved in mediating or maintaining these disease states represent novel therapies for these disorders. Examples of such kinases include, but are not limited to: (1) inhibition of c-Src (Brickell, Critical Reviews in Oncogenesis 1992, 3, 40146; Courtneidge, Seminars in Cancer Biology 1994. 5, 23946), raf (Powis, Pharmacology & Therapeutics 1994, 62, 57-95) and the cyclindependent kinases (C;DKs) 1, 2 and 4 in cancer (Pines, Current Opinion in Cell Biology 1992, 4, 144-8; Lees, Current Opinion in Cell Biology 1995, 7, 773-80; Hunter and Pines, Cell 1994, 79, 573-82), (2) inhibition of CDK2 or PDGF-R kinase in restenosis (Buchdunger, et al., Proceedings of the National Academy of Science USA 1995, 92, 2258-62), (3) inhibition of CDK5 and GSK3 kinases in Alzheimers (Hosoi, et al., Journal of Biochemistry (Tokyo) 1995, 117, 741-9; Aplin, et al., Journal of Neurochemistry 1996, 67, 699-707), (4) inhibition of c-Src kinase in osteoporosis (Tanaka, et al., Nature 1996, 383, 528-31), (5) inhibition of GSK-3 kinase in type-2 diabetes (Borthwick, et al., Biochemical & Biophysical Research Communications 1995, 210, 73845); (6) inhibition of the p38 kinase in inflammation (Badger, et al., The Journal of Pharmacology and Experimental Therapeutics 1996, 279, 145361); (7) inhibition of VEGF-R 1-3 and TIE-1 and -2 kinases in diseases which involve angiogenesis (Shawver, et al., Drug Discovery Today 1997, 2, 50-63); (8) inhibition of UL97 kinase in viral infections (He, et al., Journal of Virology 1997, 71, 40511); (9) inhibition of CSF-1 R kinase in bone and hematopoetic (diseases (Myers, et al., Bioorganic & Medicinal Chemistry Letters 1997, 7, 4214), and (10) inhibition of Lck kinase in autoimmune diseases and transplant rejection (Myers, et al., Bioorganic & Medicinal Chemistry Letters 1997, 7, 417-20).
[0008] It is additionally possible that inhibitors of certain kinases may have utility in the treatment of diseases when the kinase is not misregulated, but is nonetheless essential for maintenance of the disease state. In this case, inhibition of the kinase activity would act either as a cure or palliative for these diseases. For example, many viruses, such as human papilloma virus, disrupt the cell cycle and drive cells into the S-phase of the cell cycle (Vousden, FASEB Journal 1993, 7, 872-9). Preventing cells from entering DNA synthesis after viral infection by inhibition of essential S-phase initiating activities such as CDK2, may disrupt the virus life cycle by preventing virus replication. This same principle may be used to protect normal cells of the body from toxicity of cycle-specific chemotherapeutic agents (Stone, et al., Cancer Research 1996, 56, 3199-202; Kohn, et al., Journal of Cellular Biochemistry 1994, 54, 440-52). Inhibition of CDKs 2 or 4 will prevent progression into the cycle in normal cells and limit the toxicity of c,Aotoxics which act in S-phase, G2 or mitosis. Furthermore, CDK2/cyclin E activity has also been shown to regulate NF-kB: Inhibition of CDK2 activity stimulates NF-kB-dependent gene expression, an event mediated through interactions with the p300 coactivator (Perkins, et al., Science 1997, 275, 523-7). NF-kB regulates genes involved in inflammatory responses, (such as hematopoietic growth factors chemokines and leukocyte adhesion molecules) (Baeuerde and Henkel, Annual Review of Immunology 1994, 12, 141-79) and may be involved in the suppression of apoptotic signals within the cell (Beg and Baltirnore, Science 1996, 274, 7824; Wang, et al., Science 1996, 274, 784-7; Van Antwerp, et al., Science 1996, 274, 787-9). Thus, inhibition of CDK2 may suppress apoptosis induced by cytotoxic drugs via a mechanism which involves NF-kB. This therefore suggests that inhibition of CDK2 activity may also have utility in other cases where regulation of NF-kB plays a role in etiology of disease. A further example may be taken from fungal infections: Aspergillosis is a common infection in immuneompromised patients (Armstrong, Clinical Infectious Diseases 1993, 16, 1-7). Inhibition of the Aspergillus kinases Cdc2/CDC28 or Nim A (Osmani, et al., EMBO Journal 1991, 10, 2669-79; Osmani, et al., Cell 1991, 67, 283-91) may cause arrest or death in the fungi, improving the therapeutic outcome for patients with these infections.
SUMMARY OF THE INVENTION
[0009] In brief summary, the invention comprises compounds of the formula (I):
[0010] wherein
[0011] X is N, CH, CCF 3 , or C(C 1-12 aliphatic);
[0012] R 1 is hydrogen, C 1-12 aliphatic, thiol, hydroxy, hydroxy-C 1-12 aliphatic, Aryl, Aryl-C 1-12 aliphatic, R 6 -Aryl-C 1-12 aliphatic, Cyc, Cyc-C 1-6 aliphatic, Het, Het-C 1-12 aliphatic, C 1-12 alkoxy, Aryloxy, amino, C 1-12 aliphatic amino, di-C 1-12 aliphatic amino, di-C 1-12 aliphatic aminocarbonyl, di-C 1-12 aliphatic aminosulfonyl, C 1-12 alkoxycarbonyl, halogen, cyano, sulfonamide, or nitro, where R 6 , Aryl, Cyc and Het are as defined below;
[0013] R 2 is hydrogen, C 1-12 aliphatic, N-hydroxyimino-C 1-12 aliphatic, C 1-12 alkoxy, hydroxy-C 1-12 aliphatic, C 1-12 alkoxycarbonyl, carboxyl C 1-12 aliphatic, Aryl, R 6 -Aryl-oxycarbonyl, R 6 -oxycarbponyl-Aryl, Het, aminocarbonyl, C 1-12 aliphatic-aminocarbonyl, Aryl-C 1-12 aliphatic-aminocarbonyl, R 6 -Aryl-C 1-12 aliphatic-aminocarbonyl, Het-C 1-12 aliphatic-aminocarbonyl, hydroxy-C 1-12 aliphatic-aminocarbonyl, C 1-12 -alkoxy-C 1-12 aliphatic-aminocarbonyl, C 1-12 alkoxy-C 1-12 aliphatic-amino, di-C 1-12 aliphatic amino, di-C 1-12 aliphatic aminocarbonyl, di-C 1-12 aliphatic aminosulfonyl, halogen, hydroxy, nitro, C 1-12 aliphatic-sulfonyl, aminosulfonyl, or C 1-12 aliphatic-aminosulfonyl, where Aryl and Het are as defined below;
[0014] further wherein R 1 and R 2 are optionally joined to form a fused ring, said fused ring selected from the group as defined for Het below, or any of said fused rings optionally substituted by C 1-12 aliphatic, halogen, nitro, cyano, C 1-12 alkoxy, carbonyl-C 1-12 alkoxy or oxo;
[0015] R 3 is hydrogen, C 1-12 aliphatic, hydroxy, hydroxy C 1-12 aliphatic, di-C 1-12 aliphatic amino, di-C 1-12 aliphatic aminocarbonyl, di-C 1-12 aliphatic aminosulfonyl, C 1-12 alkoxy, Aryl, Aryloxy, hydroxy-Aryl, Het, hydroxy-Het, Het-oxy, or halogen, where Aryl and Het are as defined below;
[0016] further wherein R 2 and R 3 are optionally joined to form a fused ring, said fused ring selected from the group as defined for Het below, or any of said fused rings optionally substituted by C 1-6 aliphatic or C, aliphatic-carbonyl;
[0017] with the proviso that R 1 , R 2 , and R 3 cannot simultaneously be H;
[0018] R 4 is sulfonic acid, C 1-12 aliphatic-sulfonyl, sulfonyl-C 1-12 aliphatic, C 1-12 aliphatic-sulfonyl-C 1-6 aliphatic, C 1-6 aliphatic-amino, R 7 -sulfonyl, R 7 -sulfonyl -C 1-12 aliphatic, R 7 -aminosulfonyl, R 7 -aminosulfonyl-C 1-12 aliphatic, R 7 -sulfonylamino, R 7 -sulfonylamino-C 1-12 aliphatic, aminosulfonylamino, di-C 1-12 aliphatic amino, di-C 1-12 aliphatic aminocarbonyl, di-C 1-12 aliphatic aminosulfonyl, di-C 1-12 aliphatic amino, di-C 1-12 aliphatic aminocarbonyl, di-C 1-12 aliphatic aminosulfonyl-C 1-12 aliphatic, (R 8 ) 1-3 -Arylamino, (R 8 ) 1-3 -Arylsulfonyl, (R 8 ) 1-3 -Aryl-aminosulfonyl, (R 8 ) 1-3 -Aryl-sulfonylamino, Het-amino, Het-sulfonyl, Het-aminosulfonyl, aminoiminoamino, or aminoiminoaminosulfonyl, where R 7 , R 8 , Aryl and Het are as defined below;
[0019] R 5 is hydrogen;
[0020] and further wherein R 4 and R 5 are optionally joined to form a fused ring, said ring selected from the group as defined for Het below, or any of said used rings optionally substituted by C 1-12 aliphatic, oxo or dioxo;
[0021] R 6 is C 1-12 aliphatic, hydroxy, C 1-12 alkoxy, or halogen;
[0022] R 7 is hydrogen, C 1-12 aliphatic, C 1-12 alkoxy, hydroxy-C 1-12 alkoxy, hydroxy-C 1-12 aliphatic, carboxylic acid, C 1-12 aliphatic-carbonyl, Het, Het-C 1-12 -aliphatic, Het-C 1-12 -alkoxy, di-Het-C 1-12 -alkoxy Aryl, Aryl-C 1-12 -aliphatic, Aryl-C 1-12 -alkoxy, Aryl-carbonyl, C 1-18 alkoxyalkoxyallcoxyalkoxyaliphatic,or hydroxyl where Het and Aryl are as defined below;
[0023] R 8 is hydrogen, nitro, cyano, C 1-12 alkoxy, halo, carbonyl-C 1-12 alkoxy or halo-C 1-12 aliphatic;
[0024] Aryl is phenyl, naphthyl, pherianthryl or anthracenyl;
[0025] Cyc is cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, any one of which may have one or more degrees of unsaturation;
[0026] Het is a saturated or unsaturated heteroatom ring system selected from the group consisting of benzimidaezole, dihydrothiophene, dioxin, dioxane, dioxolane, dithiane, dithiazine, dithiazole, dithiolane, furan, imidazole, isoquinoline, morpholine, oxazole, oxadiazole, oxathiazole, oxathiazolidine, oxazine, oxadiazine, piperazine, piperadine, pyran, pyrazine, pyrazole, pyridine, pyrimidine, pyrrole, pyrrolidine, quinoline, tetrahydrofuran, tetrazine, thidiazine, thiadiazole, thiatriazole, thiazine, thiazole, thiomorpholine, thiophene, thiopyran, triazine and triazole, with the proviso that when R 2 is thiadiazine, then R 4 cannot be methylsulfone;
[0027] and the pharmaceutically acceptable salts, biohydrolyzable esters, biohydrolyzable amides, biohydrolyzable carbamates solvates, hydrates, affinity reagents or prodrugs thereof in either crystalline or amorphous form.
[0028] A more preferred genus of compounds of the present invention includes compounds of formula (1), defined as follows:
[0029] wherein
[0030] X is N, CH, or C(C 1-6 aliphatic); R 1 is hydrogen, C 1-6 aliphatic, hydroxy-C 1-6 aliphatic, Aryl-C 1-6 aliphatic, R 6 -Aryl-C 1-6 aliphatic, Cyc-C 1-6 aliphatic, Het-C 1-6 aliphatic, C 1-6 alkoxy, Aryloxy, aminocarbonyl, di-C 1-6 aliphatic amino, di-C 1-6 aliphatic aminocarbonyl, di-C 1-6 aliphatic aminosulfonyl, C 1-6 alkoxycarbonyl, halogen, or nitro, where R 6 , Aryl, Cyc and Het are as defined below;
[0031] R 2 is hydrogen, C 1-6 aliphatic, R 7 -C 1-6 aliphatic, C 1-6 alkoxy, hydroxy-C 1-6 aliphatic, C 1-6 alkoxycarbonyl, carboxyl C 1-6 aliphatic, Aryl, R 6 -Ary-oxycarbonyl, R 6 -oxycarbonyl-Aryl, Het, aminocarbonyl, C 1-6 aliphatic-aminocarbonyl, Aryl-C 1-6 aliphatic-aminocarbonyl, R 6 -Aryl-C 1-6 aliphatic-aminocarbonyl, Het-C 1-6 aliphatic-aminocarbonyl, hydroxy-C 1-6 aliphatic-aminocarbonyl, C 1-6 -alkoxy-C 1-6 aliphatic-aminocarbonyl, C 1-6 alkoxy-C 1-6 aliphatic-amino, di-C 1-6 aliphatic amino, di-C 1-6 aliphatic aminocarbonyl, di-C 1-6 aliphatic aminosulfonyl, halogen, hydroxy, nitro, sulfo, C 1-6 aliphatic-sulfonyl, aminosulfonyl, C 1-6 aliphatic-aminosulfonyl, or quaternary ammonium, where R 7 , Aryl and Het are as defined below;
[0032] further wherein R 1 and R 2 are optionally joined to form a fused ring, said fused ring selected from the group as defined for Het above, or any of said fused rings optionally substituted by halogen or oxo;
[0033] R 3 is hydrogen, C 1-6 aliphatic, hydroxy, hydroxy C 1-6 aliphatic, di-C 1-6 aliphatic amino, di-C 1-6 aliphatic aminocarbonyl, di-C 1-6 aliphatic aminosulfonyl, C 1-6 alkoxy, Aryl, Aryloxy, hydroxy-Aryl, Het, hydroxy-Het, Het-oxy, or halogen, where Aryl and Het are as defined below;
[0034] further wherein R 2 and R 3 are optionally joined to form a fused ring, said fused ring selected from the group as defined for Het above, or any of said fused rings optionally substituted by C 1-6 aliphatic or C 1-6 aliphatic-carbonyl; with the proviso that R 1 , R 2 and R 3 cannot simultaneously be H; R 4 is sulfonic acid, C 1-12 aliphiatic-sulfonyl, sulfonyl-C 1-12 aliphatic, C 1-12 aliphatic-sulfonyl-C 1-6 aliphatic, C 1-6 aliphatic-amino, R 7 -sulfonyl, R 7 -sulfonyl-C 1-12 aliphatic, R 7 -aminosulfonyl, R 7 -aminosulfonyl-C 1-12 aliphatic, R 7 -sulfonylamino, R 7 -sulfonylamino-C 1-12 aliphatic, aminosulfonylamino, di-C 1-12 aliphatic amino, di-C 1-12 aliphatic aminocarbonyl, di-C 1-12 aliphatic aminosulfonyl, di-C 1-12 aliphatic amino, di-C 1-12 aliphatic arminocarbonyl, di-C 1-12 aliphatic aminosulfonyl-C 1-12 aliphatic, (R 8 ) 1-3 -Arylamino, (R 8 ) 1-3 -Arylsulfonyl, (R 8 ) 1-3 -Aryl-aminosulfonyt, (R 8 ) 1-3 -Aryl-sulfonylamino, Het-amino, Het-sulfonyl, Het-aminosulfonyl aminoiminoamino, or aminoiminoaminosulfonyl, where R 7 , R 8 , Aryl and Het are as defined below;
[0035] R 5 is hydrogen;
[0036] and further wherein R 4 and R 5 are optionally joined to form a fused ring, said ring selected from the group as defined for Het above, or any of said used rings optionally substituted by oxo or dioxo;
[0037] R 6 is hydrogen, C 1-6 aliphatic, hydroxy, C, alkoxy, or halogen;
[0038] R 7 is hydrogen, C 1-12 aliphatic, C 1-12 alkoxy, hydroxy-C 1-12 alkoxy, hydroxy-C 1-12 aliphatic, carboxylic acid, C 1-12 aliphatic-carbonyl, Het, Het-C 1-12 -aliphatic, Het-C 1-12 -alkoxy, di-Het-C 1-12 -alkoxy Aryl, Aryl-C 1-12 -aliphatic, Aryl-C 1-12 -alkoxy, Aryl-carbonyl, C 1-18 alkoxyalkoxyalkoxyalkoxyaliphatic, or hydroxyl where Het and Aryl are as defined below;
[0039] R 8 is hydrogen or halo-C 1-6 aliphatic;
[0040] Aryl is phenyl, or naphthyl;
[0041] Cyc is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, any one of which may have one or more degrees of unsaturation;
[0042] Het is a saturated or unsaturated heteroatom ring system selected from the group consisting of benzimidazole, dihydrothiophene, dioxin, dioxane, dioxolane, dithiane, dithiazine, dithiazole, dithiolane, furan, imidazole, morpholine, oxazole, oxadiazole, oxathiazole, oxathiazolidine, oxazine, oxadiazine, piperazine, piperadine, pyran, pyrazine, pyrazole, pyridine, pyrimidine, pyrrole, pyrrolidine, tetrahydrofuran, tetrazine, thiadiazine, thiadiazole, thiatriazole, thiazine, thiazole, thiomorpholine, thiophene, thiiopyran, triazine and triazole with the proviso that when R 2 is thiadiazine, then R 4 cannot be methylsulfone; and the pharmaceutically acceptable salts, biohydrolyzable esters, biohydrolyzable amides, biohydrolyzable cart,amates, solvates, hydrates, affinity reagents or prodrugs thereof in either crystalline or amorphous form.
[0043] A highly preferred genus of compounds of the present invention includes compounds of formula (I), defined as follows:
[0044] wherein
[0045] X is N, CH, or CCH 3 ;
[0046] R 1 is hydrogen, C 1-6 aliphatic, hydroxy-C 1-6 aliphatic, di-C 1-6 aliphatic amino, di-C 1-6 aliphatic aminocarbonyl, di-C 1-6 aliphatic aminosulfonyl, Aryl-C 1-6 aliphatic, R 6 -Aryl-C 1-6 aliphatic, Cyc-C 1-6 aliphatic, Het-C 1-6 aliphatic, C 1-6 alkoxy, Aryloxy, aminocarbonyl, C 1-6 alkoxycirbonyl, halogen, or nitro, where R 6 , Aryl, Cyc and Het are as defined below;
[0047] R 2 is hydrogen, C 1-6 aliphatic, N-hydroxyimino-C 1-6 aliphatic, C 1-6 alkoxy, C 1-6 alkoxycarbonyl, Aryl, R 6 -Aryloxycarbonyl, Het, aminocarbonyl, C 1-6 aliphatic aminocarbonyl, Aryl-C 1-6 aliphatic aminocarbonyl, R 6 -Aryl-C 1-6 aliphatic aminocarbonyl, Het-C 1-6 aliphatic aminocarbonyl, di-C 1-6 aliphatic amino, di-C 1-6 aliphatic aminocarbonyl, di-C 1-6 aliphatic aminosulfonyl, hydroxy-C 1-6 aliphatic aminocarbonyl, C 1-6 -alkoxy-C 1-6 aliphatic aminocarbonyl, C 1-6 alkoxy-C 1-6 aliphatic amino, halogen, hyciroxy, nitro, C 1-6 aliphatic sulfonyl, or aminosulfonyl, C 1-6 aliphatic aminosulfonyl, where Aryl and Het are as defined below;
[0048] further wherein R 1 and R 2 are optionally joined to form a fused ring, said fused ring selected from the group as defined for Het below, or any of said fused rings optionally substituted by halaogen or oxo;
[0049] R 3 is hydrogen, C 1-6 aliphatic, hydroxy, hydroxy C 1-6 aliphatic, di-C 1-6 aliphatic amino, di-C 1-6 aliphatic aminocarbonyl, di-C 1-6 aliphatic aminosulfonyl C 1-6 alkoxy, Aryloxy, Het, or halogen, where Aryl and Het are as defined below; further wherein R 2 and R 3 are optionally joined to form a fused ring, said fused ring selected from the group as defined for Het below, or any of said fused rings optionally substituted by C 1-6 alkyl or C 1-6 alkylcarbonyl;
[0050] with the proviso that R 1 , R 2 and R 3 cannot simultaneously be H;
[0051] R 4 is R 7 -sulfonyl, R 7 -sulfonyl C 1-6 -aliphatic, C 1-6 aliphatic sulfonyl-C 1-6 aliphatic, R 7 -aminosulfonyl, di-C 1-6 aliphatic amino, di-C,6 aliphatic aminocarbonyl, di-C 1-6 aliphatic aminosulfonyl, di-C 1-6 aliphatic aminosulfonyl-C 1-6 aliphatic, R 7 -aminosulfonyl C 1-6 aliphatic, aminosulfonylamino, R 7 -C 1-6 aliphatic aminosulfonyl-C 1-6 aliphatic, Aryl, Het, R 8 -Aryl-aminosulfonyl, Het-aminosulfonyl, or aminoiminoaminosulfonyl, where R 7 , R 8 , Aryl and Het are as defined below;
[0052] R 5 is hydrogen;
[0053] and further wherein R 4 and R 5 are optionally joined to form a fused ring, said ring selected from the group as defined for Het below, or any of said used rings optionally substituted by oxo or dioxo;
[0054] R 6 is hydroxy, C 1-6 alkoxy, or halogen;
[0055] R 7 is hydrogen, C 1-6 aliphatic, hydroxy C 1-6 -alkoxy, hydroxy-C 1-6 aliphatic, C 1-6 aliphatic carbonyl, Aryl-carbonyl, C 1-12 alkoxyalkoxyalkoxyalkoxyalkyl, hydroxyl, Aryl, Aryl-C 1-6 -alkoxy, Aryl-C 1-6 -aliphatic, Het, Het-C 1-6 -alkoxy, di-Het-C 1-6 -alkoxy, Het-C 1-6 -aliphatic, di-Het-C 1-6 -aliphatic;
[0056] R 8 is trifluoromethyl;
[0057] Aryl is phenyl;
[0058] Cyc is cyclobutyl;
[0059] Het is a saturated or unsaturated heteroatom ring system selected from the group consisting of benzimidazole, dihydrothiophene, dioxolane, furan, imidazole, morpholine, oxazole, pyridine, pyrrole, pyrrolidine, thiadiazole, thiazole, thiophene, and triazole, with the proviso that when R 2 is thiadiazine, then R 4 cannot be methylsulfone;
[0060] and the pharmaceutically acceptable salts, biohydrolyzable esters, biohydrolyzable amides, biohydrolyzable carbamates, solvates, hydrates, affinity reagents or prodrugs thereof in either crystalline or amorphous form.
[0061] A preferred group of compounds of the present invention with respect to the substitutions at R 4 are compounds of formula (I):
[0062] wherein
[0063] X is NH;
[0064] R 1 is hydrogen, C 1-12 aliphatic, thiol, hydroxy, hydroxy-C 1-12 aliphatic, Aryl, Aryl-C 1-12 aliphatic, R 6 -Aryl-C 1-12 aliphatic, Cyc, Cyc-C 1-12 aliphatic, Het, Het-C 1-12 aliphatic, C 1-12 alkoxy, Aryloxy, amino, C 1-12 aliphatic amino, di-C 1-12 aliphatic aminocarbonyl, di-C 1-12 aliphatic aminosulfonyl, C 1-12 .alkoxycarbonyl, halogen, cyano, sulfonamide, or nitro, where R 6 , Aryl, Cyc and Het are as defined below;
[0065] R 2 is hydrogen, C 1-12 aliphatic, N-hydroxyimino-C 1-12 aliphatic, C 1-12 alkoxy, hydroxy-C 1-12 aliphatic, C 1-12 ialkoxycarbonyl, carboxyl C 1-12 aliphatic, Aryl, R 6 -Aryl-oxycarbonyl, R 6 -oxycarbonyl-Aryl, Het, aminocarbonyl, C 1-12 aliphatic-aminocarbonyl, Aryl-C 1-12 aliphatic-aminocarbonyl, R 6 -Aryl-C 1-12 aliphatic-aminocarbonyl, Het-C 1-12 aliphatic-aminocarbonyl, hydroxy-C 1-12 aliphatic-aminocarbonyl, C 1-12 -alkoxy-C 1-12 aliphatic-aminocarbonyl, C 1-12 alkoxy-C 1-12 aliphatic-amino, di-C 1-12 aliphatic amino, di-C 1-12 aliphatic aminocarbonyl, di-C 1-12 aliphatic aminosulfonyl, halogen, hydroxy, nitro, C 1-12 aliphatic-sulfonyl, aminosulfonyl, or C 1-12 aliphatic-aminosulfonyl, where Aryl and Het are as defined below;
[0066] further wherein R 1 and R 2 are optionally joined to form a fused ring, said fused ring selected from the group as defined for Het below, or any of said fused rings optionally substituted by halogen, nitro, cyano, C 1-12 alkoxy, carbonyl-C 1-12 alkoxy or oxo;
[0067] R 3 is hydrogen, C 1-12 aliphatic, hydroxy, hydroxy C 1-12 aliphatic, di-C 1-12 aliphatic amino, di-C 1-12 aliphatic aminocarbonyl, di-C 1-12 aliphatic aminosulfonyl, C 1-12 alkoxy, Aryl, Aryloxy, hydroxy-Aryl, Het, hydroxy-Het, Hetoxy, or halogen, where Aryl and Het are as defined below;
[0068] further wherein R 2 and R 3 are optionally joined to form a fused ring, said fused ring selected from the group as defined for Het below, or any of said fused rings optionally substituted by C 1-6 aliphatic or C 1-6 aliphatic-carbonyl;
[0069] with the proviso that R 1 , R 2 and R 3 cannot simultaneously be H;
[0070] R 4 is R 7 -aminosulfonyl, R 7 -aminosulfonyl-C 1-12 aliphatic, R 7 -sulfonylamino, R 7 -sulfonylamino-C 1-12 aliphatic, aminosulfonylamino, di-C 1-12 aliphatic aminosulfonyl, di-C 1-12 aliphatic aminosulfonyl-C 1-12 aliphatic, (R 8 ) 1-3 -Aryl-aminosulfonyl,
[0071] (R 8 ) 1-3 -Aryl-sulfonylamino, or aminoiminoaminosulfonyl, where R 7 , R 8 , Aryl and Het are as defined below;
[0072] R 5 is hydrogen;
[0073] R 6 is C 1-12 aliphatic, hydroxy, C 1-12 alkoxy, or halogen;
[0074] R 7 is hydrogen, C 1-12 aliphatic, C 1-12 alkoxy, hydroxy-C 1-12 alkoxy, hydroxy-C 1-12 aliphatic, carboxylic acid, C 1-12 aliphatic-carbonyl, Het, Het-C 1-12 -aliphatic, Het-C 1-12 -alkoxy, di-Het-C 1-12 -alkoxy Aryl, Aryl-C 1-12 -aliphatic, Aryl-C 1-12 -alkoxy, Aryl-carbonyl, C 1-18 alkoxyalkoxyalkoxyalkoxyaliphatic,or hydroxyl where Het and Aryl are as defined below;
[0075] R 8 is hydrogen, nitro, cyano, C 1-12 alkoxy, halo, carbonyl-C 1-12 alkoxy or halo-C 1-12 aliphatic;
[0076] Aryl is phenyl, naphthyl, pheranthryl or anthracenyl; Cyc is cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, any one of which may have one or more degrees of unsaturation;
[0077] Het is a saturated or unsaturated heteroatom ring system selected from the group consisting of benzimidazole, dihydrothiophene, dioxin, dioxane, dioxolane, dithiane, dithiazine, dithiazole, dithiolane, furan, imidazole, morpholine, oxazole, oxadiazole, oxathiazole, oxathiazolidine, oxazine, oxadiazine, piperazine, piperadine, pyran, pyrazine, pyrazole, pyridine, pyrimidine, pyrrole, pyrrolidine, tetrahydrofuran, tetrazine, thiadiazine, thiadiazole, thiatriazole, thiazine, thiazole, thiomorpholine, thiophene, thiopyran, triazine and triazole with the proviso that when R 2 is thiadiazine, then R 4 cannot be methylsulfone;
[0078] and the pharmaceutically acceptable salts, biohydrolyzable esters, biohydrolyzable amides, biohydrolyzable carbamates solvates, hydrates, affinity reagents or prodrugs thereof in either crystalline or amorphous form.
[0079] Due to the presence of an oxindole exocyclic double bond, also included in the compounds of the invention are their respective pure E and Z geometric isomers as well as mixtures of E and Z isomers. The invention as described and claimed does not set any limiting ratios on prevalence of Z to E isomers. Thus compound number 104 in the tables below is disclosed and claimed as the E geometric thereof, the Z geometric isomer thereof and a mixture of the E and Z geometric isomers thereof, but not limited by any given ratio(s).
[0080] Likewise, it is understood that compounds of formula (I) may exist in tautomeric forms other than that shown in the formula.
[0081] Certain of the compounds as described will contain one or more chiral, or asymmetric, centers and will therefore be capable of existing as optical isomers that are either dextrorotatory or levorotatory. Also included in the compounds of the invention are the respective dextrorotatory or levorotatory pure preparations, and mixtures thereof.
[0082] Certain compounds of formula (I) above may exist in stereoisomeric forms (e.g. they may contain one or more asymmetric carbon atoms or may exhibit cis-trans isomerism). The individual stereoisomers (enanfiomers and diastereoisomers) and mixtures of these are included within the scope of the present invention. Likewise, it is understood that compounds of formula (I) may exist in tautomeric forms other than that shown in the formula and these are also included within the scope of the present invention.
[0083] The present invention also provides compounds of formula (I) and pharmaceutically acceptable salts thereof (hereafter identified as the “active compounds”) for use in medical therapy, and particularly in the treatment of disorders mediated by CDK2 activity, such as alopecia induced by cancer chemotherapy.
[0084] A further aspect of the invention provides a method of treatment of the human or animal body suffering from a disorder mediated by a mitogen activated protein kinase which comprises administering an effective amount of an active compound of formula (I) to the human or animal patient.
[0085] Another aspect of the present invention provides the use of an active compound of formula (I), in the preparation of a medicament for the treatment of malignant tumors, or for the treatment of alopecia induced by cancer chemotherapy or induced by radiation therapy. Alternatively, compounds of formula (I) can be used in the preparation of a medicament for the treatment of a disease mediated by a kinase selected from the group consisting of ab1, ATK, bcr-ab1, Blk, Brk, Btk, c-kit, c-met, c-src, CDK1, CDK2, CDK4, CDK6, cRaf1, CSF1R, CSK, EGFR, ErbB2, ErbB3, ErbB4, ERK, Fak, fes, FGFR1, FGFR2, FGFR3, FGFR4, FGFR5, Fgr, FLK4, fit-1, Fps, Frk, Fyn, Hck, IGF-1R, INS-R, Jak, KDR, Lck, Lyn, MEK, p38, PDGFR, PIK, PKC, PYK2, ros, tie 1 , tie 2 , TRK, Yes, and Zap70. Additionally, compounds of formula (I) can be used in the preparation of a medicament for the treatment of organ transplant rejection, of inhibiting tumor growth, of treating chemotherapy-induced alopecia, chemotherapy-induced thrombocytopenia or chemotherapy-induced leukopenia, or of treating a disease state selected from the group consisting of mucocitis, restenosis, atherosclerosis, rheumatoid arthritis, angiogenesis, hepatic cirrhosis, glomerulonephritis, diabetic niephropathy, malignant nephrosclerosis, thrombotic microangiopathy, a glomerulopathy, psoriasis, diabetes mellitus, inflammation, a neurodegenerative disease, macular degeneration, actinic keratosis and hyperproliferative disorders.
[0086] Another aspect of the present invention provides the use of an active compound of formula (I), in coadministration with previously known anti-tumor therapies for more effective treatment of such tumors.
[0087] Another aspect of the present invention provides the use of an active compound of formula (I) in the preparation of a medicament for the treatment of viral or eukaryotic infections.
[0088] Other aspects of the present invention related to the inhibition of mitogen activated protein kinases are discussed in more detail below.
[0089] Compounds we have synthesized as part of the present invention which are currently preferred are listed in Tables 1 and 2 below Compounds are identified by the numbers shown in the first column; variables below in the rest of the columns are with reference to the generic structure (I). Corresponding IUPAC nomenclature are disclosed in Table 2. Since all substituents at each point of substitution are capable of independent synthesis of each other, the tables are to be read as a matrix in which any combination of substituents is within the scope of the disclosure and claims of the invention.
TABLE 1 (I) Example R 1 R 2 1 —NO 2 H 2 —CONH 2 H 3 —CH(CH 3 ) 2 H 4 —CH 2 OH H 5 H 6 —CO 2 CH 2 CH 3 H 7 I H 8 —CH 2 CH(CH 3 ) 2 H 9 —CH═C(CH 3 ) 2 H 10 —CH═C(CH 3 )CH 2 CH 3 H and —CH 2 C(CH 3 )═CHCH 3 11 —CH 2 CH(CH 3 )CH 2 CH 3 H 12 H 13 H 14 H 15 H 16 H 17 OCH(CH 3 ) 2 H 18 H 19 H 20 H 21 H —NO 2 22 H —OH 23 H —CH 3 24 H 25 H —SO 3 − Na + 26 H —CONH 2 27 H —CO 2 CH 3 28 H Br 29 H I 30 H —SO 2 NH 2 31 H —SO 2 CH 3 32 H —SO 2 NHCH 3 33 H —C(═NOH)CH 3 34 H 35 H 36 H 37 H -phenyl 38 H —CON(CH 3 ) 2 39 H 40 H 41 H 42 H 43 H 44 H —CONH(CH 2 ) 2 OCH 3 45 H —CONH(CH 2 ) 2 OH 46 H —CONH(CH 2 ) 3 OH 47 H 48 H 49 H 50 H —OCH 3 51 H —NH 3 + Cl − 52 H H 53 H H 54 H H 55 H H 56 H H 57 H H 58 H H 59 —SCH═N— 60 —SCH═N— 61 —CH 3 —NO 2 62 —CH═NNH— 63 —NH—N═CH— 64 —N—N═NH— 65 —C(Cl)═NNH— 66 —C(O)NHCH2— 67 —SCH═N— 68 —CH═CHCH═N— 69 —SCH═N— 70 —SCH═N— 71 —SCH═N— 72 —SCH═N— 73 —SCH═N— 74 —SCH═N— 75 —SCH═N— 76 —SCH═N— 77 —SCH═N— 78 —SCH═N— 79 —SCH═N— 80 —SCH═N— 81 —SCH═N— 82 —SCH═N— 83 —SCH═N— 84 —SCH═N— 85 —SCH═N— 86 H —CH 3 87 H —NHCOCH 3 88 H —OCH 3 89 H —OH 90 H —N═C(CH 3 )O— 91 H —N(COCH 3 )(CH 2 ) 2 — 92 H —OCH 2 O— 93 H —NH 2 + (Br)(CH 2 ) 2 — 94 Cl —OCH 3 95 Cl —OH 96 —CH 3 —OH 97 H H 98 H H 99 —CH 3 —OH 100 H 101 —SCH═N— 102 —CH═CHCH═N— 103 H —CO 2 CH 2 CH(CH 3 ) 2 104 —SCH═N— Example R 3 R 4 R 5 X 1 H 4′-SO 2 NH 2 H N 2 H 4′-SO 2 NH 2 H N 3 H 4′-SO 2 NH 2 H N 4 H 4′-SO 2 NHCH 3 H CH 5 H 4′-SO 2 NH 2 H N 6 H 4′-SO 2 NH 2 H CH 7 H 4′-SO 2 NH 2 H N 8 H 4′-SO 2 NH 2 H N 9 H 4′-SO 2 NH 2 H N 10 H 4′-SO 2 NH 2 H N 11 H 4′-SO 2 NH 2 H N 12 H 4′-SO 2 NH 2 H N 13 H 4′-SO 2 NH 2 H N 14 H 4′-SO 2 NH 2 H N 15 H 4′-SO 2 NH 2 H N 16 H 4′-SO 2 NH 2 H N 17 H 4′-SO 2 NH 2 H N 18 H 4′-SO 2 NH 2 H N 19 H 4′-SO 2 NH 2 H CH 20 H 4′-SO 2 NH 2 H N 21 H 4′-SO 2 NH 2 H N 22 H 4′-SO 2 NH 2 H N 23 H 4′-SO 2 NH 2 H N 24 H 4′-SO 2 NHCH 3 H N 25 H 4′-SO 2 NH 2 H N 26 H 4′-SO 2 NHCH 3 H N 27 H 4′-SO 2 NH 2 H CH 28 H 4′-SO 2 CH 3 H N 29 H —NH—N═N— CH 30 H 4′-SO 2 NH 2 H N 31 H 4′-SO 2 NH 2 H N 32 H 4′-SO 2 NHCH 3 H N 33 H 4′-SO 2 NHCH 3 H N 34 H 4′-SO 2 NH 2 H CCH 3 35 H 4′-SO 2 N(CH 3 ) 2 H CH 36 H 4′-SO 2 NH 2 H N 37 H 4′-SO 2 NH 2 H CH 38 H 4′-SO 2 NH 2 H N 39 H 4′-SO 2 NH 2 H N 40 H 4′-SO 2 NH 2 H N 41 H 4′-SO 2 NH 2 H N 42 H 4′-SO 2 NH 2 H N 43 H 4′-SO 2 NH 2 H N 44 H 4′-SO 2 NH 2 H N 45 H 4′-SO 2 NH 2 H N 46 H 4′-SO 2 NH 2 H N 47 H 4′-SO 2 NH 2 H N 48 H 4′-SO 2 NH 2 H N 49 H 4′-SO 2 NH 2 H N 50 H 4′-SO 2 NH H N 51 H 4′-SO 2 NH H N 52 —CH 2 CH 3 4′-SO 2 NH 2 H N 53 H SO 2 OC 6 H 5 H CH 54 H 4′-NHSO 2 NH 2 H CH 55 —CH 2 OH 4′-SO 2 NH 2 H CH 56 Br 4′-SO 2 NH 2 H N 57 4′-SO 2 NH 2 H N 58 —OCH 2 CH 3 4′-SO 2 NH 2 H N 59 H 4′-SO 2 NH(CH 2 ) 2 O(CH 2 ) 2 OH H CH 60 H 4′-SO 2 NH(CH 2 ) 2 OH 2 H CH 61 H 4′-SO 2 NHCH 3 H N 62 H 4′-SO 2 NH 2 H N 63 H 4′-SO 2 NH 2 H N 64 H 4′-SO 2 NH 2 H N 65 H 4′-SO 2 NH 2 H N 66 H 4′-SO 2 NHCH 3 H N 67 H 4′-CH 2 SO 2 NHCH 2 C(CH 3 ) 2 CH 2 OH H CH 68 H 4′-CH 2 SO 2 NHCH 3 H N 69 H H CH 70 H H CH 71 H 4′-SO 2 NH-C(═NH)NH 2 H CH 72 H H CH 73 H —CH 2 SO 2 CH 2 — CH 74 H 4′-CH 2 SO 2 NH 2 H CH 75 H 4′-CH 2 SO 2 NHCH 2 CH═CH 2 H CH 76 H 4′-CH 2 SO 2 CH 3 H CH 77 H 4′-SO 2 NHCH 2 C(CH 3 ) 2 CH 2 OH H CH 78 H H CH 79 H H CH 80 H H CH 81 H 4′-SO 2 NHCOCH 3 H CH 82 H H CH 83 H 4′-SO 2 NHCH 3 H N 84 H 4′-SO 2 N(CH 3 )(CH 2 ) 2 O(CH 2 ) 2 OH H CH 85 H 4′-SO 2 NH[(CH 2 ) 2 O] 4 CH 3 H CH 86 —CH 3 4′-SO 2 NH 2 H N 87 —OH 4′-CH 2 SO 2 NHCH 3 H N 88 Cl 4′-SO 2 NH 2 H N 89 —CH(CH 3 ) 2 4′-SO 2 NH 2 H N 90 4′-SO 2 NH 2 H N 91 4′-SO 2 NH 2 H N 92 4′-SO 2 NH 2 H N 93 4′-SO 2 NH 2 H N 94 Cl 4′-CH 2 SO 2 NHCH 3 H N 95 —CH 3 4′-SO 2 NH 2 H N 96 —CH 3 4′-SO 2 NH 2 H N 97 H —NHN═CH— CH 98 H —CH═NNH— CH 99 —CH 3 4′-CH 2 SO 2 NHCH 3 H N 100 H 4′-CH 2 SO 2 NHCH 3 H CH 101 H —N═N—NH— CH 102 H 4′-SO 2 NH 2 H N 103 H 4′-SO 2 NH 2 H CH 104 H H CH
[0090] Standard accepted nomenclature corresponding to the Examples set forth in this specification are set forth below. In some cases nomenclature is given for one or more possible isomers.
[0091] Example 1: 4-[N′-(4-[Nitro-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z isomer).
[0092] Example 2: 2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2.3-dihydro-1H-indole-4-carboxylic acid amide (E isomer).
[0093] Example 3: 4-[N′-(4-Isopropyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z isomer).
[0094] Example 4: 4-[(4-Hydroxymethyl-2-oxo-1,2-dihydro-indol-3-ylidenemethyl)-amino]-N-methyl-benzenesulionamide (Z-isomer).
[0095] Example 5: 4N′-12-Oxo-4-(2-pyridin-4-yl-ethyl)1,2-dihydro-indol-3-ylidene]-hydrazino)benzenesulfonamide (Z isomer).
[0096] Example 6: 2-Oxo-3-(4-sulfamoyl-phenylamino-methylene)-2,3-dihydro-1H-indole-4-carboxylic acid ethyl ester (Z-isomer).
[0097] Example 7: 4-[N′-(4-Iodo-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z isomer).
[0098] Example 8: 4-[N′-(4-Isobutyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z-isomer).
[0099] Example 9: 4-{N′-[4-(2-M1-ethyl-propenyl)-2-oxo-1,2-dihydro-indol-3-ylidene]-hydrazino}benzenesulfonamide (Z-isomer).
[0100] Example 10: 4-{N′-[4-(2-Methyl-1-butenyl)2-oxo-1,2-dihydro-indol-3-ylidene]-hydrazino}-benzenesulfonamride and 4-{N′-[4-(2-methyl-2-butenyl 2-oxo-1,2-dihydro-indol-3-ylidene]-hydrazino}benzenesulfonamide (Z-isomer).
[0101] Example 11: 4-{N′-[4-(2-methylbutyl)2-oxo-1,2-dihydro-indol-3-ylidene]-hydrazino}-benzenesulformamide (Z-isomer).
[0102] Example 12: 4-[N′-(4-(Cyclobutylmethyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z isomer).
[0103] Example 13: 4-[N′-(4-Cyclobutylidenemethyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z isomer).
[0104] Example 14: 4-(N′-{4-[2-(4-Hydroxyphenyl)ethyl]-2-oxo-1,2-dihydro-indol-3-ylidene}-hydrazino)-benznensulfonamide (Z-isomer).
[0105] Example 15: 4N′-{4-[2-(4-Hydroxyphenyl)-vinyl]-2-oxo-1,2-dihydroido-indol-3-ylidene}-hydrazino)-benznensulfonamide (Z isomer).
[0106] Example 16: 4-[N′-(2-Oxo-4-phenoxy-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (mixture of E and Z isomers).
[0107] Example 17: 4-[N′-(4-lsopropcxy-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z-isomer(.
[0108] Example 18: 4-{N′-[2-Oxo4-(1H-pyrazol-3-yl)-1,2-dihydro-indol-3-ylidene]-hydrazino}-benzenesutfonamide (Z-isomer).
[0109] Example 19: 44(5-Oxazol-5-yl-2-oxo-1,2-dihydro-indol-3-ylidenemethyl)-aminobenzenesulfonamide (Z-isomer).
[0110] Example 20: 2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazonel-2,3-dihydro-1H-indole-5-carboxylic acid 2,3,4,5,6-pentafluorophenyl ester (Z-isomer).
[0111] Example 21: 4-[N′-(5-Nitro-2-oxo-1,2-dihydro-indol-3-ylidene)hydrazino]-benzenesulfonamide (Z isomer).
[0112] Example 22: 4-[N′-(5-Hydroxy-2-oxo-1,2-dihydro-indol-3-ylidene)hydrazino]-benzenesulfonamide (Z isomer).
[0113] Example 23: 4-[N′-(5-Methyl-2-oxo-1,2-dihydro-indol-3-ylidene)hydrazino]-benzenesulfonamide (E isomer).
[0114] Example 24: N-Methyl-4-[N′-(2-oxo-5-[1,2,4]triazol-1-yl-1,2-dihydro-indol-3-ylidene)hydrazino]-benzenesulfonamide (Z isomer).
[0115] Example 25: 2-Oxo-3-[(4-sulfamoyl-phenylyhydrazono]-2,3-dihydro-1H-indole-5-sulfonic acid sodium salt (Z-isomer).
[0116] Example 26: 3-[(4-Methylsulfamoyl-phenyl)hydrazono]-2-oxo-2,3-dihydro-1H-indole-5-carboxylic acid amide (Z-isomer).
[0117] Example 27: 2-Oxo-3-(4-sulfamoyl-phenylamino-methylene)-2,3-dihydro-1H-indole-5-carboxylic acid methyl ester (Z-isomer).
[0118] Example 28: 5-Bromo-3-[(4-Methylsulfonyl-phenyl)-hydrazono]-1,3-dihydro-indol-2-one (Z-isomer).
[0119] Example 29: 3-(3H-benzotriazol-5-ylamino-methylene)-5-iodo-1,3-dihydro-indol-2-one (Z-isomer).
[0120] Example 30: 2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-sulfonic acid amide (Z-isomer).
[0121] Example 31: 4-[N′-(5-Methylsulfonyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamride (Z-isomer).
[0122] Example 32: 3-[(4-Methylsulfamoyl-phenyl)-hydrazono]-2-oxo-2,3-dihydro-1H-indole-5-sulfonic acid methyl amide (Z-isomer).
[0123] Example 33: 4-{N′-[5-(1-Hydroxyimino-ethyl)-2-oxo-1,2-dihydro-indol-3-ylidene]-hydrazino}-N-methyl-benzenesulfonamide (Z-isomer).
[0124] Example 34: 4-[1-(5-Oxazol-5-yl-2-oxo-1,2-dihydro-indol-3-ylidene)-ethylamino]-benzenesulfonamide (Z-isomer).
[0125] Example 35: N,N-Dimethyl-4-(5-oxazol-5-yl-2-oxo-1,2-dihydro-indol-3-ylidenemethyl)-amino]-benzenesulfonamide (Z-isomer).
[0126] Example 36: 4-[1-(5-Oxazol-5-yl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (mixture of E and Z isomers).
[0127] Example 37: 4-[(2-Oxo-5-phenyl-1,2-dihydro-indol-3-ylidenemethyl)amino]-benzenesulfonamide (Z-isorier).
[0128] Example 38: 2-Oxo-3[(4-sulfamoyl-phenylyhydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid dimethylamide (Z-isomer).
[0129] Example 39: 2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indol-5-carboxylic acid (furan-2-ylmethyl)amide (Z-isomer).
[0130] Example 40: 2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indol-5-carboxylic acid -2,6-dimethoxy-benzyiamide (Z-isomer).
[0131] Example 41: 2-Oxo-3[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid(2-morpholin-4-yl-ethyl)-amide (Z-isomer).
[0132] Example 42: 2-Oxo-3-[(4-sulfamoyl-phenyl)hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid (2-imidazol-1-yl-ethyl)amide (Z-isomer).
[0133] Example 43: 2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid (3-imidazol-1-yl-propyl)amide (Z-isomer).
[0134] Example 44: 2-Oxo-3-[(4-sulfamoyl-phenyl)hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid (2-methoxyethyl)amide (Z-isomer).
[0135] Example 45: 2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2-3-dihydro-1H-indole-5-carboxylic acid (2-hydroxyethylyamide (Z-isomer)
[0136] Example 46: 2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid (3-hydroxypropyl)-amide (Z-isomer).
[0137] Example 47: 2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid (3-hydroxy-2,2-dimethylpropyl)-amide (Z-isomer).
[0138] Example 48: 2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid (pyridin-3-ylmethyl)amide (Z-isomer).
[0139] Example 49: 2-Oxo-3-[(4-sulfamoyl-phenyl)hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid (pyridin-4-ylmethyl)-amide (Z-isomer).
[0140] Example 50: 4-[N′-(5-Methoxy-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z-isomer).
[0141] Example 51: 4-[N′-(5-Amino-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide hydrochloride (Z-isomer).
[0142] Example 52: 4-[N′-(6-Ethyl-2-oxo-1,2-dihydro-indol-3-ylidene)hydrazino]-benzenesulfonamide (Z isomer).
[0143] Example 53: 4-[(2-Oxo-1,2-dihydro-indol-3-ylidenemethyl)-amino]-benzensulfonic-acid-phenyl-ester (Z-isomer).
[0144] Example 54: N-{4-[(2-Oxo-1,2-dihydro-indol-3-ylidenemethyl)-amino]-phenyl}sulfamide (Z-isomer).
[0145] Example 55: 4-[(6-Hydroxymethyl-2-oxo-1,2-dihydro-indol-3-ylidenemethyl) -amino]-benzenesulfonamide (Z-isomer).
[0146] Example 56: 4-[N′-(6-Bromo-2-oxo-1,2-dihydro-indol-3-ylidene)hydrazino]benzenesulfonamide (Z-isomer).
[0147] Example 57: 4-[N′-(2-Oxo-6-phenoxy-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z-isomer).
[0148] Example 58: 4-[N′-(6-Ethoxy-2-oxo-1,2-dihydroindol-3-ylidene)-hydrazino]-benzenesulfonamide (Z-isomer).
[0149] Example 59: N-[2-(2-Hydroxyethoxy)ethyl]4-[7-oxo6,7-dihydro-1-thia-3,6-diaza-as-indacene-8-ylidenemethyl)amino]benzenesulfonamide (Z-isomer).
[0150] Example 60: N-[2-(2-Hydroxyethyl]4-[7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacene-8-ylidenemethyl)-aniino]benzenesulfonamide (Z-isomer).
[0151] Example 61: N-Methyl4-[N′-(4-methyl-5-nitro-2-oxo-1,2-dihydro-indol-3-ylidene)hydrazino]-benzenesulfonamide (Z-isomer).
[0152] Example 62: 4-[N′-(7-Oxo-6,7-dihydro-3H-pyrrolo[3,2-e]indazol-ylidene) hydrazino]-benzenesulfonamide (Z isomer).
[0153] Example 63: 4-[N′-(7-Oxo-6,7-dihydro-1H-pyrrolo[2,3g]indazol-8-ylidene) hydrazino]-benzenesulfonamide (mixture of E and Z isomers).
[0154] Example 64:-4-[N′-(7-Oxo-6,7-dihydro-3H-1,2,3,6-tetraaza-as-indacen-8-ylidene)hydrazino]-benzenesulfonamide (mixture of E and Z isomers).
[0155] Example 65: 4-[N′-(1-Chloro-7-oxo-6,7-dihydro-3H-pyrrolo[3,2-e]indazol-8-ylidene)hydrazino]-benzenesulfonamide (Z isomer).
[0156] Example 66: 4-[N′-(1,7-[)ioxo-2,3,6,7 - tetrahydro-1H-2,6-diaza-as-indacen-8-ylidene)-hydrazino]-N-methyl-benzenesulfonamide (Z-isomer).
[0157] Example 67: N-(3-Hydroxy-2,2-dimethyl-propyl)-C-{4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-phenyl}-methanesulfonamide (Z-isomer).
[0158] Example 68: N-Methyl-C-{4-[N′-(2-oxo-2,3-dihydro-pyrrolo[3,2-f]quinolin-1-ylidene)-hydrazino]-phenyl}-methanesulfonamide (Z-isomer).
[0159] Example 69: N-(1H-Indazol-6-yl)-4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen- 0 8-ylidenemethyl)-amino]-benzenesulfonamide (Z-isomer).
[0160] Example 70: 4-[(7-Oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-N-thiazol-2-yl-benzenesulfonamide (Z-isomer).
[0161] Example 71: N-(Amino-imino-methyl)-4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-benzenesulfonamide (Z-isomer).
[0162] Example 72: 4-[(7-Oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-N-pyridin-2-yl-benzenesulfonamide (Z-isomer).
[0163] Example 73: 8-[(2,2-Dioxo-1,3-dihydro-benzo[c]thiophen-5-ylamino-methylene)-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one (Z-isomer).
[0164] Example 74: {4-[(7-Oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-phenyl}-methanesulfonamide (Z-isomer).
[0165] Example 75: N-Allyl-C-{4-[(7-oxo-6,7-dihydro-1-thia-3,6-siaza-as-indacen-8-ylidenemethyl)-amino]-phenyl}-methanesulfonamide (Z-isomer).
[0166] Example 76: 8-(4-Methylsulfonylmethyl-phenylamino-methylene)-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one (Z-isomer).
[0167] Example 77: N-(3-Hydroxy-2,2-dimethyl-propyl)-4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-benzenesulfonamide (Z-isomer).
[0168] Example 78: 4-[(7-Oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-N-(3-trifluoromethyl-phenyl)-benzenesulfonamide (Z-isomer).
[0169] Example 79: 4-[(7-Oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-N-pyrimidin-2-yl-benzenesulfonamide (Z-isomer).
[0170] Example 80: N-(5-Methyl-[z, 3 , 4 ]thiadiazol-2-yl)-4-(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-benzenesulfonamide (Z-isomer).
[0171] Example 81: N-Acetyl-4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-benzenesulfonamide (Z-isomer).
[0172] Example 82: N-Benzoyl-4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-benzenesulfonamide (Z-isomer).
[0173] Example 83: N-Methyl-4-[N′(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidene)-hydrazino]-benzenesulfonamide (Z-isomer).
[0174] Example 84: N-[2-(2-Hydroxy-ethoxy)-ethyl]-N-methyl-4-(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-benzenesulfonamide (Z-isomer).
[0175] Example 85: N-(2-{2-[2-(2-.Methoxy-ethoxy)-ethoxy]-ethoxy}ethyl)-4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)amino]-benzenesulfonamide (Z-isomer).
[0176] Example 86: 4-[N′-(5,6-Dimethyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z isomer).
[0177] Example 87: N-{6-Hydroxy-3-[(4-methylsulfamoylmethyl-phenylyhydrazono]-2-oxo-2,3-dihydro-1H-indol-5-yl}-acetamide (Z isomer).
[0178] Example 88: 4-[N′-(6-Chloro-5-methoxy-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]benzene-sulfonamide (Z-isomer).
[0179] Example 89: 4-[N′-(5-Hydroxy-6-isopropyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z-isomer).
[0180] Example 90: 4-[N′-(2-Metlyl-6-Oxo-5,6-dihydro-3-oxa-1,5-diaza-s-indacen-7-ylidene)-hydrazino]-benzenesiulfonamide (Z isomer).
[0181] Example 91: 4-[N′-(5-Acetyl-2-oxo-2,5,6,7-tetrahydro-1H-pyrrolo[2,3-f]indol-3-ylideneyhydrazino]-benzenesulfonamide (Z-isomer).
[0182] Example 92: 4-[N′-(6-Oxo-5,6-dihydro-[1,3]dioxolo[4,5-f]indol-7-ylidene) hydrazino]-benzenesulfonamide (Z-isomer).
[0183] Example 93: 4-[N′-(2-Oxo-2,5,6,7-tetrahydro-1H-pyrrolo[2,3-f]indol-3-ylidene)-hydrazino]-benzenesulfonamide hydrobromide (Z-isomer).
[0184] Example 94: C-{4-[N′-(4,6-Dichloro-5-methoxy-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-phenyl}-N-methyl-methanesulfonamide (Z isomer).
[0185] Example 95: 4-[N′-(4-Chloro-5-hydroxy-6-methyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z-isomer).
[0186] Example 96: 4-[N′-(5-Hydroxy-4,6-dimethyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z-isomer).
[0187] Example 97: 3-(1H-Indazol-5-ylamino-methylene)-1,3-dihydro-indol-2-one (Z-isomer).
[0188] Example 98: 3-[(1H-Indazol-yl)-hydrazone]-1,3-dihydro-indol-2-one (Z-isomer).
[0189] Example 99: 4-[N′-(5-Hydroxy-4,6-dimethyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-phenyl}-N-methyl-methanesulfonamide (Z isomer).
[0190] Example 100: N-Methyl4-[(5-oxazol-5-yl-2-oxo-1,2-dihydro-indol-3-ylidenemethyl amino]-phenylmethanesulfonamide (Z-isomer).
[0191] Example 101: 8-(3H-Benzotriazol-5-ylaminomethylene)-6,8-dihydro-1-thia-3,6-diaza-as-indacene-7-one (Z-isomer).
[0192] Example 102: 4-[N′-2-Oxo-2,3-dihydropyrrolo[3,2-f]quinolin-1-ylidene)hydrazino]-benzenesulfonamide (Z-isomer).
[0193] Example 103: 2-Oxo-3-(4-sulfamoyl-phenylamino-methylene)2,3-dihydro-1H-indole-5-carboxylic acid isobutyl ester (Z-isomer).
[0194] Example 104: 4-[(7-Oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)amino]-N-pyridinyl-4-yl-methyl benzenesulfonamide (Z-isomer).
[0195] The invention discloses six different points of substitution on structural formula (I). Each of these points of substitution bears a substituent whose selection and synthesis as part of this invention was independent of all other points of substitution on formula (I). Thus, each point of substitution is now further described individually.
[0196] Preferred substitutions at the R 1 position include hydrogen, halogen, amide, nitro, lower alkyl, hydroxy, hydroxyalkyl, pyrimidineloweralkyl, loweralkoxycarbonyl, cyclic: loweralkyl, hydroxyphenylloweralkyl, phenoxy, alkoxy, or pyrazole, or are fused with R 2 to form fused thiazole, pyrazole, triazole, halogen-substituted diazole, acyl substituted pyrrole, and pyridine, rings. Most preferred are hydrogen, methyl and fused with R 2 for form fused thiazole and fused pyridine. Most highly preferred are to be fused with R 2 to form fused thiazole.
[0197] Preferred substitutions at the R 2 position include hydrogen, halogen, sulfate, amine, quaternary amine, amide, ester, phenyl, alkoxy, aminosulfonyl, lower alkyl sulfonyl, furanyl lower alkyl amide, pyridinyl lower alkyl amide, alkoxy-substituted phenyl lower alkyl amide, morpholino lower alkyl amide, imidazolyl lower alkyl amide, hydroxy lower alkyl amide, alkoxy lower alkyl amide, lower alkyl amide, lower alkyl sulfonamide,lower alkyl hydroxy substituted amino, nitro, halogen-substituted phenoxycarbonyl, or triazole or oxazole rings, or are fused with R 3 to form a fused oxazole, pyrrole, or dioxolane ring, which fused rings can be substituted by lower alkyl, lower alkyl carbonyt, or, when said fused ring is a hetero ring having nitrogen as the heteroatom, forming a quaternary ammonium salt ionically bonded with a halogen atom. Most preferred are hydrogen, hydroxyl, oxazolyl, or fused with R 1 to form fused thiazolyl or fused pyridyl Most highly preferred are to be fused with R 1 to form fused thiazole.
[0198] Preferred substitutions at R 3 include hydrogen, lower alkyl, hydroxy lower alkyl, halogen, phenoxy, and alkoxy. Most preferred are hydrogen and methyl. Most highly preferred is hydrogen.
[0199] Preferred substitutions at R 4 include sulfonylamino, sulfonylaminoamino, lower alkyl sulfonylamino, lower alkylsulfonyl lower alkyl, alkoxysulfonylamino, phenylcarbonylsulfonylamino, phenoxysulfonyl, hydroxy lower alkylsulfonylamino, hydroxy lower alkyisulfonylamino lower alkyl, alkyl, phenylsulfonylamino, optionally substituted by halogen substituted lower alkyl, aminoiminosulfonylamino, alkylsulfonylaminoalkyl, pyridinyt lower alkyl sulfonylamino, benzamideazolesulfonylamino, pyridylsulfonylamino, pyrimidinylsulfonylamino, thiaidiazolylsulfonylamino optionally substituted by lower alkyl, thiazolesulfonylamino, hydroxyalkoxyalkylsulfonylamino, or the group 4′-SO 2 NH[(CH 2 ) 2 O] 4 CH 3 , or are fused with R 5 to form a fused imidazole, triazole, cyclic sulfonylamino or thiaphene ring optionally disubstituted on the sulfur heteroatom by oxo. The most preferred substitutions are 2 pyridine sulfonylamino, 4 pyridine sulfonylamino, hydroxy n-butyl sulfonylamino, methylsulfonylaminomethylene, sulfonyidimethylamino, fused 1,2,3-triazole, and sulfonylamino. Most highly preferred is 2 pyridine sulfonylamino, 4 pyridine sulfonylamino and hydroxy n-butyl suffonylamino.
[0200] The preferred substitution at R 5 is hydrogen.
[0201] Preferred substitutions at X include N, CH, and CCH 3 . Most preferred is NH.
[0202] Preferred individual compounds of the present invention include any one of the following compounds:
DETAILED DESCRIPTION OF THE INVENTION
[0203] Salts encompassed within the term “pharmaceutically acceptable salts” refer to non-toxic salts of the compounds of this invention which are generally prepared by reacting the free base with a suitable organic or inorganic acid or by reacting the acid with a suitable organic or inorganic base. Representative salts include the following salts: Acetate, Benzenesulfonate, Benzoate, Bicarbonate, Bisulfate, Bitartrate, Borate, Bromide, Calcium Edetate, Camsylate, Carbonate, Chloride, Clavulanate, Citrate, Diethanolamine, Dihydrochloride, Edetate, Edisylate, Estolate, Esylate, Fumarate, Gluceptate, Gluconate, Glutamate, Glycollylarsanilate, Hexylresorcinate, Hydrabamine, Hydrobromide, Hydrocloride, Hydroxynaphtlhoate, Iodide, Isethionate, Lactate, Lactobionate, Laurate, Malate, Maleate, Mandelate, Mesylate, Metaphosphoric, Methylbromide, Methyinitrate, Methylsulfate, Monopotassium Maleate, Mucate, Napsylate, Nitrate, N-methylglucamine, Oxalate, Pamoate (Embonate), Palmitate, Pantothenate, Phosphate/diphosphate, Polygalacturonate, Potassium, Salicylate, Sodium, Stearate, Subacetate, Succinate, Tannate, Tartrate, Teoclate, Tosylate, Trifluoroacetate, Triethiodide, Trimethylammonium and Valerate.
[0204] Other salts which are not pharmaceutically acceptable may be useful in the preparation of compounds of formula (I) and these form a further aspect of the invention.
[0205] Also included within the scope of the invention are the individual isomers of the compounds represented by formula (I) above as well as any wholly or partially equilibrated mixtures thereof. The present invention also covers the individual isomers of the compounds represented by formula above as mixtures with isomers thereof in which one or more chiral asymmetric centers are inverted.
[0206] As used herein, the term “aliphatic” refers to the terms alkyl, alkylene, alkenyl, alkenylene, alkynyl, and alkynylene.
[0207] As used herein, the term “lower” refers to a group having between one and six carbons.
[0208] As used herein, the term “alkyl” refers to a straight or branched chain hydrocarbon having from one to twelve carbon atoms, optionally substituted with substituents selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower ialkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano, halogen, or lower perfluoroalkyl, multiple degrees of substitution being allowed. Examples of “alkyl” as used herein include, but are not limited to, n-butyl, n-pentyl, isobutyl, and isopropyl, and the like.
[0209] As used herein, the term “alkylene” refers to a straight or branched chain divalent hydrocarbon radical having from one to ten carbon atoms, optionally substituted with substituents, selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano, halogen, or lower periluoroalkyl, multiple degrees of substitution being allowed. Examples of “alkylene” as used herein include, but are not limited to, methylene, ethylene, and the like.
[0210] As used herein, the term “alkenyl” refers to a hydrocarbon radical having from two to ten carbons and at least one carbon-carbon double bond, optionally substituted with substituents selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano, halogen, or lower perfluoroalkyl, multiple degrees of substitution being allowed.
[0211] As used herein, the term “alkenylene” refers to an straight or branched chain divalent hydrocarbon radical having from two to ten carbon atoms and one or more carbon-carbon double bonds, optionally substituted with substituents selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano, halogen, or lower perfluoroalkyl, multiple degrees of substitution being allowed. Examples of “alkenylene” as used herein include, but are not limited to, ethene-1,2-diyl, propene-1,3-diyl, methylene-1,1-yl, and the like.
[0212] As used herein, the term “alkynyl” refers to a hydrocarbon radical having from two to ten carbons and at least one carbon-carbon triple bond, optionally substituted with substituents selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano, halogen, or lower perfluoroalkyl, multiple degrees of substitution being allowed.
[0213] As used herein, the term “alkynylene” refers to a straight or branched chain divalent hydrocarbon radical having from two to ten carbon atoms and one or more carbon-carbon triple bonds, optionally substituted with substituents selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano, halogen, or lower perfluoroalkyl, multiple degrees of substitution being allowed. Examples of “alkynylene” as used herein include, but are not limited to, ethyne-1,2-diyl, propyne-1,3-diyl, and the like.
[0214] As used herein, the tenn “cycloaliphatic” refers to the terms cycloalkyl, cycloalkylene, cycloalkenyl, c,ycloalkenylene, cycloalkynyl and cycloalkylnylene.
[0215] As used herein, “cycloalkyl” refers to a alicyclic hydrocarbon group with one or more degrees of unsaturation, having from three to twelve carton atoms, optionally substituted with, substituents selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano, halogen, or lower perfluoroalkyl, multiple degrees of substitution being allowed. “Cycloalkyl” includes by way of example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, and the like.
[0216] As used herein, the term “cycloalkylene” refers to an non-aromatic alicyclic divalent hydrocarbon radical having from three to twelve carbon atoms, optionally substituted with substituents selected from the group consisting of lower alkyl, lower alkoxy,, lower alkylsulfarnyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano, halogen, or lower perfluoroalkyl, multiple degrees of substitution being allowed. Examples of “cycloalkylene” as used herein include, but are not limited to, cyclopropyl-1,1-diyl, cyclopropyl-1,2-yl, cyclobutyl-1,2-diyl, cyclopentyl-1,3-diyl, cyclohexyl-1,4-diyl, cycloheptyl-1,4-diyl, or cyclooctyl-1,5-diyl, and the like.
[0217] As used herein, the term “cycloalkenyl” refers to a substituted alicyclic hydrocarbon radical having from three to twelve carbon atoms and at least one carbon-carbon double bond in the ring system, optionally substituted with substituents selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano, halogen, or lower perfluoroalkyl, multiple degrees of substitution being allowed. Examples of “cycloalkenylene” as used herein include, but are not limited to, 1-cyclopentene-3-yl, 1-cyclohexene-3-yl, 1-cycloheptene4-yl, and the like.
[0218] As used herein, the term “cycloalkenylene” refers to a substituted alicyclic divalent hydrocarbon radical having from three to twelve carbon atoms and at least one carbon-carbon double bond in the ring system, optionally substituted with substituents selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano, halogen, or lower perfluoroalkyl, multiple degrees of substitution being allowed. Examples of “cycloalkenylerie” as used herein include, but are not limited to, 4,5-cydopentene-1,3-diyl, 3,4-cyclohexene-1,1-diyl, and the like.
[0219] As used herein, the temi “heteroatom ring system” refers to the terms heterocyclic, heterocyclyl, heteroaryl, and heteroarylene. Non-limiting examples of such heteroatom ring systems are recited in the Summary of the Invention, above.
[0220] As used herein, the term “heterocyclic” or the term “heterocyclyl” refers to a three to twelve-membered heterocyclic ring having one or more degrees of unsaturation containing one or more heteroatomic substitutions selected from S, SO, SO 2 , O, or N, optionally substituted with substituents selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano, halogen, or lower perfluoroalkyl, multiple degrees of substitution being allowed. Such a ring may be optionally fused to one or more of another “heterocyclic” ring(s) or cycloalkyl ring(s). Examples of “heterocyclic” include, but are not limited to, tetrahydrofuran, pyran, 1,4-dioxane, 1,3-ioxane, piperidine, pyrrolidine, morpholine, tetrahydrothiopyran, tetrahydrothiophene, and the like.
[0221] As used herein, the term “heterocyclylene” refers to a three to twelve-membered heterocyclic ring diradical having one or more degrees of unsaturation containing one or more heteroatoms selected from S, SO, SO 2 , O, or N, optionally substituted with substituents selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano, halogen, or lower perfluoroalkyl, multiple degrees of substitution being allowed. Such a ring may be optionally fused to one or more benzene rings or to one or more of another “heterocyclic” rings or cycloalkyl rings. Examples of “heterocyclylene” include, but are not limited to, tetrahydrofuran-2,5-diyl, morpholine-2,3-diyl, pyran-2,4-diyl, 1,4-dioxane-2,3-diyl, 1,3-dioxane-2,4-diyl, piperidine-2,4-diyl, piperidine-1,4-diyl, pyrrolidine-1,3-diyl, morpholine-2,4-diyl, and the like.
[0222] As used herein, the term “aryl” refers to a benzene ring or to an optionally substituted benzene ring system fused to one or more optionally substituted benzene rings to form anthracene, phenanthrene, or napthalene ring systems, optionally substituted with substituents selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mnercapto, amino optionally substituted by alkyl, carboxy, tetrazolyl, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkcyl, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy, heteroaroyloxy, alkoxycarbonyl, nitro, cyano, halogen, lower perfluoroalkyl, heteroaryl, or aryl, multiple degrees of substitution being allowed. Examples of aryl include, but are not limited to, phenyl, 2-naphthyl, 1-naphthyl, biphenyl, and the like.
[0223] As used herein, the term “arylene” refers to a benzene ring diradical or to a benzene ring system diradical fused to one or more optionally substituted benzene rings, optionally substituted with substituents selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, tetrazolyl, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy, heteroaroyloxy, alkoxycarbonyl, nitro, cyano, halogen, lower perfluoroalkyl, heteroaryl, or aryl, multiple degrees of substitution being allowed. Examples of “arylene” include, but are not limited to, benzene-1,4-diyl, naphthalene-1,8-diyl, anthracene-1,4-diyl, and the like.
[0224] As used herein, the term “heteroaryl” refers to a five- to seven-membered aromatic ring, or to a polycyclic heterocyclic aromatic ring, containing one or more nitrogen, oxygen, or sulfur heteroatoms at any position, where N-oxides and sulfur monoxides and sulfur dioxides are permissible heteroaromatic substitutions, optionally substituted with substituents selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydiroxy, mercapto, amino optionally substituted by alkyl, carboxy, tetrazolyl, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy, heteroaroyloxy, alkoxycarbonyl, nitro, cyano, halogen, lower perfluoroalkyl, heteroaryl, or aryl, multiple degrees of substitution being allowed. For polycyclic aromatic ring systems, one or more of the rings may contain one or more heteroatoms. Examples of “heteroaryl” used herein are furan, thiophene, pyrrole, imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, isoxazole, oxadiazole, thiadiazole, isothiazole, pyridine, pyridazine, pyrazine, pyrimidine, quinoline, isoquinoline. benzofuran, benzothiophene, indole, and indazole, and the like.
[0225] As used herein, the term “heteroarylene” refers to a five- to seven-membered aromatic ring diradical, or to a polycyclic heterocyclic aromatic ring diradical, containing one or more nitrogen, oxygen, or sulfur heteroatoms, where N-oxides and sulfur monoxides and sulfur dioxides are permissible heteroaromatic substitutions, optionally substituted with substituents selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulifonyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, tetrazolyl, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy, heteroaroyloxy, alkoxycarbonyl, nitro, cyano, halogen, lower perfluoroalkyl, heteroaryl, or aryl, multiple degrees of substitution being allowed. For polycyclic aromatic ring system diradicals, one or more of the rings may contain one or more heteroatoms. Examples of “heteroarylene” used herein are furan-2,5-diyl, thiophene-2,4-diyl, 1,3,4-oxadiazole-2,5-diyl, 1,3,4-thiadiazole-2,5-diyl, 1,3-thiazole-2,4-diyl, 1,3-thiazole-2,5-diyl, pyridine-2,4-diyl, pyridine-2,3-diyl, pyridine-2,5-diyl, pyrimitline-2,4-diyl, quinoline-2,3-diyl, and the like.
[0226] As used herein, the term “alkoxy” refers to the group R a O, where R a is aliphatic.
[0227] As used herein, the term “alkylsulfanyl” refers to the group R a S—, where R a is aliphatic.
[0228] As used herein, the term “alkylsulfenyl” refers to the group R a S(O)—, where R a is aliphatic.
[0229] As used herein, the term “alkylsulfonyl” refers to the group R a SO 2 —, where R a is aliphatic.
[0230] As used herein, the term “acyl” refers to the group R a C(O)—, where R a is aliphatic, cycloaliphatic, or heterocyclyl.
[0231] As used herein, the term “aroyl” refers to the group R a C(O)—, where R a is aryl.
[0232] As used herein, the term “heteroaroyl” refers to the group R a C(O)—, where R a is heteroaryl.
[0233] As used herein, the term “alkoxycarbonyl” refers to the group R a OC(O)—, where R a is aliphatic.
[0234] As used herein, the term “acyloxy” refers to the group R a C(O)O—, where R a is aliphatic, cycloaliphatic, or heterocyclyl.
[0235] As used herein, the term “aroyloxy” refers to the group R a C(O)O—, where R a is aryl.
[0236] As used herein, the term “heteroaroyloxy” refers to the group R a C(O)O—, where R a is heteroaryl.
[0237] As used herein, the term “optionally” means that the subsequently described event(s) may or may not occur, and includes both conditions.
[0238] As used herein, the term “substituted” refers to substitution with the named substituent or substituents, multiple degrees of substitution being allowed.
[0239] As used herein, the terms “contain” or “containing” can refer to in-line substitutions at any position along the above-defined alkyl, alkenyl, alkynyl or cycloalkyl substituents with one or more of any of O, S, SO, SO 2 , N, or N-alkyl, including, for example, —CH 2 —O—CH 2 —, —CH 2 —SO 2 —CH 2 —, —CH 2 —NH—CH 3 and so forth.
[0240] As used herein, the term “solvate” is a complex of variable stoichiometry formed by a solute (in this invention, a compound of formula (I)) and a solvent. Such solvents for the purpose of the invention may not interfere with the biological activity of the solute. Solvents may be, by way of example, water, ethanol, or acetic acid.
[0241] As used herein, the terms “biohydrolyzable carbonate”, “biohydrolyzable ureide” and “biohydrolyzable carbamate” is a carbonate, ureide, or carbamate, respectively of a drug substance (in this invention, a compound of general formula (I) which either a) does not interfere with the biological activity of the parent substance but confers on that substance advantageous properties in vivo such as duration of action, onset of action, and the like, or b) is biologically inactive but is readily converted in vivo by the subject to the biologically active principle. The advantage is that, for example, the biohydrolyzable carbamate is orally absorbed from the gut and is transformed to (I) in plasma. Many examples of such are known in the art and include by way of example lower alkyl carbamates.
[0242] As used herein, the term “biohydrolyzable ester” is an ester of a drug substance (in this invention, a compound of general formula (I) which either a) does not interfere with the biological activity of the parent substance but confers on that substance advantageous properties in vivo such as duration of action, onset of action, and the like, or b) is biologically inactive but is readily converted in vivo by the subject to the biologically active principle. The advantage is that, for example, the biohydrolyzable ester is orally absorbed from the gut and is transformed to (I) in plasma. Many examples of such are known in the art and include by way of example lower alkyl esters, lower acyloxy-alkyl esters, lower alkoxyacyloxyalkyl esters, alkoxyacyloxy esters, alkyl acylamino alkyl esters, and choline esters.
[0243] As used herein, the term “biohydrolyzable amide” is an amide of a drug substance (in this invention, a compound of general formula (I) which either a) does not interfere with the biological activity of the parent substance but confers on that substance advantageous properties in vivo such as duration of action, onset of action, and the like, or b) is biologically inactive but is readily converted in vivo by the subject to the biologically active principle. The advantage is that, for example, the biohydrolyzable amide is orally absorbed from the gut and is transformed to (I) in plasma. Many examples of such are known in the art and include by way of example lower alkyl amides, a-amino acid amides, alkoxyacyl amides, and alkylaminoalkylcarbonyl amides.
[0244] As used herein, the term “prodrug” includes biohydrolyzable amides, biohydrolyzable esters and biohydrolyzable carbamates and also encompasses a) compounds in which the biohydrolyzable functionality in such a prodrug is encompassed in the compound of formula (I): for example, a lactam formed by a carboxylic group in R 1 and an amine in R 2 , and compounds which may be oxidized or reduced biologically at a given functional group to yield drug substances of formula (I). Examples of these functional groups are, but are not limited to, 1,4-dihydropyridine, N-alkylcarbonyl-1,4-dihydropyridine, 1,4-cyclohexadiene, tert-butyl., and the like
[0245] As used herein, the ternt “affinity reagent” is a group attached to the compound of formula (I) which does not affect its in vitro biological activity, allowing the compound to bind to a target, yet such a group binds strongly to a third component allowing a) characterization of the target as to localization within a cell or other organism component, perhaps by visualization by fluorescence or radiography, or b) facile separation of the target from an unknown mixture of targets, whether proteinaceous or not proteinaceous. An example of an affinity reagent according to b) would be biotin either directly attached to (I) or linked with a spacer of one to 50 atoms selected from the group consisting of C, H, O, N, S, or P in any combination. An example of an affinity reagent according to a) above would be fluorescein, either directly attached to (I) or linked with a spacer of one to 50 atoms selected from the group consisting of C, H, O, N, S, or P in any combination.
[0246] The term “pharmacologically effective amount” shall mean that amount of a drug or pharmaceutical agent that will elicit the biological or medical response of a tissue, system, animal or human that is being sought by a researcher or clinician.
[0247] Whenever the terms “aliphatic” or “aryl” or either of their prefixes appear in a name of a substituent (e.g. arylalkoxyaryloxy) they shall be interpreted as including those limitations given above for “aliphatic” and “aryl”. Aliphatic or cycloalkyl substituents shall be recognized as being term equivalents to those having one or more degrees of unsaturation. Designated numbers of carbon atoms (e.g. C 1-10 ) shall refer independently to the number of carbon atoms in an aliphatic or cyclic aliphatic moiety or to the aliphatic portion of a larger substituent in which the term “aliphatic” appears as a prefix (e.g. “al-”).
[0248] As used herein, the term “disubstituted amine” or “disubstituted amino-” shall be interpreted to include either one or two substitutions on that particular nitrogen atom.
[0249] As used herein, the term “oxo” shall refer to the substituent ═O.
[0250] As used herein, the term “halogen” or “halo” shall include iodine, bromine, chlorine and fluorine.
[0251] As used herein, the term “mercapto” shall refer to the substituent —SH.
[0252] As used herein, the term “carboxy” shall refer to the substituent —COOH.
[0253] As used herein, the term “cyano” shall refer to the substituent —CN.
[0254] As used herein, the term “aminosulfonyl” shall refer to the substituent —SO 2 NH 2 .
[0255] As used herein, the term “carbamoyl” shall refer to the substituent —C(O)NH 2 .
[0256] As used herein, the term “sulfanyl” shall refer to the substituent —S—.
[0257] As used herein, the term “sulfenyl” shall refer to the substituent —S(O)—.
[0258] As used herein, the term “sulfonyl” shall refer to the substituent —S(O) 2—.
[0259] The compounds of formula (I) can be prepared readily according to the following reaction General Synthesis Scheme (in which all variables are as defined before) and Examples or modifications thereof using readily available starting materials, reagents and conventional synthesis procedures. In these reactions, it is also possible to make use of variants which are themselves known to those of ordinary skill in this art, but are not mentioned in greater detail.
[0260] General Synthesis Scheme
[0261] The most preferred compounds of the invention are any or all of those specifically set forth in these examples. These compounds are not, however, to be construed as forming the only genus that is considered as the invention, and any combination of the compounds or their moieties may itself form a genus. The following examples further illustrate details for the preparation of the compounds of the present invention. Those skilled in the art will readily understand that known variations of the conditions and processes of the following preparative procedures can be used to prepare these compounds. All temperatures are degrees Celsius unless noted otherwise.
Abbreviations used in the Examples are as follows: g grams mg milligrams L liters mL milliliters M molar N normal mM millimolar i.v. intravenous p.o. per oral s.c. subcutaneous Hz hertz mol moles mmol millimoles mbar millibar psi pounds per square inch rt room temperature min minutes h hours mp melting point TLC thin layer chromatography R f relative TLC mobility MS mass spectrometry NMR nuclear magnetic resonance spectroscopy APCl atmospheric pressure chemical ionization ESI electrospray ionization m/z mass to charge ratio t r retention time Pd/C palladium on activated carbon ether diethyl ether MeOH methanol EtOAc ethyl acetate TEA triethylamine DIEA diisopropylethylamine THF tetrahydrofuran DMF N, N-dimethylformamide DMSO dimethylsulfoxide DDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinone LAH lithium aluminum hydride TFA trifluoroacetic acid LDA lithium diisopropylamide THP tetrahydropyranyl NMM N-methylmorpholine, 4-methylmorpholine HMPA hexamethylphosphoric triamide DMPU 1,3-dimethypropylene urea d days ppm parts per million kD kiloDalton LPS lipopolysaccharide PMA phorbol myristate acetate SPA scintillation proximity assay EDTA ethylenediamine tetraacetic acid FBS fetal bovine serum PBS phosphate buffered saline solution BrdU bromodeoxyuridine BSA bovine serum albumin FCS fetal calf serum DMEM Dulbecco's modified Eagle's medium pfu plaque forming units MOI multiplicity of infection
[0262] Reagents are commercially available or are prepared according to procedures in the literature. The physical data given for the compounds exemplified is consistent with the assigned structure of those compounds. 1 H NMR spectra were obtained on VARIAN Unity Plus NMR spectrophotometers at 300 or 400 Mhz. Mass spectra were obtained on Micromass Platform II mass spectrometers from Micromass Ltd. Altrincham, UK, using either Atmospheric Chemical Ionization (APCI) or Electrospray Ionization (ESI) Analytical thin layer chromatography (TLC) was used to verify the purity of some intermediates which could not be isolated or which were too unstable for full characterisation, and to follow the progess of reactions. Unless otherwise stated, this was done using silica gel (Merck Silica Gel 60 F254). Unless otherwise stated, column chromatography for the purification of some compounds, used Merck Silica gel 60 (230400 mesh), and the stated solvent system under pressure.
[0263] Procedure A
[0264] First method for 1H-indol-2,3-dione (isatin) formation: preparation of 6-H-1-thia-3,6-diaza-as-indacen-7,8-dione.
[0265] To a 1-L flask was added a magnetic stir bar, 85 g of sodium sulfate, and 100 mL of water. The mixture was magnetically stirred until all the solids were dissolved. To the resultant aqueous solution was added a solution of 6-aminobenzothiazole (4.96 g, 33.0 mmol) in 50 mL of 1N aqueous hydrochloric acid and 10 mL of ethanol. The mixture was stirred, and chloral (6.0 g, (36 mmol) was added. To the resultant solution was added a solution of hydroxyl amine hydrochloride (7.50 g, 108 mmol) in 30 mL of water. The final mixture was heated with stirring to a gentle boil until all solids dissappeared, and heating was continued for an additional 15 min. The flask was removed from the heat, and the solution was poured onto 500 g of ice. The mixture was stirred as the product precipatated from solution. The precipatate was collected by suction filtration, washed thoroughly with water, filtered, and air dried to provide 6.9 g (94%) of N-benzothiazol-6-yl-2-hydroxyimino-acetamide: 1 H NMR (DMSO-d 6 ): δ 12.2 (s, 1H), 10.4 (s, 1H), 9.2 (s, 1H), 8.5 (s, 1H), 7.9 (d, 1H), 7.7 (m, 1H), 7.7 (s, 1H); APCI-MS m/z 220 (M−H) − . To a 1-L 3-neck round bottom flask was placed a magnetic stir bar and 100 nil of concentrated sulfuric acid. The flask was fitted with a thermometer to monitor the temperature of the reaction. The sulfuric acid was heated to 100° C., and 10.0 g (45.2 mmol) of N-benzothiazol6-yl-2-hydroxyimino-acetamide was; added slowly. The solution was heated for -1 h, and the reaction mixture was poured into 750 g of ice and water. The residual reaction mixture in the reaction vessel was washed out with an additional 20 mL of cold water. The aqueous slurry was stirred for about 1 h and filtered. The solid was washed thoroughly with water, filtered, and air dried to yield 4.3 g (46%) of 6-H-1-thia-3,6-diaza-as-indacen-7,8-dione: 1 H NMR (DMSO-d 6 ): δ 11.1 (s, 1H), 9.2 (s, 1H), 8.2 (d, 1H), 7.0 (d, 1H); APCI-MS m/z 203 (M−H) − .
[0266] Procedure B
[0267] Second method for 1H-indol-2,3-dione (isatin) formation: preparation of 6-phenoxy-1H-indole-2,3-dione
[0268] To a stirred solution of 1.0 g (6.0 mmol) of chloral hydrate in 25 mL of water was added 7.0 g (22 mmol) of sodium sulfate decahydrate, followed by a solution of 1.18 g (17.0 mmol) of hydroxylamine hydrochloride in 10 mL of water. A solution of 1.0 g (5.4 mmol) of 3-phenoxyaniline in 10 mL of 1.0 N HCl was then added with stirring. The resulting suspension was warmed, and 40 mL of 95% EtOH was added to dissolve the suspenion. The solution was refluxed for 0.75 h and then cooled to ambient temperature. The resulting solid was collected by vacuum filtration and air dried to afford 0.95 g (67%) of 2-hydroxyimino-N-(3-phenoxyphenyl)acetamide as a solid: 1 H NMR (DMSO-d 6 ): δ 6.42 (d, J=8.4 Hz, 1H), 7.03 (d, J=7.9 Hz, 2H), 7.18 (t, J=7.3 Hz, 1H), 7.25-7.50 (m, 5H), 7.64 (s, 1H), 10.29 (s, 1H), 12.21 (s, 1H); APCI-MS: m/z 255 (M−H) − . A suspension of 0.15 g (0.58 mmol) of 2-hydroxyimino-N-(3-phenoxyphenyl)acetamide in 0.4 mL of BF 3 etherate was heated to 85° C. for 0.75 h. The mixture was cooled to rt and 10 g of crushed ice was added. The resulting solid was collected by vacuum filtration and subjected to flash chromatography on silica gel (hexane/EtOAc 1.5:1) to afford 6-phenoxy-1H-indole-2,3-dione as a solid (0.018 g, 13%): 1 H NMR (DMSO-d 6 ): δ 6.44 (d, J=2.0 Hz, 1H), 6.56 (dd, J=2.0, 8.4 Hz, 1H), 7.08 (d, J=8.2 Hz, 1H), 7.22-7.29 (m, 1H), 7.38-7.46 (m, 2H), 7.52 (d, J=8.4 Hz, 1H), 9.05 (s, 1H); APCI-MS: m/z 255 (M+Na) + .
[0269] Procedure C
[0270] Third method for 1H-indol-2,3-dione (isatin) formation (Hewawasam and Meanwell, Tetrahedron Letters 1994, 35, 7303-6): preparation of 4-isopropoxy-1H-indol-2,3-dione and conversion to 4-[N′-(4-isopropoxy-2-oxo-1,2-dihydro-indol-3-ylidene)hydrazino]-benzenesulfonamide.
EXAMPLE 17
4-[N′-(4-Isopropoxy-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide
[0271] A solution of 3.78 g (25.0 mmol) of 3-isopropoxy aniline and di-tert-butyl dicarbonate in 25 mL of THF was heated to reflux for 2 h. The solution was cooled to ambient tempurature, and solvent was removed in vacuo. The residue was dissolved in 100 mL of EtOAc, and the solution was washed with three 50-mL portions of 0.5 M citric acid and 50 mL of brine. The solution was dried over MgSO 4 and removal of solvent in vacuo afforded N-(t-butyloxy-carbonyl)-3-isopropoxyaniline as a white solid (5.75 g, 92%): mp 79-81° C.; 1 H NMR (DMSO-d 6 ): δ 1.21 (d, J=6.0 Hz, 6H), 1.43 (s, 9H), 4.46 (septet, J=6 Hz, 1H), 6.47 (dd, J=2.1, 8.1 Hz, 1H), (3.94 (d, J=8.1 Hz, 1H), 7.0-7.1 (m, 2H), 9.23 (s, 1H); APCI-MS: m/z 274 (M+Na) + . To a solution of 2.5 g (10 mmol) of N-(t-butyloxycarbonyl)-3-isopropoxyaniline in 15 mL of dry THF at −78° C. was added 15 mL (25 mmol) of 1.7 M t-butyllithium in hexanes. The mixture was stirred at 20° C. for 2 h. A solution of 1.84 g (12.5 mmol) of diethyl oxalate in 10 mL of dry THF was added slowly over 5 min, and the mixture was stirred at −20° C. for 2 h. The reaction mixture was then poured into 100 mL of 1.0 N HCl and extracted with two 100-mL portions of EtOAc. Solvent was removed in vacuo, and the residue was dissolved in 100 mL of a 1:1 mixture of EtOH and 6 N HCl and heated to reflux for 1 h. The mixture was cooled to ambient temperature and was extracted with four 100-mL portions of EtOAc. The combined extracts were evaporated to dryness to provide crude 4-isopropoxy-1H-inrdol-2,3-dione, which was dissolved in 10 mL of EtOH containing 0.50 g (2.2 mmol) of 4-sulfonamidophenylhydrazine hydrochloride. The solution was heated to 80° C. for 1 h and cooled to ambient temperature. The resulting solid was collected by vacuum filtration and purified by flash chromatography on silica gel (EtOAc/hexane 3:2) to afford[the title compound as a yellow solid (0.052g, 1.4%): mp >250° C.; 1 H NMR (DMSO 6 ): δ 3.35 (d, J=6 Hz, 6H), 4.74 (septet, J=6 Hz, 1H), 6.48 (d, J=7.7 Hz, 1H), 6.69 (d, J=8 Hz, 1H), 7.14-7.2 (m, 3H), 7.47 (d, J=8.7 Hz, 2H), 7.75 (d, J=8.7 Hz, 2H), 11.01 (s, 1H), 12.79 (s, 1H); APCI-MS: m/z 373 (M−H) − . Anal. Calcd for C 17 H 18 N 4 O 4 S: C, 54.53; H. 4.85; N, 14.96; S, 8.56. Found: C, 54.46; H, 4.84; N, 14.90; S, 8.50.
[0272] Procedure D
[0273] First method for 1,3-dihydro-indol-2-one (oxindole) formation (Gassman and van Bergen, Journal of the American Chemical Society 1974, 96, 5508-12): preparation of 6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one.
[0274] A 2-L three-neck round bottom flask was fitted with an internal thermometer, 250-mL addition funnel, magnetic stir bar and septa. The flask was charged with nitrogen, 200 mL of dry THF, and 6-aminobenzothiazole (15.2 g, 0.100 mol). The mixture was stirred and cooled in a dry ice-acetone bath to an internal temperature of −74° C. A solution of tert-butyl hypoclorite (11.0 g, 0.103 mol) in 50 mL of dichloromethane was added over a 15 min period. The resultant solution was stirred for an additional 3 h at dry ice-acetone bath temperature. To the reaction was then added by slow, dropwise addition a solution of ethyl methylthioacetate (13.8 g, 0.103 mol) in 50 mL of dichoromethane. The resultant solution was stirred for an additional 3 h at dry ice-acetone bath temperature. A solution of triethyl amine (25.3 g, 0.250 mol) and 50 ml of dichloromethane was added at dry ice-acetone bath temperature, and the solution was stirred for 0.5 h. The cooling bath was removed, and the reaction was allowed to warm to rt. The reaction was then concentrated to a thick residue. The thick oil was resuspended in 200 mL of ether and 600 mL of 0.25 M hydrochloric acid. The mixture was allowed to stir for 24 h. The resulting solid was filtered from the mixture and triturated with water and ether. The solid was then resuspended in cold MeOH, filtered and dried under vacum for 16 h to yield 18.7 g (79%) of 8-methylsulfanyl-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one: 1 H NMR (DMSO-d 6 ) δ 10.8 (s, 1H), 9.2 (s, 1H), 8.0 (d, 1H), 7.1 (d, 1H), 1.8 (s, 3H); APCI-MS m/z 235 (M−H) − . To a 500-mL erlenmeyer flask was added a stir bar, 8.1 g (0.034 moles) of 8-methylsulfanyl6,8-dihydro-1-thio-3,6-diaza-as-indacen-7-one and 100 mL of glacial acetic acid. The mixture was stirred until all the starting material had dissolved. The reaction mixture was then diluted with 100 mL of THF. Zinc metal (16 g, 325 mesh) was then added. The heterogeneous mixture was then stirred and heated to 60° C. for 2.5 h. The mixture was vacuum filtered through a one half inch pad of celite. The residue on the filter pad was washed with additional THF. The filtrates were combined and concentrated to a wet solid. The solid was triturated with MeOH, filtered and air dried to yield 4.51 g (70%) of 6.8-dihydro-1-thia-3,6-diaza-as-indacen-7-one as a free-flowing solid: 1 H NMR (DMSO-d 6 ): δ 10.5 (s, 1H), 9.1 (s, 1H), 7.9 (d, 1H), 7.0 (d, 1H), 3.6 (s, 2H); APCI-MS m/z 191 (M+H) + .
[0275] Procedure E
[0276] Second method for 1,3-dihydro-indol-2-one (oxindole) formation (Johnson and Aristoff, Journal of Organic Chemistry 1990, 55, 1374-5): preparation of 2-oxo-2,3-dihydro-1H-indole-5-carboxylic acid methyl ester and conversion to 2-oxo34-sulfamoyl-phenylamino-methylene)-2,3-dihydro-1H-indole-5-carboxylic acid methyl ester (Z-isomer).
EXAMPLE 27
2-Oxo-3-(4,-sulfamoyl-phenylamino-methylene)-2,3-dihydro-1H-indole-5-carboxylic Acid Methyl Ester (Z-Isomer)
[0277] A solution of 2.66 g (20.0 mmol) of ethyl (methylthio)acetate dissolved in 200 mL of dichloromethane was cooled with stirring to −70° C. and 2.7 g (20.0 mmol) of sulfuryl chloride was added. The reaction was stirred for 30 min. at −70° C., and a solution of 3.0 g (20 mol) of methyl 4-aminobenzoate and 4.3g (20 mmol) of Proton Sponge® in 250 mL of dichloromethane was added dropwise over 1 h. The resulting pink slurry was treated with 2.3 g (23 mmol) of TEA in one portion, and the solution was allowed to warm to rt. The solution was washed with three 250-mL portions of water, dried over MgSO 4 , and concentrated to give an oil. This was chromatographed on silica gel eluting with hexane:EtOAc (1:1) to yield 2.0 g (42% yield) of 3-methylthio-2-oxo-2,3-dihydro-1H-indole-5-carboxylic acid methyl ester: 1 H NMR (DMSO-d 6 ): δ 1.97 (s, 3H), 3.35 (s, 3H), 4.67 (s, 1H), 6.97 (d, J=8.2 Hz, 1H), 7.84 (is, 1H), 7.91 (d, J=8.2 Hz, 1H), 10.97 (s, 1H). A solution of 2.0 g (8.4 mmol) of 3-methylthio-2-oxo-2,3-dihydro-1H-indole-5-carboxylic acid methyl ester in 20 mL of acetic acid was treated with 10 g of zinc powder. The reaction mixture was stirred for 2 h at rt, filtered through celite and concentrated to dryness. The residue was chromatographed on silica gel eluting with hexane:EtOAc (1:1) to yield 1.6 g (99% yield) of 2-oxo-2,3-dihydro-1H-indole-5-carboxylic acid meathyl ester as a pink solid: 1 H NMR (DMSO-d6): δ 3.52 (s, 2H), 3.77 (s, 3H), 6.8-7 (d, J=8.2 Hz, 1H), 7.74 (s, J=1H), 7.80 (d, J=8.2 Hz, 1H), 10.72 (br s, 1H). Conversion to the 3-dimethylaminomethylene-2-oxo-2,3-dihydro-1H-indole-5-carboxylic acid methyl ester (mixture of E and Z isomers) was carried out via Procedure G in 49% yield: 1 H NMR (DMSO-d 6 ): δ 3.29 Z (s, 6H), 3.31 E (s, 6H)3, 3.76 Z (s, 3H), 3.76 E (s, 3H), 6.74 Z (d, J=8.1 Hz, 1H), 6.81 E (d, J=8.2 Hz, 1H), 7.47-7.50 Z (m, 1H), 7.50-7.52 E (m, 1H), 7.57 E (dd, J=1.3, 8.2 Hz, 1H), 7.74 Z (s, 1H), 7.89 Z (s, 1H), 7.94 E (s, 1H), 10.33 Z (bs, 1H), 10.43 E (bs, 1H). The title compound was prepared in 41% yield from 3-[(dimethylamino)lmethyleneloxindole-5-carboxylic acid methyl ester and 4-aminobenzenesulfonarnide according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 3.81 (s, 3H), 6.92 (d, .J=8.2 Hz, 1H), 7.26 (s, 2H), 7.60 (d, J=8.4 Hz, 2H), 7.69 (d, J=8.2 Hz, 1H), 7.75 (d, J=8.4 Hz, 2H), 8.29 (s, 1H), 8.86 (d, J=12.4 Hz, 1H), 10.80 (d, J=12.4 Hz, 1H), 10.94 (s, 1H); APCI-MS m/z 372 (M−1) − . Anal. Calcd for C 17 H 15 N 3 O 5 S: C, 54.68, H, 4.05; N, 11.25; S, 8.59. Found C, 54.65, H, 4.12; N, 11.17; S, 8.49.
[0278] Procedure F
[0279] Third method for 1,3-dihydro-indol-2-one (oxindole) formation (Seibert, Chemie Berichte 1947, 80, 494-502): preparation of 3-H-pyrrolo[3,2-f]quinoline-2-one.
[0280] A solution of 2.3 g (12 mmol) of 3 -H-pyrrolo[3,2-f]quinoline 1,2-dione and 2.0 ml (0.06 mol) of hydrazine in 50 ml of DMF and 50 ml of ethanol was stirred at reflux for 2 h. The resulting suspension was allowed to cool to ambient temperature and was then chilled in an ice bath and filtered. The solid was washed with a small volume of ethanol and allowed to air dry to give 1-hydrazono-1,3-dihydropyrrolo[3,2-f]quinolin-2-one as an orange solid (1.8 g, 73%): 1 H NMR (DMSO-d 6 ): δ 7.37 (d, J=8.8 Hz, 1H), 7.47 (dd, J=8.4, 4.2 Hz, 1H), 7.81 (d, J=8.8 Hz, 1H),, 8.71 (dd, J=4.2, 1.6 Hz, 1H), 8.80 (d, J=8.4 Hz, 1H), 9.90 (brd, J=14.7 Hz, 1H), 10.89 (brd, J=14.7 Hz, 1H), 10.95 (brs, 1H); ESI-MS m/z 213 (M+H) + . A solution 1.8 g (8.5 mmol) of 1-hydrazono-1,3-dihydropyrrolo[3,2-f]quinolin-2-one in 50 ml of freshly prepared 0.5 M sodium ethoxide solution was stirred at reflux for 3 h. The solution was diluted with 50 ml of water, neutralized with acetic acid, and concentrated on a rotary evaporator until cloudy. The solution was stored in a refrigerator overnight. The solid was filtered off, and the filtrate was extracted with three 80-ml portions of EtOAc. A solution of the solid in MeOH/EtOAc was combined with the extracts and passed through a short pad of silica gel, eluting with EtOAc. The solution was then concentrated to a small volume on a rotary evaporator, and the resulting suspension was diluted with an equal volume of ethanol, sonicated, and filtered to give 3-H-pyrrcilo[3,2-f]quinoline-2-one as a light green solid (0.52 g, 33%); 1 H NMR (DMSO-d 6 ): δ 3.80 (s, 2H), 7.35 (d, J=8.8 Hz, 1H), 7.44 (dd, J=8.4, 4.2 Hz, 1H), 7.88 (d, J=8.8 Hz, 1H), 8.08 (d, J=8.4 Hz, 1H), 8.70 (dd, J=4.2, 1.6 Hz, 1H), 10.57 (br s, 1H); APCI-MS m/z 183 (M−H) − .
[0281] Procedure G
[0282] Method for isatin hydrazone formation: preparation of C-{4-[N′-(5-hydroxy4,6-dimethyl-2-oxo-1,2-dihydroindol(3-ylidene)hydrazino]phenyl}N-methylmethanesulfonamide.
EXAMPLE 99
C{4-[N′-(5-hydroxy4,6-dimethyl-2-oxo-1,2-dihydroindol(3-ylidene)hydrazino]phenyl}-N-methylmethanesulfonamide.
[0283] 4,6-Dimethyl-5-hydroxy-1H-indol-2,3-dione was prepared from 3,5-dimethyl-4-hydroxyaniline according to Procedure A: 1 H NMR (DMSO-d 6 ): δ 2.17 (s, 3H), 2.30 (s, 3H), 6.45 (s, 1H), 8.29 (s, 1H), 10.65 (s, 1H); ESI-MS m/z 190 (M−H) − . A mixture of 100 mg (0.52 mmol) of 4,6-dimethyl-5-hydroxy-1H-indol-2,3-dione and 144 mg (0 57 mmol) of C-(4-hydrazinophenyl{N-methylmethanesulfonamide hydrochloride in 5 ml of EtOH was heated to 80° C. for 1 h. Upon cooling 10 ml of H 2 O was added and the solid was collected by vacuum filtration and dried in a vacuum oven at 60° C. to afford the title compound as a yellow solid (79 mg, 79%); mp 252-255° C.; 1 H NMR (DMSO-d 6 ): δ 2.16 (s, 3H), 2.44 (s, 3H) 2.52 (d, J=4.9 Hz, 3H), 4.25 (s, 2H), 6.47 (s, 1H), 6.84 (q, J=4.9 Hz, 1H), 7.28 7.34 (m, 4H), 7.92 (s, 1H), 10.69 (s, 1H), 12.87 (s, 1H); APCI-MS m/z 411 (M+Na) + . Anal. Calcd for C 18 H 20 N 4 O 4 S: C, 55.66; H, 5.19; N, 14.42; S, 8.25. Found: C, 55.56; H, 5.21; N, 14.25; S, 8.08.
[0284] Procedure H
[0285] Method for dimethylaminomethinyloxindole formation: preparation of 8-dimethylamino-methylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one.
[0286] To a suspension of 1.0 g (5.3 mmol) of 6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one in 7.5 mL of DMF was added 1.38 g (6.80 mmol) of N,N-dimethylformamidedi-t-butyl acetal. The mixture was stirred at ambient temperature for 1 h and diluted with 7.5 mL of Et 2 O. The resulting precipitate was isolated filtration to afford 8-dimethylamino-methylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one as a tan solid (1.0 g, 77%): 1 H NMR (DMSO-d 6 ): δ 3.33 (bs, 3H), 3.59 (bs, 3H), 6.97 (d, J=8.4, 1H), 7.33 (s, 1H), 7.62 (d, J=8.4, 1H), 9.13 (s,1H), 10.29 (s, 1H1); APCI-MS: m/z 246 (M+H) + .
[0287] Procedure I
[0288] Method for ethoxymethinyloxindole formation: preparation of 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one.
[0289] To a 250-ml round bottom flask was added a stir bar, 6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one (4.0 g, 0.021 mol), 40 mL of glacial acetic and diethoxymethyl acetate (17.0 g, 0.105 moles). The flask was fitted with a reflux condensor and charged with nitrogen. The reaction was heated to reflux for 8 h. The flask was cooled, the stir bar was removed and the reaction was concentrated to a wet solid. The solid was triturated with a solution of ether and ethanol. The mixture was filtered, the solid was washed with an ethanol-ether solution, and the solid was dried under vacuum to yield 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one: 1 H NMR (DMSO-d 6 ): δ 10.5 (s, 1H), 9.1 (s, 1H), 7.8 (d, 1H), 7.7 (s, 1H), 7.0 (d, 1H), 4.5 (q, 2H), 1.4 (t, 3H); APCI-MS m/z 245 (M−H) − .
[0290] Procedure J
[0291] Method for vinylogous urea formation: preparation of 4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-N-pyridin-2-yl-benzenesulfonamide.
EXAMPLE 72
4-[(7-Oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8 ylidenemethyl)-amino]-N-pyridin-2-yl-benzenesulfonamide
[0292] To a 25 ml round bottom flask was added a stir bar, 246 mg (1.00 mmol) of 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one, 249 mg (1.00 mmol) of sulfapyridine and 10 ml of ethanol. The flask was fitted with a water-cooled reflux condenser, and the mixture was heated to reflux using an oil bath with stirring for 18 h. The reaction was allowed to cool and was filtered. The precipitate was washed with excess ethanol and dried under vacuum to yield 321 mg (71%) of the title compound: 1 H NMR (DMSO-d 6 ): δ 11.9 (br s, 1H), 11.2 (d, 1H), 10.9 (s, 1H), 9.3 (s, 1H), 8.1 (d, 2H), 7.9 (m, 3H), 7.8 (m, 1H), 7.6 (d, 2H), 7.2 (d, 1H), 7.2 (d, 1H), 6.9 (t, 1H); C 21 H 15 N 5 O 3 S 2 : APCI-MS m/z 450 (M+H) + .
[0293] Note: One equivalent of strong acid, e.g., HCl or methanesulfonic acid, is generally required in this reaction. The acid can be supplied as the aniline salt or as a separate component. Similar conditions can be used for condensing anilines with 3-dimethylaminomethylene-, 3-t-butoxymethylene-, and 3-hydroxymethylenesubstituted 2,3-dihydro-1H-indol-2-ones.
[0294] Procedure K
[0295] Method for 5-N-substituted amide formation: preparation of 2-oxo-3[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid dimethylamide
EXAMPLE 38
2-Oxo-3[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid dimethylamide
[0296] To 100 mg (0.190 mmol) 2-oxo-3[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid pentafluorophenyl ester in 5 mL acetonitrile was added 50 μL (5.6 M in ethanol, 0.28 mmol) of a solution of dimethylamine and 20 μL (0.25 mmol) of pyridine, and the reaction was stirred overnight. The solution was concentrated, and the resulting solid was triturated with EtOAc to give the title compound as a yellow solid (39 mg, 53%): mp >230° C.; 1 H NMR (DMSO-d 6 ): δ 12.71 (s, 1H), 11.22 (s, 1H), 7.75 (d, J=8.8 Hz, 2H), 7.60 (s, 1H), 7.58 (d, J=8.8 Hz, 2H), 7.31 (dd, J=1.7, 8.1 Hz, 1H), 7.23 (s, 2H), 6.93 (d, J=8.0 Hz, 1H), 2.95 (s, 611); APCI-MS: m/z 386 (m-H). Anal. Calcd for C 17 H 17 N 5 O 5 S.½H 2 O: C, 51.51; H, 4.58; N, 17.67. Found: C, 51.69; H, 4.25; N, 17.63.
[0297] Procedure L
[0298] Method for introducing 4-substituents via palladium-catalyzed coupling: preparation of 4-(N′-{4-[2-(4-hydroxyphenyl)-vinyl]-2-oxo-1,2-dihydro-indol-3-ylidene}-hydrazino)-benzenesulfonamide (Z isomer).
EXAMPLE 15
4-(N′-{4-[2-(4-Hydroxyphenyl)-vinyl]-2-oxo-1,2-dihydro-indol-3-ylidene}-hydrazino)benzenesulfonamide (Z Isomer)
[0299] A mixture of 1.0 g (3.6 nimol) of 4-iodo-1H-indole-2,3-dione (Snow, et al., Journal of the American Chemical Society 1977, 99, 373444), 0.42 g (4.2 mmol) of TEA, 0.06 g (0.27 mmol) of palladium(II) acetate, 0.16 g (0.54 mmol) of tri-totylphosphine and 5.0 g (4.2 mmol) of a 10% solution of 4-vinylphenol in propylene glycol was suspended in 15 mL of dry acetonitrile in a pyrex sealed tube and heated to 100° C. for 4 h. The mixture was cooled to rt, quenched with 50 mL of 10% hydrochloric acid and extracted with two 100 mL-portions of EtOAc. The combined extracts were dried over MgSO 4 and concentrated to give a brown solid, which was subjected to chromatography on silica gel, eluting with hexane:EtOAc (3:1), to yield 0.125 g (13%) of trans-4-[2-(4-hydroxyphenyl) vinyl]-1H-indole-2,3-dione as; a red solid: 1 H NMR (DMSO-d 6 ): δ 6.6-7.6 (m, 8H), 7.77 (d, J=16.4 Hz, 1H), 9.85 (bs, 1H), 11.00 (bs, 11H); APCI-MS m/z 264 (M−1) − . Condensation of trans-4-[2-(4-hydroxyphenyl)vinyl]-1H-indole-2,3-dione and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G gave the title compound in 27% yield as an orange solid: 1 H NMR (DMSO-d 6 ): δ 6.78 (d, J=7.8 Hz, 1H), 6.88 (d, J=8.7 Hz, 2H), 7.26 (t, J=7.8 Hz, 1H), ), 7.29 (s, 2H), 7.36 (d, J=16.5 Hz, 1H), 7.47 (d, J=7.8 Hz, 1H), 7.53 (d, J=8.7 Hz, 2H), 7.57 (d, J=8.7 Hz, 2H), ), 7.81 (d, J=8.7 Hz, 2H), 8.03 (d, J=16.5 Hz, 1H), 9.78 (s, 1H), 11.17 (s, 1H), 13.02 (s, 1H); APCI-MS m/z433 (M−1) − .
[0300] Procedure M
[0301] Method for reducing 4-alkenyl substituents: preparation of 4-(N′-{4-[2-(4-hydroxyphenyl)-ethyl]-2-oxo-1,2-dihydro-indol-3-ylidene}-hydrazino)-benzenesulfonamide
EXAMPLE 14
4N′-(4-[2-(4-Hydroxyphenyl)-ethyl]-2-oxo-1,2-dihydro-indol-3-ylidene}-hydrazino)-benzenesulfonamide.
[0302] A mixture of 0.028 g (0.64 mmol) of 4-(N′4-[2-(4-hydroxyphenyl)-vinyl]-2-oxo-1,2-dihydro-indol-3-ylidene)hydrazino)-benzenesulfonamide (Z isomer) and 0.015 g of 10% palladium on charcoal in 60 mL of MeOH:THF (4:1) was subjected to hydrogenation on a Parr apparatus at 50 psi for 1 h. The mixture was filtered through celite, and the filtrate was concentrated to give 0.026 g (93%) of the title compound as a yellow solid: 1 H NMR (DMSO-d 6 ): δ 2.82 (t, J=8.0 Hz, 2H), 3.23 (t, J=8.0 Hz, 2H), 6.69 (d, J=8.4 Hz, 2H), 6.78 (d, J=7.7 Hz, 1H), 6.89 (d, J=7.7 Hz, 1H), ), 7.07 (d, J=8.4 Hz, 2H), 7.18 (t, J=7.7 Hz, 1H), 7.26 (s, 2H), 7.45 (d, J=8.8 Hz, 2H), 7.71 (d, J=8.8 Hz, 2H), 9.20 (bs, 1H), 11.12 (s, 1H), 13.02 (s, 11H); APCI-MS m/z435 (M−1) − .
EXAMPLE 1
4-[N′-(4-Nitro-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z Isoimer)
[0303] The title compound was prepared from 4-nitro-1H-indole-2,3-dione (Gassman, et al., Journal of Organic Chemistry 1977, 42, 1344-8) and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G in 33% yield: 1 H NMR (DMSO-d 6 ): δ 7.23 (d, J=7.7 Hz, 1H), 7.31 (s, 2H), 7.47 (t, J=7.9 Hz, 1H), 7.56 (d, J=7.9 Hz, 2H), 7.59 (d, J=7.2 Hz, 1H), 7.83 (d, J=7.7 Hz, 2H), 11.59 (s, 1H), 13.20 (s, 1H); APCI-MS m/z 361 (M) − . Anal. Calcd for C 14 H 11 N 5 O 5 S: C, 46.54, H, 3.07; N, 19.38; S, 8.87. Found C, 46.62, H, 3.09; N, 19.46; S, 8.81.
EXAMPLE 2
2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-4-carboxylic Acid Amide (E Isomer)
[0304] 1H-Indole-2,3-dione-4-cadroxamide was prepared from aniline-3-carboxamide according to Procedure A in 3% yield: 1 H NMR (DMSO-d 6 ): δ 7.17 (d, J=8.1 Hz, 1H), 7.32 (d, J=8.1 Hz, 1H), ), 7.56 (t, J=8.1 Hz, 1H), 8.02 (bs, 2H), 11.86 (bs, 1H); APCI+MS m/z 191 (M+1) − . Condensation of 1 H-indole-2,3-dione-4-carboxamide with 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G gave the title compound in 31% yield: 1 H NMR (DMSO-d 6 ): δ 7.11 (d, J=8.3 Hz, 1H), 7.18 (s, 2H), 7.27 (d, J=8.8 Hz, 2H), 7.32 (d, J=7.0 Hz, 1H), 7.51 (d, J=7.4 Hz, 1H), 7.75 (d, J=8.8 Hz, 2H), 8.0 (bs, 2H), 10.40 (s, 1H), 10 80 (s, 1H); APCI-MS m/z 359 (M) − . Anal. Calcd for C 15 H 13 N 5 O 4 S.0.12H 2 O: C, 49.83, H, 3.69; N, 19.37; S, 8.86. Found C, 49.71, H, 3.71; N, 19.32; S, 8.84.
EXAMPLE 3
4-[N′-(4-Isopropyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z Isomer)
[0305] The title compound was prepared from 4-isopropyi-1H-indole-2,3-dione (Krantz and Young, 1989, U.S. Pat. No. 4,873,232) and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G in 73% yield: 1 H NMR (DMSO-d 6 ): 1.30 (d, J=6.7 Hz, 6H), 3.82 (septet, J=6.7 Hz, 1H), 6.76 (d, J=7.8 Hz, 1H), 7.01 (d, J=7.8 Hz, 1H), 7.23 (t, J=7.8 Hz, 1H), 7.24 (s, 2H), 7.48 (d, J=8.7 Hz, 2H), 7.79 (d, J=8.7 Hz, 2H), 11.10 (s, 1H), 13.05 (s, 1H); APCI-MS m/z 357 (M−1). Anal. Calcd for C 17 H 18 N 4 O 3 S: C, 56.97, H, 5.06; N, 15.63; S, 8.95. Found C, 56.88, H, 5.12; N, 15.73; S, 8.91.
EXAMPLE 4
4-[(4-Hydroxymethyl-2-oxo-1,2-dihydro-indol-3-ylidenemethyl)-amino]-N-methyl-benzenesulfonamide
[0306] A mixture of 3.0 g (20 mmol) of 3-aminobenzyl alcohol, 3.36 g (22.0 mmol) of t-butyldimethylsilyl chloride and 1.52 g (22.0 mmol) of imidazole were dissolved in 20 mL of DMF. The solution was stirred at rt for 16 h and then diluted with 250 mL of hexane and 250 mL of EtOAc. The organic phase was washed twice with brine, dried over MgSO 4 and concentrated to give 4.8 g of 3-([t-butyldimethylsilyloxy]methyl-benzenamine as a clear oil. This was dissolved in 100 mL of CH 2 Cl 2 , cooled with stirring to −65° C. and 2.17 g (20.0 mmol) of t-butyl hypochlorite was added. After 10 min of stirring, a solution of 2.68g (20.0 mmol) of ethyl methylthioaceatate in 10 mL of CH 2 Cl 2 was added, and the solution was stirred for 1 h. TEA (2.02 g, 20.0 mmol) was added and the reaction was warmed to rt over 1 h. The solution was washed with water and concentrated to an oil. This was redissolved in 100 mL of ether, 12 mL of 2 N hydrochloric acid was added!, and the mixture was stirred overnight. The ether phase was separated and concentrated to an oil. This was chromatographed on silica gel eluting with hexane:EtOAc (initially a 3:1 ratio increasing to 1:2) to yield 0.82 g (20%) of 4-hydroxymethyl-3-methylsulfanyl-1,3-dihydro-indol-2-one: 1 H NMR (DMSO-d 6 ): δ 1.89 (s, 3H), 4.45 (s, 1H), 4.62 (m, 2H), 5.1 (bs, 1H), 6.87 (d, J=7.7 Hz, 1H), 7.02 (d, J=7.7 Hz, 1H), 7.17 (t, J=7.7 Hz, 1H), 10.44 (s, 1H). Further elution yielded 0.53g (13%) of 6-hydroxymethyl-3-methysulfanyl-1,3-dihydro-indol-2-one: 1 H NMR (DMSO-d 6 ): δ 1.99 (s, 3H), 4.48 (s, 2H), 4.50 (s, 1H), 5.1 (bs, 1H), 6.84 (s, 1H), 6.94 (d, J=7.6 Hz, 1H), 7.22 (d, J=7.6 Hz, 1H), 10.54 (s, 1H).
[0307] A solution of 0.82 g (3.9 mmol) of 4-hydroxymethyl-3-methylsulfanyl-1,3-dihydro-indol-2-one in DMF (20 mL) was treated with 0.65 g (4.3 mmol) of t-butyldimethylsilyl chloride and 0.3 g (4.4 mmol) of imidazole and stirred for 24 h. The solution was diluted with 75 mL of hexane and 75 mL of EtOAc. The organic phase was washed with brine, dried over MgSO 4 and concentrated to give 1.2 g (95%) of 3-methylsulfanyl-4-(t-butyldimethylsilyloxy)methyl-1,3-dihydro-indol-2-one as a clear oil which crystallised upon storage at rt: 1 H NMR (DMSO-d 6 ): δ 0.051 (s, 3H), 0.064 (s, 3H), 0.881 (s, 9H), 1.87 Cs, 3H), 4.43 (s, 1H), 4.79 (d, J=14.2 Hz, 111), 4.88 (d, J=14.2 Hz, 1H), 6.70 (d, J=7.9 Hz, 1H), 7.00 (d, J=7.9 Hz, 1H),′ 7.19 (t. J=7.9 Hz, 1H), 10.48 (s, 1H); APCI-MS m/z 346 (M+23) + .
[0308] A solution of 1.2 g (3.7 mmol) of 3-methylsulfanyl-4-(t-butyldimethylsilyloxy)-methyl-1,3-dihydro-indol-2-one in THF (25 mL) was stirred with saturated ammonium chloride solution (20 mL), and activated zinc dust (5 g) was added. The mixture was stirred for 60 h at rt. The organic phase was separated, dried over MgSO 4 and concentrated to give 1.16 g of impure 4(t-butyldimethylsilytoxy)methyl-1,3-dihydro-indol-2-one as an off-white solid: 1 H NMR (DMSO-d 6 ): δ 0.11 (s, 6H), 0.86 (s, 9H), 3.42 (s, 2H), 4.67 (s, 2H), 6.74 (d, J=7.7 Hz, 1H), 6.95 (d, J 7.7 Hz, 1H), 7.18 (t, J=7.7 Hz, 1H), 10.40 (s, 1H). A solution of 0.64 g (2.3 mmol) of 4-(t-butyldimethylsilyloxy)methyl-1,3-dihydro-indol-2-one in DMF dimethylacetal (5 mL) was heated to 100° C. for 1 h. The excesss DMF dimethylacetal was removed under high vacuum, and the resulting dark oil was chromatographed on silica gel, eluting with EtOAc, to give 0.34 g (44%) of 3-dimethylaminomethylene-4-(t-butyldimethyl-silyloxy)methyl-1,3-dihydro-indol-2-one as a white solid: 1 H NMR (DMSO-d 6 ): 8-0.03 (s, 6H), 0.81 (s, 9H), 3.29 (s, 6H), 4.64 (s, 2H), 6.66 (d, J=7.3 Hz, 1H), 6.73 (d, J=7.3 Hz, 1H), 6.79 (t, J=7.3 Hz, 1H), 7.76 (s, 1H), 9.97 (s, 1H) ); APCI-MS m/z 333 (M+1) + . A solution of 0.115 g (0.34 mmol) of 3-dimethylaminomethylene-4-(t-butyldimethylsilyloxy)methyl-1,3-dihydro-indol-2-one in ethanol (10 mL) was treated with 0.076 g (0.34 mmol) N-methylsulfanilamide hydrochloride. The solution was refluxed for 0.5 h and cooled to rt. The resulting yellow precipitate was isolated by filtration, washed with ethanol and dried to yield 0.048 g (38%) of the title compound: 1 H NMR (DMSO-d 6 ): δ 2.37 (d, J=5.0 Hz, 3H), 4.67 (s, 2H), 5.3 (bs, 1H), 6.78 (d, J=7.5 Hz, 1H), 6.93 (d, J=7.5 Hz, 1H), 6.99 (t, J=7.5 Hz, 1H), 7.33 (q, J=5.0 Hz, 1H), 7.44 (d, J=8.6 Hz, 2H), 7.71 (d, J=8.6 Hz, 2H), 8.32 (d, J=12.2 Hz, 1H), 10.67 (s, 1H), 11.26 (d, J=12.2 Hz, 1H); APCI-MS m/z 358 (M−1) − . Anal. Calcd for C 17 H 17 N 3 O 4 S: C, 56.81, H, 4.77; N, 11.69, S, 8.92. Found C, 56.89, H, 4.81; N, 11.70; S, 8.84.
EXAMPLE 5
4-{N′-[2-Oxo-4-(2-pyridin-4-yl-ethyl)-1,2-dihydro-indol-3-ylidene]-hydrazino}-benzenesulfonamide (Z Isomer)
[0309] A mixture of 3.0 g (20 mmol) of 3-nitroiodobenzene, 3.5 mL (25 mmol) of TEA, 0.045 g (0.20 mmol) of p)atladium(II) acetate and 2.77 g (25.0 mmol) of 4-vinylpyridine was suspended in 4 mL of dry acetonitrile in a pyrex sealed tube and heated to 100° C. for 48 h. The mixture was cooled to rt and was quenched with 200 mL of 10% hydrochloric acid. The resulting yellow solid was isolated by filtration and partitioned between 250 mL of EtOAc and 250 mL of I N aqueous sodium hydroxide. The organic phase was dried over MgSO 4 and concentrated to give 3.0 g (66%) of 4-[2-(3-nitrophenyl)ethenyl]-pyridine as a yellow solid: 1 H NMR (DMSO-d 6 ): δ 3.04.6 (br s, 1H), 7.71-7.78 (m, 2H), 8.07 (d, d=15.8 Hz, 1H), 8.138.16 (m, 3H), 8.24 (d, J=8.0 Hz, 1H), 8.56 (s, 1H), 8,84 (d, J=5.7 Hz, 2H); ESI-MS m/z 227 (M+1) + . A portion (1.3 g, 7.1 mmol) of this solid was dissolved in 100 mL of EtOAc, and 0.5 g of 10% palladium on charcoal was added. The mixture was hydrogenated on a Parr apparatus at 40 psi for 1.5 h. Another 0.5 g batch of 10% palladium on charcoal was added and the mixture was subjected to further hydrogenation for 1 h. The palladium catalyst was removed by filtration through a pad of celite, and the filtrate was concentrated to give 1.13 g (100%) of 3-(4-pyridinyl)ethylaniline: 1 H NMR (DMSO-d 6 ): δ 2.69 (m, 2H), 2.80 (m, 2H), 4.9 (bs, 2H), 6.33 (d, J=7.7 Hz, 2H), 6.38 (s, 1H), 6.86 (t, J=7.7 Hz, 11H), 7.20 (d, J=5.8 Hz, 2H), 8.41 (d, J=5.8 Hz, 2H). Conversion of 3-[2-(4-pyridinyl)ethyl]-aniline to 4-(2-pyddin4-ylethyl)-1H-indole-2,3-dione was accomplished according to Procedure A in 24% overall yield: 1 H NMR (DMSO-d 6 ): δ 2.80 (m, 2H), 3.10 (m, 2H), 6.70 (d, J=8.0 Hz, 1H), 6.81 (d, J=8.0 Hz, 1H), 7.24 (m, 2H), 7.40 (t, J=8.0 Hz, 1H), 8.42 (bs, 2H), 11.00 (s, 1H). Conversion of 4-(2-pynidin-4-yl-ethyl)-1H-indole-2,3-dione to the title compound was accomplished according to Procedure G in 40% overall yield: 1 H NMR (DMSO-d 6 ): δ 2.98 (t, J=7.9 Hz, 2H), 3.30 (m, 2H, underneath water peak), 6.78 (d, J=7.7 Hz, 1H), 6.88 (d, J=7.6 Hz, 1H), 7.17 (t, J=7.6 Hz, 1H), 7.25 (s, 2H), 7.29 (d, J=6.0 Hz, 2H), 7.37 (d, J=8.8 Hz, 2H), 7.66 (d, J=8.8 Hz, 2H), 8.47 (d, J=6.0 Hz, 2H), 11.13 (s, 1H), 12.98 (s, 1H); APCI-MS m/z 420 (M−1) − . Anal. Calcd for C 21 H 19 N 5 O 3 S.0.15 HCl: C, 55.93, H, 4.43; N, 15.53; S, 7.11. Found C, 56.05, H. 4.36; N, 15.38; S, 7.18.
EXAMPLE 6
2-Oxo-3-(4-sulfamoyl-phenylamino)-methylene]-2,3-dihydro-1H-indole-4-carboxylic Acid Ethyl Ester (Z Isomer)
[0310] The title compound was prepared from 2-oxo-2,3-dihydro-1H-indole-4-carboxylic acid ethyl ester (Connolly and Durst, Synlett 1996, 6634; Kozikowski and Kuniak, Journal of Organic Chemistry 1978, 43, 20834) and sulfanilamide according to Procedure J in 14% overall yield: 1 H NMR (DMSO-d 6 ): δ 1.33 (t, J=7.1 Hz, 3H), 4.37 (q, J=7.1 Hz, 2H), 7.10 (d, J=7.6 Hz, 1H), 7.15 (t, J=7.6 Hz, 1H), 7.30 (s, 2H), 7.41 (d, J=8.6 Hz, 2H), 7.57 (d, J=7.6 Hz, 1H), 7.82 (d, J 8.6 Hz, 2H), ), 9.50 (d, J 12.6 Hz, 1H), 10.96 (s, 1H), 11.75 (d, J=12.6 Hz, 1H); APCI-MS maz 386 (M−1).
EXAMPLE 7
4-[N′-(4-Iodo-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z Isomer)
[0311] The title compound was prepared from 4-iodo-1H-indole-2,3-dione (Snow, et al., Journal of the American Chemical Society 1977, 99, 373444) and 4-sulfonamidophenyl-hydrazine hydrochloride according to Procedure G in 87% overall yield: 1 H NMR (DMSO-d 6 ): δ 6.93 (d, J=7.6 Hz, 1H), 6.99 (t, J=7.6 Hz, I H), 7.25 (s, 2H), 7.50 (d, J=7.6 Hz, 1H), 7.66 (d, J=8.7 Hz, 2H), 7.77 (d, J=8.7 Hz, 2H), 11.17 (s,1H), 12.94 (s,1H); APCI-MS m/z 441 (M−1) − . Anal. Calcd for C 14 H 11 IN 4 O 3 S: C, 38.02, H, 2.51; I, 28.70; N, 12.67; S, 7.25. Found C, 38.05, H, 2.51; I, 28.78; N, 12.64; S, 7.19.
EXAMPLE 8
4N′-(4-Isobutyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide
[0312] A mixture of 0.20 g (1.0 mmol) of 4-(2-methyl-propenyl)-1H-indole-2,3-dione and 0.05 g of 10% palladium on charcoal in 25 mL of EtOAc was subjected to hydrogenation on a Parr apparatus at 46 psi for 1 h. The mixture was filtered through celite, and the filtrate was concentrated to dryness. The solid was purified by chromatography on silica gel, eluting with hexane:EtOAc (4:1), to furnish 0.027 g (13%) of 4-isobutyl-1H-indole-2,3-dione: 1 H NMR (DMSO-d 6 ): δ 0.89 (d, J=6.7 Hz, 6H), 1.86 (nonet, J=6.7 Hz, 1H), 2.72 (d, J=6.7 Hz, 1H), 6.74 (d, J=7.8 Hz, 1H), 6.86 (d, J=7.8 Hz, 1H), 7.48 (t, J=7.8 Hz, 1H), 11.03 (s, 1H).
[0313] Condensation of 4-isobutyl-1H-indole-2,3-dione and 4-sulfonamido-phenylhydrazine hydrochloride according to Procedure G gave the title compound in 65% yield: 1H NIMR (DMSO-d 6 ): δ 0.96 (d, J=6.4 Hz, 6H), 2.05 (m, 1H), 2.87 (d, J=7.0 Hz, 2H), 6.79 (d, J=7.6 Hz, 1H), 6.85 (d, J=7.6 Hz, 1H), 7.20 (t, J=7.6 Hz, 1H), 7.26 (s, 2H), 7.51 (d, J=8.5 Hz, 2H), 7.81 (d, J=8.5 Hz, 2H), 11.13 (s, 1H), 13.03 (s, 1H); APCI-MS m/z 371 (M−1) − .
EXAMPLE 9
4-{N′-[4-(2-Methyl-propenyl)-2-oxo-1,2-dihydro-indol-3-ylidene]-hydrazino}-benzenesulfonamide
[0314] By methods described in Procedure L, 4-(2-methyl-propenyl)-1H-indole-2,3-dione was prepared from 4-iodo-1H-indole-2,3-dione and isobutylene in 34% yield: 1 H NMR (DMSO-d 6 ): δ 1.82 (s, 3H), 1.90 (s, 3H), 6.79 (d, J=7.9 Hz, 1H), 6.94 (d, J=7.9 Hz, 1H), 7.47 (t, J=7.9 Hz, 1H), 10.97 (s, 1H); APCI-MS m/z 200 (M−1) − . Condensation of 4-(2-methyl-propenyl)-1H-indole-2,3-dione and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G gave the title compound as a yellow solid (51% yield): 1 H NMR (DMSO-d 6 ): δ 1.84 (s, 3H), 2.04 (s 3H), 6.78 (s, KH), 6.79 (d, J=7.8 Hz, 1I), 6.96 (d, J=7.8 Hz, 111), 7.24 (t, J=7.8 Hz, 1H), 7.24 (s, 2H), 7.48 (d, J=8.8 Hz, 2H), 7.80 (d, J=8.8 Hz, 2H), 11.11 (s, 1H), 12.91 (5s, 1H); APCI-MS m/z 369 (M−1) − . Anal. Calcd for C18H18N403S: C, 58.36, H, 4.90; N, 15.12; S, 8.66. Found C, 58.41, H, 4.87; N, 15.18; S, 8.56.
EXAMPLE 10
4-{N′-[4-(2-Methyl-1-butenyl)-2-oxo-1,2-dihydro-indol-3-ylidene]-hydrazino}-benzenesulfonamide and 4-{N′-[4-(2-methyl-2-butenyl)-2-oxo-1,2-dihydro-indol-3-yliidene]-hydrazino}-benzenesulfonamide
[0315] Coupling of 4-iodoisatin and 2-methyl-1-butene according to Procedure L gave a mixture of isomers [the major pair of isomers was E/Z-4-(2-methyl-1-butenyl)-1H-indole-2,3-dione and the minor pair of isomers was E/Z-4-(2-methyl-2-butenyl)-1H-indole-2,3-dione] in 21% yield.: 1 H NMR (DMSO-d 6 , integral ratios are normalized to the KH singlet observed at δ 10.97): δ 1.06 (m. 2.6H), 1.47 (s, 1.05H), 1.83 (m, 1.41H), 1.88 (s, 1.1H), 2.19 (m, 1.6H), 3.50 (s, 0.26H), 5.22 (m, 0.16H), 6.60-6.72 (m, 2H), 6.76-6.82 (m, 0.23H), 6.86 (d, J=7.7 Hz, 0.35H), 7.46 (d, J=7.6 Hz, 0.42H), 7.4-7.6 (m, 1H), 10.97 (s, 1H); APCI-MS m/z 214 (M−1) − . Condensation of the mixture of E/Z-4-(2-methyl-1-butenyl)-1H-indole-2,3-dione and EZ4-(2-methyl-2-butenyl 1H-indole-2,3-dione and 4-sulfonamidophenyl-hydrazine hydrochloride according to Procedure G gave the title compound mixture as a yellow solid (51% yield): 1 H NMR (DMSO-d 6 , integral ratios are normalized to the 1H singlet observed at δ 11.11): δ 1.07 (t, J=7.5 Hz, 1.3H), 1.21 (t, J=7.5 Hz, 1.3H), 1.54 (d, J=6.5 Hz, 0.7H), 1.63 (s, 0.7H), 1.86 (s, 1.2H), 2.03 (s;, 1.1H), 2.21 (q, J=7.7 Hz, 0.7H), 2.32 (q, J=7.7 Hz, 0.8H), 3.71 (s, 0.4H), 5.2 (m, 0.2H), 6.72-6.85 (m, 2.1H), 6.89 (d, J=7.9 Hz, 0.39H), 6.97 (d, J=7.9 Hz, 0.42H), 7.18-7.26 (m, 3.1H), 7.47-7.51 (m, 2.1H), 7.77-7.81 (m, 2.1H), 11.11 (s, 1H), 12.89 (s, 0.3H), 12.97 (s, 0.35H), 13.02 (s, 0.24H); APCI-MS m/z 383 (M−1) − .
EXAMPLE 11
4-{N′-[4-(2-methylbutyl)-2-oxo-1,2-dihydro-indol-3-ylidene]-hydrazino}-benzenesulfonamide
[0316] Reduction of the mixture of 4-{N′-[4-(2-methyl-1-butenyl)-2-oxo-1,2-dihydro-indol-3-ylidene]-hydrazino}-benzenesulfonamide and 4-{N′-[4-(2-methyl-2-butenyl{2-oxo-1,2-dihydro-indol-3-ylidene]-hydrazino}-benzenesulfonamide according to Procedure M gave the title compound in 79% yield: 1 H NMR (DMSO-d 6 ): δ 0.87-0.90 (m, 6H), 1.21-1.25 (m, 2H), 1.47-1.63 (m, 1H), 2.82 (dd, J=12.6, 8.1 Hz, 1H), 2.95 (dd, J=12.6, 6.6 Hz, 1H), 6.77 (d, J=7.7 Hz, 1H), 6.84 (d, J=7.7 Hz, 1H), 7.18 (t, J=7.7 Hz, 1H), 7.25 (s, 2H), 7.49 (d, J=8.6 Hz, 2H), 7.79 (d, J=8.6 Hz, 2H), 11.12 (s, 1H), 13.04 (s, 1H); APCI-MS m/z 385 (M−1) − .
EXAMPLE 12
4-[N′-(4-Cyclobutylmethyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonzamide (Z Isomer)
[0317] Reduction of 4-[N′-(4-cyclobutylidenemethyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide according to methods described in Procedure M gave the title compound in 94% yield: 1 H NMR (DMSO-d 6 ):δ 1.81 (m, 4H), 1.96 (m, 2H), 2.73 (m, 1H), 3.07 (d, J=7.2 Hz, 2H), 6.76 (d, J=7.8 Hz, 1H), 6.86 (d, J=7.8 Hz, 1H), 7.17 (t, J=7.8 Hz, 1H), 7.24 (s, 2H), 7.48 (d, J=8.6 Hz, 2H), 7.79 (d, J=8.6 Hz, 2H), 11.08 (s, 1H), 12.93 (s, 1H); APCI-MS m/z 383 (M−1) − .
EXAMPLE 13
4-[N′-(4-(Cyclobutylidenemethyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z Isomer)
[0318] By methods described in Procedure L, 4-cyclobutylidenemethyl-1H-indole-2,3-dione was prepared from 4-iodo-1H-indole-2,3-dione and methylene cyclobutene in 25% yield: 1 H NMR (DMSO-d 6 ): δ 2.08 (quintet, J=7.8 Hz, 2H), 2.91 (m, 2H), 3.06 (m, 2H), (3.67 (d, J=7.7 Hz, 1H), 6.94 (d, J=7.7 Hz, 1H), 6.96 (s, 1H), 7.47 (d, J=7.7 Hz, 1H), 11.00 (bs, 1H); APCI-MS m/z 211 (M-l)-. Condensation of 4-(cyclobutylidenemethyl)-1H-indole-2,3-dione and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G gave the title compound in 76% yield: 1 H NMR (DMSO-d 6 ): δ 2.11 (quintet, J=7.8 Hz, 2H), 3.00 (t, J=7.8 Hz, 2H), 3.06 (t, J=7.8 Hz, 2H), 6.74 (d, J=7.7 Hz, 1H), 6.97 (d, J=7.7 Hz, 1H), 7.07 (s, 1H), 7.21 (t, J=7.7 Hz, 1H), 7.25 (s, 2H), 7.47 (d, J=8.7 Hz, 2H), 7.81 (d, J=8.7 Hz, 2H), 11.12 (s, 1H), 13.03 (s, 1H); APCI-MS m/z 381 (M−1).
EXAMPLE 14
See Procedure M
EXAMPLE 15
See Procedure L
EXAMPLE 16
4-[N′-(2-Oxo-4-phenoxy-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Mixture of E and Z Isomers)
[0319] The title compound was prepared from 3-phenoxyaniline and 4-sulfonamidophenyl-hydrazine hydrochloride according to Procedure C: mp >250° C.; 1 H NMR (DMSO-d 6 ): δ 6.42 E (d, J=8.4 Hz, 1H), 6.70 E (d, J=7.7 Hz, 1H), 6.76 Z (d, J=8.2 Hz, 1H), 6.82 Z (d, J=7.8 Hz, 1H), 6.99 Z (d, J 8.1 Hz, 2H), 7.06 Z (d, J=8.8 Hz, 2H), 7.1-7.6 E (m, 10H), 7.1-7.6 Z (m, 6H), 7.62 Z (d, J=8.8 Hz, 2H), 7.74 E i,d, J=8.7 Hz, 2H), 10.88 E (s, 1H), 11.18 E (s, 1H), 11.27 Z (s, 1H), 12.77 Z (s, 1H); APCI-MS: m/z 407 (M−H) − . Anal. Calcd for C 20 H 16 N 4 O 4 S: C, 58.81; H, 3.95; N, 13.72; S, 7.85. Found: C, 58.53; H, 4.02; N, 13.66; S, 7.79.
EXAMPLE 17
See Procedure C
EXAMPLE 18
4-{N′-[2-Oxo-4-(1H-pyrazol-3-yl)-1,2-dihydro-indol-3-ylidene]-hydrazino}-benzenesulfonamide
[0320] 4-(1H-Pyrazol-3-yl)-1H-indole-2,3-dione was prepared from 3-(1H-pyrazol-3-yl)aniline according to Procedure A. The title compound was prepared from 4-(1H-pyrazol-3-yl)isatin and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G: 1 H NMR (DMSO-d 6 ): δ 6.72 (s, 1H), 7.22 (s, 2H), 7.39 (s, 1H), 7.48-7.60 (m, 4H), 7.76 (d, J=8.7 Hz, 2H), 7.77 (s, 1H), 11.11 (s, 1H), 12.93 (s, 1H); ESI-MS: m/z 381 (M−H) − .
EXAMPLE 19
4-[(5-Oxazol-5-yl-2-oxo-1,2-dihydro-indol-3-ylidenemethyl)amino]-benzenesulfonamide (Z-Isomer)
[0321] The title compound was prepared in 68% yield from ethoxymethylene-5-oxazol-5-yl-1,3-dihydro-indol-2-one and 4-aminobenzenesulfonamide hydrochloride according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 10.79 (d,1H), 10.73 (s, 1H), 8.76 (d, 1H), 8.38 (s, 1H), 8.0 (s, 1H), 7.77 (d, 2H), 7.56 (d, 2H), 7.43 (s, 1H), 7.40 (d, 1H), 7.26 (s, 2H), 6.91 (d, 1H); APCI-MS: m/z 381 (MH) − .
EXAMPLE 20
2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono-2,3-dihydro-1H-indole-5-carboxylic Acid Pentafluorophenyl Ester
[0322] 2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid was prepared from 1H-indole-2,3-dione5-carboxyiic acid and 4-sulfonamidophenyl-hydrazine hydrochloride according to Procedure G. To a suspension of 2.75 g (7.63 mmol) of the 2-oxo-3[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid in 20 mL DMF was added 1.38 mL (8.03 mmol) pentafluorophenyltrifluoroacetate (PFPTFA), 0.69 mL (8.53 mmol) pyridine, and the suspension was stirred under N 2 for 20 min. TLC (silica gel, 20% MeOH/CH 2 Cl 2 ) indicated residual starting material remained, and the reaction was treated with 10 mL DMF and additional PFPTFA and pyridine (equal portions to above). The reaction was stirred overnight and then poured into 400 mL ether. The solution was washed with two 500-mL portions of water, and 300 mL of EtOAc was added to dissolve precipitate. The solution was washed with 500 mL water, dried over Na 2 SO 4 , filtered through silica gel and concentrated to remove ether. The resulting solid was collected by filtration, washed 50 mL 1:1 ethylaceltate:hexanes and dried overnight in a vacuum oven at 70° C. to give the title compound as a bright yellow solid (2.30 g, 57%): mp >230° C.; 1 H NMR (DMSO-d 6 ): δ 12.77 (s, 1H), 11.68 (s, 1H), 8.32 (d, J=1.9 Hz, 1H), 8.11 (dd, J=1.9 Hz, J=8.2 Hz, 1H), 7.79 (d, J=8.9 Hz, 2H), 7.67 (d, J=8.9 Hz, 2H), 7.28 (s, 2H), 7.16 (d, J=8.4 Hz, 1H); APCI-MS: m/z 525 (M−H) − . Anal. Calcd for C 21 H 11 N 4 O 5 SF 5 : C, 47.92; H, 2.11; N, 10.64. Found: C, 48.00; H, 2.13; N, 10.54.
EXAMPLE 21
4-[N′-(5-Nitro-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z Isomer)
[0323] The title compound was prepared from 5-nitro-1H-indole-2,3-dione (Gassman, et al., Journal of Organic Chemistry 1977, 42, 1344-8) and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G in 94% yield: 1 H NMR (DMSO-d 6 ): δ 7.14 (d, J=8.6 Hz, 1H), 7.33 (s, 2H), 7.75 (d, J=8.8 Hz, 2H), 7.84 (d, J=8.8 Hz, 2H), 8.23 (dd, J=2.2, 8.6 Hz, 1H), 8.42 (d, J=2.2 Hz, 1H), 11.76 (s, 1H), 12.78 (s, 1H). Anal. Calcd for C 14 H 11 N 5 O 5 S: C, 46.54, H, 3.07; N, 19.38. Found C, 46.76, H, 3.13; N, 19.23.
EXAMPLE 22
4-[N′-(5-Hydroxy-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z Isomer)
[0324] The title compound was prepared from 5-hydroxy-1H-indole-2,3-dione (Ijaz, et al., Indian Journal of Chemistry 1994, 33B, 288-9) and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G in 30% yield: 1 H NMR (DMSO6): δ 6.79 (dd, J=2.2, 8.3 Hz, 1H), 6.72 (d, J=8.3 Hz, 1H), 6.98 (d, J=2.2 Hz, 1H), 7.25 (s, 2H), 7.53 (d, J=8.7 Hz, 2H), 7.78 (d, J=8.7 Hz, 2H), 9.20 (s, 1H), 10.80 (s, 1H), 12.82 (s, 1H); APCI-MS m/z 331 (M−H) − .
EXAMPLE 23
4-[N′-(5-Methyl-2-oxo-1,2-dihydroindol-3-ylidene)-hydrazino]-benzenesulfonamide (E Isomer)
[0325] The title compound was prepared from 5-methyl-i H-indole-2,3-dione (Gassman, et al., Journal of Organic Chemistry 1977, 42, 1344-8) and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G in 86% yield: 1 H NMR (DMSO-d 6 ): S 2.3 (s, 3H), 6.76 (d, J=7.9 Hz, 1H), 7.11 (d, J=7.9 Hz, 1H), 7.20 (s, 2H), 7.57 (d, J=8.8 Hz, 2H), 7.77 (d, J=8.8 Hz, 2H), 8.02 (s, 1H), 10.51 (s, 1H), 10.62 (s, 1H); APCI-MS m/z 329 (M−1) − . Anal. Calcd for C 15 H 14 N 4 O 3 S: C, 54.54, H, 4.27; N, 16.96; S, 9.71. Found C, 54.54, H, 4.32; N, 16.87; S, 9.62.
EXAMPLE 24
N-Methyl4-[N′-(2-oxo-5-[1,2,4]triazol-1-yl-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z Isomer)
[0326] 5-[1,2,4]Triazol-1-yl-1H-indole-2,3-dione was prepared from 4-[1,2,4]-triazol-1-yl-phenylamine according to Procedure A in 6% yield: 1 H NMR (DMSO-d 6 ): δ 7.04 (d, J=8.4 Hz, 1H), 7.97 (d, J=2.2 Hz, 1H), 8.01 (dd, J=2.2, 8.4 Hz, 1H), 8.20 (s, 1H), 9.26 (s, 1H), 11.19 (bs, 1H); APCI-MS m/z 215 (M+1) + . Condensation of 5-[1,2,4]triazol-1-yl-1H-indole-2,3-dione with 4-hydrazino-N-methyl-phenylsulfonamide according to Procedure G gave the title compound in 86% yield: 1 H NMR (DMSO-d 6 ): δ 2.38 (d, J=5.0 Hz, 3H), 7.05 (d, J=8.4 Hz, 1H), 7.30 (q, J=5.0 Hz, 1H), 7.65 (d, J=8.7 Hz, 2H), 7.72 (d, J=8.7 Hz, 3H), 8.01 (s, 1H), 8.20 (s, 1H), 9.2:3 (s, 1H), 11.27 (s, 1H), 12.80 (s, 1H); Anal. Calcd for C 14 H 15 N 7 O 3 S.1.3H20: C, 48.52, H, 4.22; N, 23.30; S, 7.62. Found C, 48.53, H, 4.25; N, 23.17; S, 7.55.
EXAMPLE 25
2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-sulfonic Acid Sodium Salt
[0327] The title compound was prepared from 1H-indole-2,3-dione-5-sulfonic acid and 4-sulfonamidophenylhydrazine according to Procedure G: 1 H NMR (DMSO-d 6 ): δ 6.83 (d, J=8.0 Hz, 1H), 7.22 (s, 2H), 7.50 (dd, J=1.7, 8.0 Hz, 1H), 7.56 (d, J=8.7 Hz, 2H), 7.76 (d, J=8.7 Hz, 2H), 7.77 (d, J=1.7 Hz, 1H), 11.12 (s, 1H), 12.70 (s, 1H); APCI-MS: m/z 395 (M−H) − . Anal. Calcd for C 14 H 11 N 4 O 6 S 2 Na.0.9H 2 O.0.2 C 2 H 6 O: C, 38.97; H, 3.18; N, 12.62; S, 14.45. Found: C, 38.84; H, 3.31; N, 12.63; S, 14.59.
EXAMPLE 26
3-[(4-Methylsulfamoyl-phenyl)-hydrazono]-2-oxo-2,3-dihydro-1H-indole-5-carboxylic Acid Amide
[0328] The title compound was prepared from 1H-indole-2,3-dione-5-carboxylic acid amide and 4-N-methylsulfonamidophenylhydrazine according to Procedure G: mp >250° C.; 1 H NMR (DMSO-d 6 ): δ 2.37 (d, J=5.0 Hz, 3H), 6.94 (d, J=8.2 Hz,1H), 7.26 (bs,1H), 7.30 (q, J=5.1 Hz, 1H), 7.62 (d, J=8.7 Hz, 2H), 7.72 (d, J=8.7 Hz, 2H), 7.82 (dd, J 1 =1.5 Hz, J 2 =8.2 Hz, 1H), 7.96 (bs, 1H), 8.12 (s, 1H), 11.30 (s, 1H), 12.73 (s, 1H); APCI-MS: m/z 372 (M−H) − .
EXAMPLE 27
See Procedure E
EXAMPLE 28
5-Brorno-3-[(4-methylsulfonyl-phenyl)-hydrazono]-1,3-dihydro-indol-2-one
[0329] The title compound was prepared in 72% yield from 5-bromo-1H-indole-2,3-dione (Meth-Cohn and Goon, Tetrahedron Letters 1996, 37, 93814) and 4-methylsulfonylphenylhydrazine according to Procedure G: 1 H NMR (DMSO-d 6 ): δ 12.7 (s, 1H), 11.3 (s, 1H), 7.9 (d, 2H), 7.7-7.8 (m, 3H), 7.4 (dd,1H), 6.9 (d, 1H), 3.2 (s, 3H); ESI-MS m/z 392 (M−H) − .
EXAMPLE 29
3-(3H-Benzotriazol-5-ylimino-methylene)-5-iodo-1,3-dihydro-indol-2-one
[0330] The title compound was prepared in 43% yield from 3-hydroxymethylene-1,3-dihydro-indo[-2-one and 5-aminobenzotriazole according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 10.8 (d, 1H), 10.7 (s, 1H), 8.8 (d, 1H), 8.0 (s, 1H), 7.8-7.9 (br nm), 7.5 (d, 1H), 7.3 (d, 1 H); ESI-MS ,m/z 404 (M+H) + .
EXAMPLE 30
2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-sulfonic Acid Amide
[0331] The title compound was prepared from 1H-indole-2,3-dione-5-sulfonic acid amide and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G: mp >250° C.; 1 H NMR (DMSO-d 6 ): δ 7.04 (d, J=8.4 Hz, 1H), 7.25 (s, 2H), 7.26 (s, 2H), 7.60 (d, J=8.9 Hz, 2H), 7.70 (dd, J=8.2, 1.9 Hz, 1H), 7.78 (d, J=8.7 Hz, 2H), 7.98 (d, J=16 Hz, 1H), 11.43 (s, 1H), 12.75 (s, 1H); APCI-MS m/z 395 (M) − . Anal. Calcd for C 14 H 13 N 5 O 5 S 2 .0.5H 2 O: C, 41.58; H. 3.49; N, 17.32; S, 15.86. Found: C, 41.67; H, 3.46; N, 17.26; S, 15.78.
EXAMPLE 31
4-[N′-(5-Methylsulfonyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide
[0332] 5-Methylsulfonyl-1H-indole-2,3-dione was prepared from 4-methylsulfonylaniline according to Procedure A: 1 H NMR (DMSO-d 6 ): δ 3.21 (s, 3H), 7.07(d, J=8.3 Hz, 1H), 7.92 (d, J=1.7 Hz, 1H), 8.05 (dd, J=8.2, 2.0 Hz, 1H), 11.46 (s,1H); APCI-MS m/z 225 (M) − . The title compound was prepared from 5-methylsulfonyl-1H-indole-2,3-dione and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G: mp >250 0 C; 1 H NMR (DMSod6): δ 3.20 (s, 3H), 7.11 (d, J=8.3 Hz, 1H), 7.26 (s, 2H), 7.65 (d, J=8.9 Hz, 2H), 7.78 (d, J=8.7 Hz, 2H), 7.79 (dd, J=8.2,1.9 Hz, 1H), 8.06 (d, J=1.6 Hz, 1H), 11.54 (s, 1H), 12.75 (s, 1H); APCI MS m/z 394 (M) − . Anal. Calcd for C 15 H 14 N 4 O 5 S 2 .0.9H 2 O: C, 43.87; H, 3.8B; N, 13.64; S, 15.62. Found: C, 43.96; H, 3.80; N, 13.58; S, 15.67.
EXAMPLE 32
3-[(4-Methylsulfamoyl-phenyl)-hydrazono]-2-oxo-2,3-dihydro-1H-indole-5-sulfonic Acid Methylamide
[0333] 1H-indole-2,3-dione-5-sulfconic acid methylamide was prepared from N-methylsulfonamidoaniline hydrochloride according to Procedure A: 1 H NMR (DMSO-d 6 ): δ 2.37 (d, J=4.7′ Hz, 3H), 7.04 (d, J=8.4 Hz, 1H), 7.45 (q, J=5.0 Hz, 1H), 7.73 (s, 1H), 7.91 (d, J=8.4 Hz, 1H), 11.38 (s, 1H); APCI-MS m/z 239 (M−H) − . The title compound was prepared from 1H-indole-2,3-dione-5-sulfonic acid methylamide and 4-(N-methylsulfonamido)phenylhydrazine according to Procedure G: mp >250 0 C; 1 H NMR (DMSO-d 6 ): δ 2.38 (d, J=4.9 Hz, 6H), 7.08 (d, J=8.2 Hz, 1H), 7.3:3(q, J=5.2 Hz, 1H), 7.35 (q, J=4.9 Hz, 1H), 7.65 (d, J=8.7 Hz, 2H), 7.66 (dd, J=8.1, 1.8 Hz, 1H), 7.73 (d, J=8.8 Hz, 2H), 7.91 (d, J=1.5 Hz, 1H), 11.48 (s, 1H), 12.77 (s, 1H); APCI-MS m/z422 (M−H) − . Anal. Calcd for C 16 H 17 N 5 O 5 S 2 : C, 45.38; H, 4.05; N, 16.54. Found: C, 45.46; H, 4.04; N, 16.45.
EXAMPLE 33
4N′-[5-(1-Hydroxyimino-ethyl)-2-oxo-1,2-dihydro-indol-3-ylidene]-hydrazino]-N-methyl-benzenesulfonamide
[0334] 5-(1-Hydroxyiminoethyl)-1H-indole-2,3-dione was prepared from 4-aminoacetophenone according to Procedure A: 1 H NMR (DMSO-d 6 ): δ 2.00 (s, 3H), 6.83 (d, J=8.6 Hz, 1H), 7.60 (dd, J=8.5, 2.1 Hz, 1H), 7.77 (d, J=1.7 Hz, 1H), 9.99 (s, 1H), 10.91 (s, 1H); APCI-MS m/z 203 (M−H) − . The title compound was prepared from 5-(1-hydroxyiminoethyl1H-indole-2,3-dione and 4N-methylsulfonamido)phenylhydrazine according to Procedure G: mp >250° C.; 1 H NMR (DMSO-d 6 ): δ 2.00 (s, 3H), 2.37 (d, J=4.9 Hz, 3H), 6.85 (d, J=8.4 Hz, 1H), 7.31 (q, J=5.0 Hz, 1H), 7.37 (dd, J=8.4, 1.8 Hz, 1H), 7.56 (d, J=8.7 Hz, 2H), 7.74 (d, J=8.8 Hz, 211), 7.91 (d, J=1.9 Hz, 1H), 9.88 (s, 1H), 10.99 (s, 1H), 12.79 (s, 1H); APCI-MS m/z 386 (M−H)K. Anal. Calcd for C 17 H 17 N 5 O 4 S: C, 52.70; H, 4.42; N, 18.08. Found: C, 52.80; H, 4.50; N, 17.90.
EXAMPLE 34
4-41-(5-Oxazol-5-yl-2-oxo-1,2-dihydro-indol-3-ylidene)-ethylamino]-benzenesulfonamide
[0335] 3-(1-Dimethylaminoethylidene)-5-(oxazol-5-yl)-1,3-dihydroindol-2-one was prepared from 5-(oxazol-5-yl)-1,3-dihydroindol-2-one and N,N-dimethylacetamide dimethyi acetal according to Procedure H. Condensation of 3-(1-dimethylaminoethylidene)-5-(oxazol-5-yl)-1,3-dihydroindol-2-one and sulfanilamide according to Procedure J provided the title compound: mp >250° C; 1 H NMR (DMSO-d 6 ): δ 2.51 (s, 0.8H, DMSO), 2.61 (s, 3H), 6.97 (d, J=8.2 Hz, 1H), 7.37 (s, 2H), 7.40 (dd, J=8.0, 1.5 Hz, 1H), 7.45 (d, J=8.8 Hz, 2H), 7.56 (s, 1H), 7.66 (d, J=1.2 Hz, 1H), 7.83 (d, J=8.5 Hz, 21), 8.34 (s, 1H), 10.85 (s, 1H), 12.33 (s, 111); APCI-MS m/z 395 (M−H) − . Anal. Caled for C 19 H 16 N 4 O 4 S.0.1 C 2 H 6 OS.0.6H 2 O: C, 55.56; H, 4.32; N, 13.50; S, 8.50. Found: C, 55.53; H, 4.32; N, 13.27; S, 8.58.
EXAMPLE 35
N,N-Dimethyl-4-[(5-oxazol-5-yl-2-oxo-1,2-dihydro-indol-3-ylidenemethyl)-amino]-benzenesulfonamide
[0336] 3-Methylsulfanyl-5-oxazol-5-yl-1,3-dihydro-indol-2-one was prepared from 4-oxazol-5-yl-aniline according to Procedure D: 1 H NMR (DMSO-d 6 ): δ 10.7 (s, 1H), 8.3 (s, 1H), 7.5 (s, 3H), 6.9 (d, 1H), 4.5 (s, 1H), 2.0 (s, 3H); APCI-MS m/z 247 (M+H) + . 5-Oxazol-5-yi-1,3-dihydroindol-2-one was prepared from 3-methylsulfanyl-5-oxazol-5-yl-1,3-dihydro-indol-2-one according to Procedure D: 1 H NMR (DMSO-d 6 ): δ 10.5 (,s, 1H), 8.3 (s, 1H), 7.5 (m, 3H), 6,8 (d, 1H), 3.5 (s, 2H); APCI-MS m/z 201 (M+H) + . 3-Ethoxymethylene-5-oxazol-5-yl-1,3-dihydro-indol-2-one was prepared from 5-oxazol-5-yl-1,3-dihydro-indol-2-one according to Procedure I: 1 H NMR (DMSO-d 6 ): δ 10.43 (s, 1H), 8.37 (s, 1H), 7.76 (s, 1H), 7.51 (m, 2H), 6.90, (d, 1H), 4.43 (q, 2H), 1.4 (t, 3H): APCI-MS m/z 255 (M−H) + . The title compound was prepared in 36% yield from 3-ethoxymethylene-5-oxazol-5-yl-1,3-dihydro-indol-2-one and N,N-dimethyl-4-aminobenzenesulfonamide according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 10.9 (d, 1H), 10.8 (s, 1H), 8.8 (d, 1H), 8.4 (s, 1H), 8.0 (s, 1H), 7.7 (br d, 4H), 7.5 (m, 2H), 7.0 (d, 1H), 2.6 (s, 6H); APCI-MS m/z 409 (M−H) − .
EXAMPLE 36
4-[1,5-Oxazol-5-yl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (5:1 E:Z Isomer Mixture)
[0337] The title mixture of isomers was prepared from 5-(oxazol-5-yl)-1H-indole-2,3-dione and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G: mp >250° C.; 1 H NMR (DMSO-d 6 ): δ (5:1 ratio of Z:E isomers), E 6.97 (d, J=8.2 Hz, 1H), Z 7.00 (d, J=8.2 Hz, 1H), E 7.23 (s, 2H), Z7.25 (s, 2H), Z 7.61 (d, J=9.1 Hz, 2H), E 7.61 (,d, J=9.1 Hz, 2H), Z 7.62 (dd, J=8.2, 1.7 Hz, 1H), Z 7.65 (s, 1H), E 7.65 (s, 1H), E 7.65 (dd, J=8.2, 1.5 Hz, 1H), Z 7.78 (d, J=8.9 Hz, 2H), E 7.81 (d, J=8.9 Hz, 2H), Z 7.90 (d, J=1.7 Hz, 1H), Z 8.40 (s, 1H), E 8.43 (s, 1H), E 8.47 (d, J=1.3 Hz, 1H), E 10.83 (s, 1H), E 10.98 (s, 1H), Z 11.25 (s, 1H), Z 12.78 (s, 1H); ESI-MS m/z 382 (M−H) − . Anal. Calcd for C 17 H 13 N 5 O 4 S.1.2H 2 O.0.4 C 2 H 6 O: C, 50.49; H, 4.24; N, 16.54. Found: C, 50.50; H, 4.15; N, 16.56.
EXAMPLE 37
4-[(2-Oxo-5-phenyl-1,2-dihydro-indol-3-ylidenemethyl)-amino]-benzenesulfonamide (Z-Isomer)
[0338] A solution of 0.62 g (3.0 mmol) of 5-phenyl-1,3-dihydro-indol-2-one (Hewawasam and Meanwell, Tetrahedron Letters 1994, 35, 73036) in 10 mL of DMF was treated with 0.90 g (4.5 mmol) of DMF di-tert-butyl acetal for 2 h at rt. DMF was removed under high vaccum, and the residue was subjected to chromatography on silica gel, eluting with hexane:EtOAc (1:1), to yield 0.09 g (10%) of 3-tert-butoxymethylene-5-phenyl-1,3-dihydro-indol-2-one: 1 H NMR (DMSO-d 6 ): δ 1.46 (s, 9H), 6.85 (d, J=8.0 Hz, 1H), 7.27 (t, J=7.3 Hz, 1H), 7.34-7.39 (m, 1H), 7.41 (d, J=7.5 Hz, 2H), 7.53 (d, J=7.5 Hz, 2H), 7.72 (s, 1H), 7.83 (s, 1H), 10.28 (s, 1H); APCI+MS m/z 316 (M+23) + . Further elution with EtOAc:MeOH (98:2) gave 0.11 g (14%) of 3-dimethylaminomethylene-5-phenyl-1,3-dihydro-indol-2-one.
[0339] A solution of 0.09 g (0.31 mmol) of 5-phenyl-3-tert-butoxymethylene-1,3-dihydro-indol-2-one, 0.053 g (0.31 mmol) of sulfanilamide, and 2 drops of conc. HCl in 15 mL of ethanol was refluxed for 1 h and cooled to rt. The resulting yellow solid was isolated by filtration, washed with ethanol and dried to give 0.068 g (56%) of the title compound: 1 H NMR (DMSO-d 6 ): δ 6.90 (d, J=8.2 Hz, 1H), 7.25 (s, 2H), 7.29 (t, J 7.5 Hz, 1H), 7.34 (dd, J=1.6, 8.2 Hz, 1H), 7.43 (d, J=7.5 Hz, 2H), 7.55 (d, J 8.8 Hz, 2H), 7.64 (d, J=7.5 Hz, 2H), 7.77 (d, J=8.8 Hz, 2H), 7.99 (d, J=1.6 Hz, 1H), 8.74 (d, J=12.5 Hz, 1H), 10.62 (s, 1H), 10.76 (d, J=12.5 Hz, 1H); APCI-MS m/z 390 (M−H) − .
EXAMPLE 38
See Procedure K
EXAMPLE 39
2-Oxo-3-.[(4-sulfamoyl-phenyl)-hydrazono]2,3-dihydro-1H-indol-5-carboxylic acid (furan-2-ylmethyl)-amide (Z-Isomer)
[0340] The title compound was prepared from 2-oxo-3[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid pentafluorophenyl ester and 2-aminomethylfuran according to Procedure K: mp >250° C.; 1 H NMR (DMSO-d 6 ): δ 4.51 (d, J=5.5 Hz, 2H), 6.31 (d, J=3 Hz, 1H), 6.44 (d, J=3 Hz), 7.02 ( d, J=8.3, 1H), 7.30 (s, 2H), 7,66 (m, 3H), 7.88 (m, 3H), 8.18 (s, 1H), 9.02 (brt, J=5.5 Hz, 1H), 11.4 (s, 1H), 12.8 (s, 1H); APCI-MS m/z438 (M−H); Anal. Calcd for C 20 H 17 N 5 O 5 S.½H 2 O: C, 53.57; H, 4.05; N, 15.62; S, 7.15. Found: C, 53.91; H, 4.01; N, 15.13; S, 6.78.
EXAMPLE 40
2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indol-5-carboxylic acid-2,6-dimethoxybenzylamide (Z-Isomer)
[0341] The title compound was prepared from 2-oxo-3[(4-sulfamoyi-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid pentafluorophenyi ester and 2,6-dimethoxybenzyiamine according to Procedure K: mp >250° C.; 1 H NMR (DMSO-d 6 ): δ 3.76 (s, 6H), 4.43 (d, J 4.2 Hz, 2H), 6.65 (d, J=8.4 Hz, 2H), 6.91 (d, J=8.2 Hz, 1H), 7.23 (s, 2H), 7.25 (d, J=8.2 Hz, 1H), 7.56 (d, J=8.6 Hz, 2H), 7.79 (m, 3H), 8.07 (s, 1H), 8.13 (brs, 1H), 11.27 (s, 1H), 12.76 (s, 1H); APCI-MS m/z 532 (M+Na) + ; Anal. Calcd for C 24 H 23 N 5 O 6 S.½H 2 O: C, 55.59; H. 4.67; N, 13.51; S, 6.18. Found: C, 55.69; H, 4.64; N, 13.61; S, 6.09.
EXAMPLE 41
2-Oxo-3[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid (2-morpholin-4-yl-ethyl)-amide (Z-Isomer)
[0342] The title compound was prepared from 2-oxo-3[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid pentafluorophenyl ester and 2N-morpholino)ethylamine according to Procedure K: mp 210-212° C.; Anal. Calcd for C 21 H 24 N 6 O 5 S.¼H 2 O: C, 52.88; H, 5.18; N, 17.62. Found: C, 52.91; H, 5.24; N, 17.35.
EXAMPLE 42
2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid (2-imidazol-1-yl-ethyl)-amide (Z-Isomer)
[0343] The title compound was prepared from 2-oxo-3[(4-suffamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid pentafluorophenyl ester and 2-(N-imidazolo)ethylamine according to Procedure K: mp >230° C.; Anal. Calcd for C 20 H 18 N 7 O 4 S: C, 53.09; H, 4.01; N, 21.67. Found: C, 52.83; H, 4.24; N, 21.55.
EXAMPLE 43
2-Oxo-3-[(4-sulfamoyl-phenyl)hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid (3-imidazol-1-yl-propyl)-amide (Z-Isomer)
[0344] The title compound was prepared from 2-oxo-3[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid pentafluorophenyl ester and 3-(N-morpholino)propylamine according to Procedure K: mp >230° C.; Anal. Calcd for C 21 H 21 N 7 O 4 S.½H 2 O: C, 52.93; H, 4.65; N, 20.58. Found: C, 52.93; H, 4.40; N, 20.17.
EXAMPLE 44
2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic Acid (2-.methoxyethyl)-amide (Z-Isomer)
[0345] The title compound was prepared from 2-oxo-3[(4-suffamoyi-phenyl) -hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid pentafluorophenyl ester and 2-methoxyethylamine according to Procedure K: mp >230 “C; Anal. Calcd for C 18 H 9 N 5 O 5 S: C, 51.79; H, 4.59; N, 16.78. Found: C, 51.69; H, 4.54; N, 16.72.
EXAMPLE 45
2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic Acid (2-hydroxyethyl)-amide (Z-Isomer)
[0346] The title compound was prepared from 2-oxo-3[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid pentafluorophenyl ester and 2-hydroxyethylamine according to Procedure K: mp >230 0C; Anal. Caled for C 17 H 17 N 5 O 5 S: C, 50.61; H, 4.25; N, 17.36. Found: C, 50.53; H, 4.28; N, 17.27.
EXAMPLE 46
2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid (3-hydroxypropyl)-amide (Z-Isomer)
[0347] The title compound was prepared from 2-oxo-3[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid pentafluorophenyl ester and 2-hydroxypropylamine according to Procedure K: mp >230 0C; Anal. Calcd for C 18 H 19 N 5 O 5 S.⅓H 2 O: C, 51.06; H, 4.68; N, 16.54. Found: C, 51.07; H, 4.45; N, 16.45.
EXAMPLE 47
2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic Acid (3-hydroxy-2,2-dimethylpropyl)-amide (Z-Isomer)
[0348] The title compound was prepared from 2-oxo-3[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid pentafluorophenyl ester and 3-hydroxy-2,2-dimethylpropylamine according to Procedure K: mp >230 “C; Anal. Calcd for C 20 H 23 N 5 O 5 S: C, 53.92; H, 5.20; N, 15.72. Found: C, 54.04; H, 5.17; N, 15.77.
EXAMPLE 48
2-Oxo-3-[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic Acid (pyrildin-3-ylmethyl)-amide (Z-Isomer)
[0349] The title compound was prepared from 2-oxo-3[(4-sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic acid pentafluorophenyl ester and (3-pyridyl)methylamine according to Procedure K: mp 211-215° C.; Anal. Calcd for C 21 H 18 N 6 O 4 S.H 2 O: C, 53.84; H, 4.30; N, 17.94. Found: C, 54.29; H, 4.03; N. 17.82.
EXAMPLE 49
2-Oxo-3-[(4—sulfamoyl-phenyl)-hydrazono]-2,3-dihydro-1H-indole-5-carboxylic Acid (pyridin-4-ylmethyl}-amide (Z-Isomer)
[0350] The title compound was prepared from 2-oxo-3[(4-sulfamoyl-phenyl)-hydrazono)-2,3-dihydro-iH-indio(e5-carboxylic acid pentafluorophenyl ester and (4-pyridyl)methylamine according to Procedure K: mp 211-215° C.; Anal. Calcd for C 21 H 18 N 6 O 4 S.¾H 2 O. C, 54.36; H. 4.24; N, 18.11. Found: C, 54.41; H, 4.20; N, 18.12.
EXAMPLE 50
4-[N”-(5-Methoxy-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonainide (Z-Isomer)
[0351] The title compound was prepared from 5-methoxy-1H-indole-2,3-dione (Gassman, et al., Journal of Organic Chemistry 1977, 42, 1344-8) and 4-hydrazinobenzenesulfonamide hydrochloride according to Procedure G: mp >250° C.; 1 H NMR (DMSO-d 6 d): δ 3.80 (s, 3H), 6.87 (s, 2H), 7.20 (s, 1H), 7.28 (s, 2H), 7.60 (d, J=8.8 Hz, 2H), 7.81 (d, J=8.8 Hz, 2H), 10.93 (s, 1H), 12.85 (s, 1H); APCI-MS m/z 344.9 (M−H) − .
EXAMPLE 51
4-[N′-(5-Amino-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide Hydrochloride (Z-Isomer)
[0352] The title compound was prepared from 5-amino-1H-indole-2,3-dione and 4-hydrazinobenzenesulfonamide hydrochloride according to Procedure G: 1 H NMR (DMSO-d 6 ): δ 6.95 (d, J=8 Hz, 1H), 7.2 (d, J=8 Hz, 1H), 7.26 (s, 2H), 7.46 (s, 1H), 7.5 (d, J=8 Hz, 2H), 7.8 (d, J=8 Hz, 2H), 9.7 (br s, 3H), 11.2 (s, 1H), 12.8 (s, 1H); APCI-MS m/z 330.2 (M−H) − .
EXAMPLE 52
4-[N′-(6-Ethyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z Isomer)
[0353] The title compound was prepared from 6-ethyl-1H-indole-2,3-dione (Krantz and Young, 1989, U.S. Pat. No. 4,873,232) and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G in 79% yield: 1 H NMR (DMSO-d 6 ): δ 1.16 (t, J=7.5 Hz, 3H), 2.60 (q, J=7.5 Hz, 2H), 6.74 (s, 1H), 6.89 (d, J=7.5 Hz, 1H), 7.22 (s, 2H), 7.46 (d, J=7.5 Hz, 1H), 7.50 (d, J=8.7 Hz, 1H), 7.75 (d, J=8.7 Hz, 2H), 11.02 (s, 1H), 12.70 (s, 1H); APCI-MS m/z 343 (M−H) − . Anal. Calcd for C 16 H 16 N 4 O 3 S.0.32H 2 O: C, 54.88, H, 4.79; N, 16.00; S, 9.16. Found C, 54.81, H. 4.59; N, 16.06; S, 9.04.
EXAMPLE 53
4-[(2-Oxo-1,2-dihydro-indol-3-ylidenemethyl)-amino]-benzensulfonic Acid Phenyl Ester (Z-Isomer)
[0354] The title compound was prepared in 23% yield from 3-hydroxymethylene-1,3-dihydro-indol-2-one and phenyl 4-aminobenzenesulfonate according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 10.8 (d, 1H), 10.5 (s, 1H), 8.6 (d, 1H), 7.7 (d, 2H), 7.6 (m, 3H), 7.4 (m, 2H), 7.3 (m, 1H), 7.0 (m., 3H), 6.9 (t, 1H), 6.8 (d, 1H); APCI-MS m/z 391 (M−H) − .
EXAMPLE 54
N-{4-[(2-Oxo-1,2-dihydro-indol-3-ylidenemethyl)-amino]-phenyl}sulfamide (Z-Isomer)
[0355] The title compound was prepared from 3-hydroxymethylene-1,3-dihydro-indol-2-one and 4-aminophenylsulfamide according to Procedure J in 52% yield: 1 H NMR (DMSO-d 6 ): δ 6.85 (d, J=7.5 Hz, 1H), 6.93 (t, J=7.5 Hz, 1H), 7.01 (t, J=7.5 Hz, 1H), 7.08 (s, 2H), 7.21 (d, J=8.8 Hz, 2H), 7.36 (d, J=8.8 Hz, 2H), 7.57 (d, J=7.5 Hz, 1H), 8.53 (d, J=12.7 Hz, 1H), 9.38 (s, 1H), 10.48 (s, 1H), 10.70 (d, J=12.7 Hz, 1H): APCI-MS m/z 329 (M−H) − . Anal. Calcd for C 15 H 14 N 4 O 3 S: C, 54.54, H, 4.27; N, 16.96; S. 9.71. Found C, 54.48, H, 4.30; N, 16.90; S, 9.63.
EXAMPLE 55
4-[(6-Hydroxymethyl-2-oxo-1,2-dihydro-indol-3-ylidenemethyl)-amino]-benzenesulfonamide (Z-Isomer)
[0356] A solution of 0.42 g (:2.0 mmol)of 6-hydroxymethyl-3-methysulfanyl-1,3-dihydro-indol-2-one in DMF (10 mL) was treated with 0.32 9 (2.1 mmol) of t-butyldimethylsilyl chloride and 0.15 g (2.2 mmol) of imidazole and stirred for 16 h. The solution was diluted with 50 mL of hexane and 50 mL of EtOAc, washed with brine, dried over MgSO 4 and concentrated to give 0.28 g (43%) of 3-methylsulfanyl-6-(t-butyldimethylsilyloxy)methyl-1,3-dihydro-indol-2-one as a clear oil which crystallised upon storage at rt: 1 H NMR (DMSO-d 6 ): δ 0.01 (s, 6H), 0.97 (s, 9H), 2.00 (s, 3H), 4.52 (s, 1H), 4.72 (s, 2H), 6.85 (s, 1H), 6.96 (d, J=7.7 Hz, 1H), 7.25 (d, J=7.7 Hz, 1H), 10.54 (s, 1H). A solution of 0.28g (0.86 mmol) of 3-methylsulfanyl-4-(t-butyldimethylsilyloxy)methyl-1,3-dihydro-indol-2-one in THF (10 mL) was stirred with saturated ammonium chloride solution (10 mL), and activated zinc dust (2 g) was added. The mixture was stirred 16 h at rt. The organic phase was separated, dried over MgSO 4 and concentrated to give 0.32 g of impure 4-(t-butyldimethylsilyloxy)methyl-1,3-dihydro-indol-2-one as a gummy white solid: 1 H NMR (DMSO-d 6 ): δ 0.04 (s, 6H), 0.87 (s, 9H), 3.39 (s, 2H), 4.62 (s, 2H), 6.75 (s, 1H), 6.81 (d, J 7.5 Hz, 1H), 7.10 (d, J=7.5 Hz, 1H), 10.30 (bs, 1H). A solution of 0.32 g (1.2 mmol) of 4-(t-butyldimethylsilyloxy)methyl-1,3-dihydro-indol-2-one in DMF dimethylacetal (3 mL) was heated to 100° C. for 0.75 h. The excess DMF dimethylacetal was removed under high vacuum, and the resulting dark oil was chromatographed on silica gel, eluting with EtOAc/MeOH (98:2), to give 0.16 g (41%) of 3-dimethylaminomethylene-6-(t-butyldimethylsilyloxy)methyl-1,3-dihydro-indol-2-one (11:9 mixture of E and Z isomers) as a yellow solid: 1 H NMR (DMSO-d 6 , peak areas normalized using the combined peak areas for δ 9.88 and 9.66 as 1H): δ 0.21 (s, 2.70H), 0.34 as, 3.3H), 0.85 (s, 4.05H), 0.86 (s, 4.95H), 3.25 (s, 2.70H), 3.30 (s, 3.30H), 4.58 (s, 0.9H), 4.59 (s, 1.1H), 6.64-6.71 (m, 2H), 7.16 (d, J=7.7 Hz, 0.45H), 7.29 (d, J=8.3 Hz, 0.55H), 7.33 (s, 0.55H), 7.47 (s, 0.45H), 9.88 (s,0.55H) 9.96 (s, 0.45H); APCI-MS m/z 331 (M+1) + . A solution of 0.334 9 (1.00 mmol) of 3-dimethylamino-methylene-6-(t-butyldimethylsilyloxy)methyl-1,3-dihydro-indol-2-one in 2-methylpropanol (3 mL) was treated with 0.174 g (1.00 mmol) of sulfanilamide and 0.25 g (4.0 mmol) of acetic acid. The solution was refluxed for 3 h and cooled to rt. The resulting yellow precipitate was isolated by filtration, washed with ethanol and dried to yield 0.134 g (29%) of 6-([t-butyldimethyl-silyloxy]methyl-2-oxo-1,2-dihydro-indol-3-ylidenemethyl)-amino)-benzenesulfonamide (Z isomer).: 1 H NMR (DMSO-d 6 ): δ 0.05 (s, 6H), 0.87 (s, 9H), 4.65 (s, 2H), 6.81 (s, 1H), 6.85 (d, J=8.0 Hz, 1H), 7.23 (s, 2H), 7.49-7.51 (m, 3H), 7.75 (d, J=8.4 Hz, 2H), 8.56 (d, J=12.3 Hz, 1H), 10.52 (s, 1H), 10.76 (d, J=12.3 Hz. 1H); APCI-MS m/z 458 (M−H) − . To a solution of 0.125 g (2.80 mmol) of 6-([t-butyldimethylsilyloxy]methyl-2-oxo-1,2-dihydro-indol-3-ylidenemethyl)-amino]-benzenesulfonamide in THF (5 mL) was added 0.27 mL of a 1 M solution of t-butylammonium fluoride in THF, and the mixture was stirred at rt for 1 h. The resulting yellow precipitate vas isolated by filtration, washed with THF and dried. Chromatographic purification of the solid on silica gel, eluting with a hexane to EtOAc gradient, gave 0.053 g (55%) of the title compound: 1 H NMR (DMSO-d 6 ): δ 4.43 (d, J=5.8 Hz, 2H), 5.08 (t, J=5.8 Hz, 1H), 6.82 (s, 1H), 6.85 (d, J=8.2 Hz, 1H), 7.23 (s, 2H), 7.50 (d, J=7.5 Hz, 2H), 7.74 (d, J=8.7 Hz, 3H), 8.56 (d, J=12.2 Hz, 1H), 10.54 (s, 1H), 10.75 (d, J=12.1 Hz, 1H); APCI-MS m/z 345 (M−H) − . Anal. Calcd for C 16 H 15 N 3 O 4 S.0.5 H 2 O: C, 54.43, H. 4.55; N, 11.86, S, 9.05. Found C, 54.47, H, 4.63; N, 11.66; S, 8.86.
EXAMPLE 56
4-[N′-(6-Bromo-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z-Isomer)
[0357] The title compound was prepared from 6-bromo-1H-indole-2,3-dione (Meth-Cohn and Goon, Tetrahedron Letters 1996, 37, 93814) and 4-hydrazinobenzenesulfonamidje hydrochloride according to Procedure G: mp >250° C.; 1 H NMR (DMSO-d 6 ): δ 7.05 (s, 1H), 7.23 (d, J=8.1 Hz, 1 fH), 7.50 (d, J=8.1 Hz, 1H), 7.56 (d, J=8.7 Hz, 2H), 7.75 (d, J=8.7 Hz, 2H), 11.2 (s, 1H), 12.7 (s, 1H); APCI-MS m/z 395 (M−H) − .
EXAMPLE 57
4-[N′-(2-Oxo-6-phenoxy-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z-Isomer)
[0358] The title compound was prepared from 6-phenoxy-1H-indole-2,3-dione and 4-sulfonamidophenylhydrazine according to Procedure G in 87% yield: mp >250° C.; 1 H NMR (DMSO-d 6 ): δ 6.42 (d, J=2.2 Hz, 1H), 6.73 (dd, J 1 =2.2 Hz, J 2 =8.5 Hz, 1H), 7.17 (d, J=8 Hz, 2H), 7.25 (s, 1H), 7.28 (d, J=7.4 Hz, 2H), 7.49 (t, J=7.9 Hz, 2H), 7.73 (d, J=8.8 Hz, 2H), 7.82 (d, J=8.8 Hz, 2H), 8.25 (d, J=8.5 Hz, 2H), 10.61 (s, 1H), 10.65 (s, 1H); APCI-MS: m/z 431 (M+Na) + . Anal. Calcd for C 20 H 16 N 4 O 4 S.0.25H 2 O: C, 58.17; H, 4.03; N, 13.57; S, 7.76. Found: C, 58.45; H, 4.39; N, 13.40; S, 7.63.
EXAMPLE 58
4-[N ′-(4-Ethoxy-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z-Isomer)
[0359] The title compound was prepared from 3-ethoxyaniline and 4-hydrazinobenzene sulfonamide hydrochloride according to Procedure C: mp >250,° C.; 1H NMR (DMSO-d 6 ): δ 1.43 (t, J=7.0 Hz, 3H), 4.13 (q, J=7.0 Hz, 2H), 6.50 (d, J=7.6 Hz, 1H), 6.68 (d, J=8.4 Hz, 1H), 7.15-7.21 (m, 3H), 7.46 (d, J=8.8 Hz, 2H), 7.74 (d, J=8.8 Hz, 2H), 11.03 (s, 1H), 12.78 (s, 1H); APCI-MS: m/z 359 (M−H) − . Anal. Calcd for C 16 H 16 N 4 O 4 S: C, 53.32; H. 4.47; N, 15.55; S, 8.90. Found: C, 53.21; H. 4.50; N, 15.66; S, 8.85.
EXAMPLE 59
N-[2-(2-Hydroxyethoxy)ethyl]4-[7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacene-8-ylidenemethyl)-amino]benzenesuffonamide (Z-Isomer)
[0360] The title compound was prepared from 4-amino-N-(2-(2-hydroxyethoxy)ethyl)-benzenesulfonamide (see Example 84) and 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 2.88 (q, J=6.0 Hz, 2H), 3.31 (t, J=5.0 Hz, 2H), 3.36 (t, J=5.8 Hz, 2H), 3.42 (t, J=5.1 Hz, 2 Hz), 4.5 (br s, 1H), 7.10 (d, J=8.4 Hz, 1H), 7.59 (d, J=8.8 Hz, 2H), 7.60 (t, J=6.0 Hz, 1H), 7.77 (d, J=8.7 Hz, 2H), 7.81 (d, J=8.6 Hz, 1H), 8.07 (d, J=12.2 Hz, 1H), 9.25 (s, 1H), 10.91 (s, 1H), 11.16 (d, J=12.2 Hz, 1H); APCI-MS m/z 459 (M−H) − . Anal. Calcd for C 20 H 20 N 4 O 5 S 2 .H 2 O : C, 50.20; H, 4.63; N, 11.71. Found: C, 50.06; H. 4.59; N, 11.68.
EXAMPLE 60
N-[2-(2-Hydroxyethyl]-4-[7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacene-8-ylidenemethyl)-amino]benzenesulfonamide (Z-Isomer)
[0361] The title compound was prepared in 51% yield from N-(2-hydroxyethyl)-4-aminobenzene sulfonamide and 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 11.18 (d,1H), 10.9 (s, 1H), 9.25 (s, 1H), 8.06 (d, 1H), 7.8 (d, 1H), 7.76 (d, 2H), 7.58 (d, 2H), 7.52 (t, 1H), 7.1 (d, 1H), 4.66 (t, 1H), 3.35 (q, 2H), 2.76 (q, 2H); APCI-MS m/z 415 (MH) − .
EXAMPLE 61
N-Methyl-4-[N′-(4-methyl-5-nitro-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z-Isomer)
[0362] 4-Methyl-5-nitro-1H-indole-2,3-dione was prepared from 3-methyl-4-nitroaniline according to Procedure A: 1 H NMR (DMSO-d 6 ): δ 11.5 (s, 1H), 8.2 (d, 1H), 6.8 (d, 1H), 2.7 (s, 3H); APCI-MS m/z 205 (M−H) − . The title compound was prepared in 84% yield from 4-methyl-5-nitro-1H-indole-2,3-dione and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G: 1 H NMR (DMSO-d 6 ): 13.0 (s, 1H), 11.6 (s, 1H), 7.9 (d,1H), 7.7 (d, 2H), 7.6 (d, 2H), 7.3 (q, 1H), 6.9 (d, 1H), 2.8 (s, 3H), 2.4 (d, 3H); APCI-MS m/z 388 (M−H) − .
EXAMPLE 62
4-[N′-(7-Oxo-6,7-dihydro-3H-pyrrolo[3,2e]indazol-8-ylidene)-hydrazino]-benzenesulfonamide (Z Isomer)
[0363] The title compound was prepared from 3,6-dihydro-pyrrolo[3,2-e]indazole 7,8-dione (Cuny, et al., Chemie Berichte 1981, 114, 1624-35) and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G in 8% yield: 1 H NMR (DMSO-d 6 ): δ 7.02 (d, J 8.7 Hz, 1H), 7.28 Z (s, 2H), 7.51 (d, J=8.6 Hz, 2H), 7.68 (d, J=8.8 Hz, 1H), 7.82 (d, J=8.7 Hz, 2H), 8.34 (s, 1H), 10.98 (s, 1H), 12.90 (s, 1H), 13.20 (s, 1H); APCI-MS m/z 356 (Mr. Anal. Calcd for C 15 H 12 N 6 O 3 S.1.46H 2 O.0.2 EtOAc: C, 47.41, H. 4.16; N, 20.99; S, 8.01. Found C, 47.40, H, 3.70; N, 21.00; S, 7.85.
EXAMPLE 63
4-[N′-(7-Oxo-6,7-dihydro-1H-pyrrolo[2,3g]indazol-8-ylidene)-hydrazino]-benzenesulfonaimide (Mixture of E and Z Isomers)
[0364] The title compound was prepared from isatin 1,6-dihydropyrrolo[2,3-g]indazole7,8-dione (Lichtenthaler and Cuny, Heterocycles 1981, 15, 1053-9) and 4-sulfonamidophenyl-hydrazine hydrochloride according to Procedure G in 76% yield: 1 H NMR (DMSO-d 6 ): δ 6.82 Z (d, J=8.3 Hz, 1H), 6.87 E (d, J=8.5 Hz, 1H), 7.24 E (s, 2H), 7.27 Hz (s, 2H), 7.43 E (d, J=8.6 Hz, 2H), 7.73 Z (d, J=8.3 Hz, 1H), 7.78 Z (d, J=8.8 Hz, 2H), 7.85 E (d, J=8.8 Hz, 2H), 7.89 E (d, J=8.5 Hz, 1H), 7.89 Z (d, J=,B.5 Hz, 2H), 8.12 Z (s, 1H), 8.56 E (s, 1H), 10.67 E (s, 1H), 11.20Z(s, 1H), 12.836Z(s, 1H), 13.27 E(s, 1H), 13.27Z(s, 1H), 14.27 E (s, 1H); APCI-MS m/z 355 (M−H) − . Anal. Calcd for C 15 H 12 N 6 O 3 S: C, 50.56, H, 3.39; N, 23.58; S, 9.00. Found C, 50.65, H, 3.40; N, 23.59; S, 8.97.
EXAMPLE 64
4-[N′-(7-Oxo-6,7-dihydro-3H-1,2,3,6-tetraaza-as-indacen-8-ylidene)-hydrazino]-benzenesulfonamide (Mixture of E and Z Isomers)
[0365] 1,6-Dihydro-1,2,3,6-tetraaza-as-indacene-7,8-dione was prepared according to Procedure A in 56% yield: 1 H NMR (DMSO-d 6 ): δ 6.93 (d, J=8.6 Hz, 1H), 8.32 (d, J=8.6 Hz, 1H), 11.14 (s, 1H); APCI-MS m/z 189 (M+1) + . Condensation of 1,6-dihydro-1,2,3,6-tetraaza-as-indacene-7,8-dione with 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G gave the title compound in 15% yield: 1 H NMR (DMSO-d 6 ): δ 7.06 Z (d, J=8.4 Hz, 1H), 7.24 E (d, J=8.4 Hz, 1H), 7.:30 Z (s, 2H), 7.30 E (s, 2H), 7.55 E (d, J=8.5 Hz, 2H), 7.82 Z (d, J=8.5 Hz, 2H), 7.82 E (d, J=8.5 Hz, 1H), 7.90 E (d, J=8.7 Hz, 2H), 7.90 Z (d, J=8.8 Hz, 2H), 7.98 Z (d, J=8.4 Hz, 1H), 10.86 E (s, 1H), 11.35 Z (s, 1H), 12.87 Z (s, 1H), 12.95 E (s, 1H), 16.00 Z (s, 1H), 16.25 E (s, 1H); APCI-MS m/z 356 (M−H) − . Anal. Calcd for C 14 H 11 N 7 O 3 S.H 2 O: C, 44.80, H, 3.49; N. 26.12; S, 8.54. Fourd C, 44.72, H, 3.46; N, 26.05; S, 8.48.
EXAMPLE 65
4-[N′-(1-Chloro-7-oxo-6,7-dihydro-3H-pyrrolo[3,2-e]indazol-8-ylidene)-hydrazino]-benzenesulfonamide (Z-Isomer)
[0366] 1-Chloro-3,6-dihydro-pyrrolo[3,2e]indazole-7,8-dione was prepared from 5-amino-3-chloroindazole according to Procedure A in 38% yield: 1 H NMR (DMSO-d 6 ): δ 7.08 (d, J=7.9 Hz, 1H), 7.92 (d, J=7.9 Hz, 1H), 10.95 (s, 1H), 13.70 (s, 1H). Condensation of 1-chloro-3,6-dihydro-pyrrolo[3,2-e]indazole-7,8-dione and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G gave the title compound in 45% yield: 1 H NMR (DMSO-d 6 ): δ 7.11 (d, J=8.8 Hz, 1H), 7.26 (s, 2H), 7.51 (cf, J=8.8 Hz, 1H), 7.64 (d, J=8.8 Hz, 2H), 7.82 (d, J=8.8 Hz, 2H), 11.17 (s, 1H), 13.25 (s, 1H), 13.41 (s, 1H): APCI-MS m/z 389/391 (M−H) − . Anal. Calcd for C 15 H 11 CIN 6 O 3 S: C, 44.86, H, 3.06; N, 20.93; S, 7.98. Found C, 45.02, H, 3.31; N, 20.92; S, 7.77.
EXAMPLE 66
4-[N′-(1,7-Dioxo-2,3,6,7-tetrahydro-1H-2,6-diaza-as-indacen-8-ylidene)-hydrazino]-N-methyl-benzenesulfonamide (Z-Isomer)
[0367] A solution of 16.2 g (100 mmol) of 6-aminophthalimide, 9.6 g (100 mmol) of methanesulfonic acid, and 4.0 g of 10% Pd/C in 140 mL of TFA was hydrogenated overnight at 50 psi. The catalyst was filtered off and and the filtrate concentrated on a rotary evaporator. The residue was diluted with 70 mL of ice water, adjusted to pH 8 with K 2 CO 3 , and chilled in an ice bath. The resulting solid was filtered to give 6.7 g of a 5:4 ratio of 5-amino:6-amino lactam isomers. Recrystallization from hot ethanol/water afforded 1.45 g of undesired isomer. The filtrate was preabsorbed onto silica gel and chromatographed with TEA:MeOH:methylene chloride (1:2:47). The resulting solid was slurried in methylene chloride/MeOH and filtered to afford a low yield of 5-amino-2,3-dihydro-isoindol-1-one: 1 H NMR (DMSO-d 6 ): δ 4.13 (s, 2H), 5.67 (s, 2H), 6.55 (dd, J=8.7, 1.9 Hz, 1H), 6.55 (d, J=1.9 Hz, 1H), 7.25 (d, J=8.7 Hz, 1H), 7.83 (s, 1H); APCI-MS m/z 149 (M+H) + .
[0368] 2,6-Dihydro-1H-2,6-diaza-as-indacene-3,7,8-trione was prepared from 5-amino-2,3-dihydro-isoindol-1-one according to Procedure X: 1 H NMR (DMSO-d 6 ): δ 4.46 (s, 2H), 6.94(d, J=8.1 Hz, 1H), 7.80(d, J=8.0 Hz, 1H), 8.51 (s, 1H), 11.28 (s, 1H); APCI-MS m/z 201 (M−H) − . The title compound was prepared from 2,6-dihydro-1H-2,6-diaza-as-indacene-3,7,8-trone and 4-(N-methylsulfonamido)phenylhydrazine according to Procedure G: mp >250° C.; 1 H NMR (DMSO-d 6 ): δ 2.37 (d, J=4.9 Hz, 3H), 4.56 (s, 2H), 6.99 (d, J=7.9 Hz, 1H), 7.31 (q, J=5.2 Hz, 1H), 7.55 (d, J=8.1 Hz, 1H), 7.60 (d, J=8.8 Hz, 2H), 7.72 (d, J=8.7 Hz, 2H), 8.50 (s, 1H), 11.35 (s, 1H), 12.70 (s, 1H); APCI-MS m/z 384 (M−H) − . Anal. Calcd for C 17 H 15 N 5 O 4 S 0.75H 2 O: C, 51.19; H, 4.17; N, 17.56. Found: C, 51.29; H, 4.15; N, 17.47.
EXAMPLE 67
N-(3-Hydroxy-2,2-dimethyl-propyl)-C-{4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-phenyl}-methanesulfonamide (Z-Isomer)
[0369] A solution of 3.16 g (30.6 mmol) of 3-amino-2,2-dimethylpropanol in 10 mL of CH 2 Cl 2 was added at once to a solution of 2.40 g (10.2 mmol) of 4-nitrophenylmethanesulphonyl chloride (Lee, et al., Journal of the American Chemical Society 1987, 109, 7472-7; Macor, et al., Tetrahedron Letters 1992, 33, 8011-4) in 40 mL of CH 2 Cl 2 . The mixture was stirred at rt for 15 min, the solvent was removed in vacuo and the residue was redissolved in 50 mL of EtOAc. The solution was washed with three 50-mL portions of 1.0 N HCl and concentrated in vacuo. Purification of the residue by flash chromatography on silica gel (hexane/EtOAc 1:1) afforded N-(3-hydroxy-2,2-dimethyl-propyl)-(4-nitrophenyl)-methanesulfonarnide as a white solid (0.84 g, 27%): 1 H NMR (DMSO-d 6 ): δ 0.74 (s, 6H), 2.78 (d, J=6.4 Hz, 2H), 3.11 (d, J=5.3 Hz, 2H), 4.47 (t, J=5.3 Hz, 1H), 4.52 (s, 2H), 7.02 (t, J=6.4 Hz, 1H), 7.65 (d, J=8.8 Hz, 2H), 8.25 (d, J=8.8 Hz, 2H); APCI-MS: m/z 301 (M−H) − . A mixture of 0.66 g (2.2 mmol) of N-(3-hydroxy-2,2-dimethyl-propyl)(4-nitro-phenyl)-methanesulfonamide and 0 06 g Pd/C 10 % in 50 mL of MeOH was shaken on a Parr hydrogenator for 3.5 h. The catalyst was removed via filtration, and 0.273 mL (3.28 mmol) of conc. HCl was added. The solvent was removed in vacuo, and the solid residue was redissolved in 20 mL of EtOH and added to 0.486 g (1.98 mmol) of 8-dimethylaminomethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one. The mixture was heated to reflux for 4.5 h and cooled to ambient tempurature. The solid was collected by vacuum filtration, washed with water, and dried in a vacuum oven at 70° C. to afford the title compound as a yellow solid (0.66 g, 70%): mp 229-230° C. (dec); IH NMR (DMSO-d 6 ): δ 0.74 (s, 6H), 2.73 (d, J=6.4 Hz, 2H), 3.08 (d, J=5.3 Hz, 2H), 4.27 (s, 2H), 4.43 (t, J=5.3 Hz, 1H), 6.84 (t, J=6.4 Hz, 1H), 7.09 (d, J=8.3 Hz, 1H), 7.37 (d, J=8.5 Hz, 2H), 7.42 (d, J=8.5 Hz, 2H), 7.77 (d, J=8.3 Hz, 1H), 8.03 (d, J=12.3 Hz, 1H), 9.24 (s, 1H), 10.84 (s, 1H), 11.04 (d, J=12.3 Hz, 1H); ESI-MS: m/z471 (M−H) − . Anal. Calcd for C 22 H 24 N 4 O 4 S 2 .0.5H 2 O: C, 54.87; H, 5.23; N, 11.63; S, 13.32. Found: C, 54.90; H, 5.26; N, 11.68; S, 13.25.
EXAMPLE 68
N-Methyl -C-{4-[N′(2-oxo-2,3-dihydro-pyrrolo[3,2f-]quinolin-1-ylidene)-hydrazino]-phenyl}-methanesulfonamide (Z-Isomer)
[0370] 2-Hydroxyimino-N-quinolin-6-yl-acetamide was prepared in 61% yield from 6-aminoquinoline according to Procedure A: 1 H NMR (DMSO-d 6 ): δ 12.4 (s, 1H), 10.8 (s, 1H), 9.0 (d, 1H), 8.8 (d, 1H), 8.7 (s, 1H), 8.2 (s, 2H), 7.81 (m, 1H), 7.78 (s, 1H); C 11 H 9 N 3 O 2 : APCI-MS m/z 216 (M+H) + . To a 1-L 3-neck round bottom flask was placed a magnetic stir bar and 110 mL of concentrated sulfuric acid. The flask was fitted with a thermometer to monitor the temperature of the reaction. The sulfuric acid was heated to 100° C. followed by slow addition of 2-hydroxyimino-N-quinolin-6-yl-acetamide (26.0 g, 0.121 mol). Heat to the reaction was maintained for approximately 1 h. The flask was removed from the heat source, and the reaction was poured slowly and carefully onto a mixture of 1 Kg of ice and 200 g of sodium carbonate. The residual reaction mixture in the reaction vessel was washed out with an additional 40 mL of cold water. The resulting aqueous slurry was stirred for about 1 h and filtered. The solid was washed thoroughly with water, filtered, and air dried to yield 7.31 g (31%) of 3-H-pyrrolo[3,2-f]quinoline-1,2-dione: 1 H NMR (DMSO-d 6 ): δ 11.1 (s, 1H), 8.8 (d, 1H), 8.7 (d, 1H), 8.2 (d, 1H), 7.6 (m, 1H), 7.4 (d, 1H); APCI-MS m/z 197 (M−H) − . The title compound was prepared in 77% yield from 3-H-pyrrolo[3,2-f]quinoline-1,2-dione and 4-hydrazinophenyimethane sulfonamide according to Procedure G: 1 H NMR (DMSO-d 6 ): δ 13.1 (s, 1H), 11.5 (s, 1H), 9.3 (d, 1H), 8.9 (d, 1H), 8.0 (d, 1H), 7.9 (m, 1H), 7.6 (d, 1H), 7.6(d, 2H), 7.4 (d, 2H), 6.9(d, 1H), 4.3 (s, 2H), 2.55 (d, 3H); APCI-MS m/z 396 (M+H) + .
EXAMPLE 69
N-(1H-Indazol-6-yl)4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-arnino]-benzenesulfonamide (Z-Isomer)
[0371] The title compound was przepared in 16% yield from 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-inclacen-7-one and 4-amino-N-(1H-indazol-6-yl) benzenesulfonamide according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 12.9 (s, 1H), 11.1 (d, 1H), 10.9 (s, 1H), 10.4 (s, 1H), 9.3 (s, 1H), 8.1(d, 1H), 8.0 (s, 1H), 7.8 (d, 1H), 7.8 (d, 2H), 7.7 (d, 1H), 7.6 (d, 2H), 7.3 (s, 1H), 7.1 (d, 1H), 6.9 (d, 1H); APCI-MS m/z487 (M−H) − .
EXAMPLE 70
4-[(7-Oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenmethyl)-amino]-N-thiazol-2-yl-benzenesulfonamide (Z-Isomer)
[0372] The title compound was prepared in 33% yield from 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one and 4-amino-N-(thiazol-2-yl)-benzenesulfonamide according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 12.7 (s, 1H), 11.2 (d, 1H), 10.9 (s, 1H), 9.3 (s, 1H), 8.1 (d, 1H), 7.8 (t, 3H), 7.6 (d, 2H), 7.3 (d, 1H), 7.2 (d, 1H), 6.8 (dE, 1H); APCI-MS m/z 456 (M+H) + and 454 (M−H) − .
EXAMPLE 71
N(Amino-imino-methyl)-4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-benzenesulfonamide (Z-Isomer)
[0373] The title compound was prepared in 26% yield from 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one and 4-amino-N-(amino-imino-methyly benzenesulfonamide according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 11.2 (d, 1H), 10.9 (s, 1H), 9.3 (s, 1H), 8.1 (d, 1H), 7.85 (d, 1H), 7.8 (d, 2H), 7.5 (d, 2H), 7.4 (d, 1H), 7.3 (d, 1H), 6.5 (d, 1H), 5.7 (s, 1H); C 17 H 14 N 6 O 3 S 2 : APCI-MS m/z 415 (M+H) + .
EXAMPLE 72
See Procedure J
EXAMPLE 73
8-(2,2-Dioxo-1,3-dihydro-benzo[c]thiophene-5-ylamino-methylene)-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one (Z-Isomer)
[0374] The title compound was prepared in 37% yield from 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one and 2,2-dioxo-1,3-dihydrobenzo[c]thiophene-5-ylamine according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 11.11 (d,1H:), 10.89 (s, 1H), 9.27 (s, 1H), 8.06 (d, 1H), 7.82 (d, 1H), 7.47 (m, 2H), 7.13 (d, 1H), 6.98 (d, 1H), 6.5 (m, 2H); APCI-MS m/z 384 (M+H) + .
EXAMPLE 74
{4-[-(7-Oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-phenyl}-methanesulfonamide (Z-Isomer)
[0375] The title compound was prepared in 25% yield from 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one and 4-aminophenylmethane sulfonamide according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 11.1 (d,1H), 10.9 (s, 1H), 9.3 (s, 1H), 8.1 (d, 1H), 7.8 (d, 1H), 7.5 (q, 4H), 7.2 (d, 1H), 6.9 (s, 2H), 4.2 (s, 2H); APCI-MS rnLz 387 (M+H) + .
EXAMPLE 75
N-Allyl-C-{4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-phenyl}-methansulfonamide (Z-Isomer)
[0376] The title compound was prepared in 26% yield from 8-ethoxymethylene-6,8-dihydro-i-thia-3,6-diaza-as-indacen-7-one and N-allyl-4-aminophenylmethane sulfonamide according to Procedure J: 1 H NMR (DMSO 6): δ 11.1 (d, 1H), 10.9 (s 1H), 9.3 (s, 1H), 8.1 (d, 1H), 7.8 (d, 1H), 7.5 (q, 4H), 7.3 (t, 1H), 7.1 (d, 1H), 5.8 (m, 1H), 5.2 (d, 1H), 5.1 (d, 1H), 4.4 (s, 2H), 3.6 (t, 2H); APCI-MS m/z 427 (M+H) + .
EXAMPLE 76
8-(4-Methylsulfonylmethyl-phenylamino-methylene)-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one (Z-Isomer)
[0377] The title compound was prepared in 66% yield from 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one and 4-methylsulfonylmethylaniline according to Procedure J: 1 H NMR (DMSO-d 6 ): 811.1 (d, 1H), 11.0 (s, 1H), 9.3 (s, 1H), 8.1 (d, 1H), 7.8 (d, 1H), 7.5 (q, 4H), 7.1 (d, 1H), 4.45 (s, 2H), 2.9 (s, 3H); APCI-MS m/z 384 (M−H) − .
EXAMPLE 77
N-(3-Hydroxy-2,2-dimethyl-propyl)4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-benzenesulfonamide (Z-Isomer)
[0378] The title compound was prepared from 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one and 4-amino-N-(3-hydroxy-2,2-dimethyl-propyl)benzenesulfonamide according to Procedure J: mp >250 0 C; 1 H NMR (DMSO-d 6 ): δ 0.74 (s, 6H), 2.52 (d, J=6.7 Hz, 2H), 3.06 (bs, 2H), 4.43 (bs, 1H), 7.10 (d, J=8.3 Hz, 1H), 7.32 (t, J=6.7 Hz, 1H), 7.58 (d, J=8.8 Hz, 2H), 7.77 (d, J=8.8 Hz, 2H), 7.81 (d, J=8.3 Hz, 1H), 8.07 (d, J=12.2 Hz, 1H), 9.26 (s, 1H), 10.91 (s, 1H), 11.16 (d, J=12.3 Hz, 1H); APCI-MS: m/z 457 (M−H) − . Anal. Calcd for C 21 H 22 N 4 O 4 S 2 : C, 55.01; H, 4.84; N, 12.22; S. 138. Found: C, 54.90; H. 4.86; N, 12.25; S, 13.94.
EXAMPLE 78
4-[(7-Oxo-6,7-dihydro-4-thia-3,6-diaza-as-indacen-8 ylidenemethyl)-amino]-N-(3-trifluoromethyl-phenyl)-benzenesulfonamide (Z-Isomer)
[0379] The title compound was prepared in 29% yield from 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-inciacen-7-one and N-(3-trifluoromethylphenyl)-4-aminobenzenesulfonamide according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 11.2 (d, 1H), 10.9 (s, 1H), 10.7 (s, 1H), 9.3 (s, 1H), 8.1 (d, 1H), 7.8 (m, 3H), 7.5 (m, 4H), 7.1 (d, 1H); APCI-MS m/z 515 (M−H) − .
EXAMPLE 79
4-[(7-Oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-N-pyrimidin-2-yl-benzenesulfonamide (Z-Isomer)
[0380] The title compound was prepared in 29% yield from 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one and 4-amino-N-pyrimidin-2-yl-benzenesulfonamide according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 11.18 (d, 1H), 10.94 (s, 1H), 9.28 (s, 1H), 8.52 (d, 1H) 8.08 (d, 1H), 7.99 (d, 1H), 7.84 (d, 1H), 7.6 (d, 1H), 7.13 (d,i 1H), 7.06 (m, 1H), 7.01 (m, 1H),; APCI-MS m/z 449 (M−H) − .
EXAMPLE 80
N-(5-Methyl-[1,3,4]thiadiazol-2-yl)4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-benzenesulfonamide (Z-Isomer)
[0381] The title compound was prepared in 36% yield from 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-incdacen-7-one and 4-amino-N-(5-methyl[1,3,4]thiadiazol-2-yl)-benzenesulfonamide according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 11.2 (d, 1H), 10.9 (s, 1H), 9.3 (s, 1H), 8.1 (d, 1H), 7.8 (m, 3H), 7.6 (d, 2H), 7.1 (d, 1H); ESI-MS m/z 469 (M−H) − .
EXAMPLE 81
N-Acetyl-4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-berizenesulfonamide (Z-Isomer)
[0382] The title compound was prepared in 26% yield from 8 -ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one and N-acetyl-4-aminobenzenesulfonamide according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 12.0 (s, 1H), 11.2 (d, 1H), 10.9 (s, 1H), 8.1 (d, 1H), 7.9 (m, 3H), 7.6 (d, 2H), 7.1 (d, 1H), 2.0 (s, 3H); ESI-MS m/z 413 (M−H) − .
EXAMPLE 82
N-Benzoyl-4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-benzenesulfonamide (Z-Isomer)
[0383] The title compound was prepared in 25% yield from 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one and N-benzoyl-4-aminobenzenesulfonamide according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 12.5 (br s, 1H), 11.2 (d, 1H), 10.9 (s, 1H), 9.3 (s, 1H), 8.1 (d, 1H), 8.0 (d, 2H), 7.9 (t, 3H), 7.65 (t, 3H), 7.5 (t, 2H), 7.2 (d, 1 H); ESI-MS m/z 475 (M−H) − .
EXAMPLE 83
N-Methyl-4-[N′-(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidene)-hydrazino]-benzenesulfonamide (Z-Isomer)
[0384] 6H-1-Thia-3,6-diaza-as-indacene-7,8-dione was prepared from 6-aminobenzothiazole according to Procedure A: 1 H NMR (DMSO6): δ 7.10 (d, J=8.4 Hz, 1 H), 8.31 (d, J=8.5 Hz, 1 1 H), 9.35 (s, 1H), 11.19 (s, I1H); ESI-MS m/z 204 (M)-,. The title compound was prepared from 6H-1-thia-3,6-diaza-as-indacene-7,8-dione and 4-sulfonamidophenythydrazine hydrochloride according to Procedure G: mp >260°; 1 H NMR (DMSO-d 6 ): δ 2.39 (d, J=5.1 Hz, 3H), 7.12 (d, J=8.4 Hz, 1H), 7.32 (q, J=5.1 Hz, 1H), 7.63 (d, J=8.8 Hz, 2H), 7.76 (d, J=8.7 Hz, 2H), 7.99 (d, J=8.6 Hz, 1H), 9.30 (s, 1H), 11.26 (s, 1H), 12.69 (s, 1H); APCI-MS m/z 387 (M) − . Anal. Calcd for C 16 H 13 N 5 O 3 S 2 .0.33H 2 O: C, 48.85; H, 3.50; N, 17.80; S, 16.30. Found: C, 48.89; H, 3.40; N, 17.67; S, 16.23.
EXAMPLE 84
N-[2-(2-Hydroxy-ethoxy)-ethyl]-N-methyl-4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-benzenesulfonamide (Z-Isomer)
[0385] To a solution of 3.3 g (31 mmol) of 2-(2-aminoethoxy)ethanol in 30 mL of MeOH was added 7.0 g (30 mmol) of N-acetylsulfanilyl chloride, followed by 3.3 g (33 mmol) of TEA. The reaction mixture was stirred for 30 min at rt and then acidified with 5 mL (60 mmol) of concentrated HCl and stirred at reflux for 75 min. After cooling, the mixture was diluted with 40 mL of water and made basic with solid NaHCO 3 . MeOH was removed on a rotary evaporator, and the residual aqueous solution was extracted with four 50-mL portions of EtOAc. The combined extracts were dried over Na 2 CO 3 , and the solvent was removed on a rotary evaporator to give 4-amino-N-(2-(2-hydroxyethoxy)ethyl)-benzenesulfonamide as a viscous oil (7.5 g, 96%): 1 H NMR (DMSO-d 6 ): δ 2.77 (q, J=6.0 Hz, 2H), 3.30 (t, J=4.9 Hz, 2H), 3.31 (t, J=6.5 Hz, 2H), 3.41 (q, J=5.2 Hz, 2H), 4.54 (t, J=5.5 Hz, 1H), 5.89 (s, 2H), 6.57 (d, J=8.7 Hz, 2H), 7.10 (t, J=7.37 (d, J=8.6 Hz, 2H); ESI-MS rn/s 259 (M−H) − . To a solution of 0.63 g (2.4 mmol) of 4-amino-N-(2-(2-hydroxyethoxy)ethyl)-benzenesulfonamide in 10 mL of THF was added 0.10 g (2.5 mmol) of 60% sodium hydride. The mixture was stirred for 1 h at rt, 1 mL of DMSO and 0.2 mL (3 mmol) of methyl iodide were added to the resulting suspension. The reaction mixture was stirred 2 h at rt and then poured into 15 mL of half saturated NaCl solution and extracted with 30 mL of EtOAc. The organic solution was dried with MgSO 4 and concentrated on a rotary evaporator. The residue was chromatographed on silica gel with EtOAc to give 4-amino-N-(2-(2-hydroxyethoxy)ethyl)N-methyl-benzenesulfonamide as an oil (0.43 g, 65%): 1 H NMR (DMSO-d 6 ): δ 2.59 (s, 3H), 2.96 (t, J=5.9 Hz, 2H), 3.36 (t, J=5.2 Hz, 2H), 3.43 (t, J=5.2 Hz, 2H), 3.47 (t, J=5.9 Hz, 2H), 4.55 (t, J=5.4 Hz, 1H), 5.99 (s, 2H), 6.59 (d, J=8.7 Hz, 2H), 7.34 (d, 8.8 Hz, 2H); APCI-MS m/z 297 (M+Na) + . The title compound was prepared from 4-amino-N-(2-(2-hydroxyethoxy)ethyl)-N-methyl-benzenesulfonamide and 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one according to Procedure J: mp 165° C.; 1 H NMR (DMSO-d 6 ): δ 2.71 (s, 3H), 3.11 (t, J=5.6 Hz, 2H), 3.37 (t, J=5.0 Hz, 2H), 3.44 (dt, J=5.1, 5.0 Hz, 2H), 3.52 (t, J=5.6 Hz, 2H), 4.56 (brt, J=5.2 Hz, 1H), 7.10 (d, J=8.4 Hz, 1H), 7.61 (d, J=8.7 Hz, 2H), 7.75 (d, J=87 Hz, 2H), 7.81 (d, J=8.5 Hz, 1H), 8.06 (d, J=12.0 Hz, 1I), 9.25 (s, 1H), 10.91 (s, 1H), 11.16 (d, J=12.0 Hz, 1H); APCI-MS m/z 474 M − . Anal. Calcd for C 21 H 22 N 4 O 5 S 2 .H 2 O: C, 51.21; H, 4.91; N, 11.37. Found: C, 51.18; H, 4.88; N, 11.33.
EXAMPLE 85
N-(2-{2-[2-(2-Methoxy-ethoxy)-ethoxy]-ethoxy}-ethyl)-4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-benzenesulfonamide (Z-Isomer)
[0386] A solution of 2.3 g (6.3 mmol) of toluene-4-sulfonic acid 2-{2-[2-(2-methoxy-ethoxy)-ethoxy]ethoxy)ethyl ester and ˜4 mL (˜60 mmol) of ammonium hydroxide in 10 mL of ethanol was stirred overnight at −60° C. The solvent was removed on a rotary evaporator, and the residue was sequentially redissolved in ethanol and concentrated several times. The residue was then dissolved in ethanol, treated with ˜1.5 mL of TEA and concentrated on a rotary evaporator. This residue was dissolved in 10 mL of THF, and 1.4 g (6.0 mmol) of 4-N-acetylsulfanilyl chloride and 1 mL (7 mmol) of TEA were added. The reaction mixture was stirred 1.5 h at it and then 30 min at reflux. The solution was concentrated onto silica gel and chromatographed with an EtOAc to 5% MeOH/EtOAc gradient to give 4-N-(2-{2-[2-(2-methoxy-ethoxy)-ethoxy]-ethoxy}ethyl)sulfonamidophenyl]acetamide as an oil (1.92 g, 79%): 1 H NMR (DMSO-d 6 ): δ 2.05 (s, 3H), 2.83 (q, J=5.9 Hz, 2H), 3.19 (s, 3H), 3.30-3.48(m, 14H), 7.52 (t, J=5.8 Hz, 1H), 7.68 (d, J=9.0 Hz, 2H), 7.72 (d, J=8.8 Hz, 2H), 10.27 a(S 1H); APCI-MS m/z 403 (M−H) − . A solution of 1.9 g (4.7 mmol) of N-[4-(2-{2-[2-(2-methoxy-ethoxy)ethoxy]-ethoxy}ethylsulfamoyl)-phenyl]-acetamide and 0.45 g (4.7 mmol) of methanesulfonic acid in 15 mL of ethanol was stirred at ˜70° C. for 1 d. Excess TEA was added and the solvent was removed on a rotary evaporator. The residue was applied to a short column of silica gel and eluted with EtOAc to give 4-(N-(2-{2-[2-(2-methoxyethoxy)ethoxylethoxy}ethyl)-sulfonamidoaniline as an oil (1.2 g, 70%): 1 H NMR (DMSO-d 6 ): δ 2.76 (q, J=6.0 Hz, 2H), 3.20 (s, 3H), 3.32 (t, J=6.2 Hz, 2H), 3.37-3.48 (m, 12H), 5.88 (s, 2H), 6.56 (d, J=8.6 Hz, 2H), 7.11 (t. J=6.0 Hz, 1H), 7.37 (d, J=8.7 Hz, 2H); APCI-MS m/z 361 (M−H) − . The title compound was prepared from 4-(N-(2-{2-[2-(2-methoxyethoxy)ethoxy]ethoxyethyl)sulfonamidoaniline and 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one according to Procedure J: mp 158-159° C.; 1 H NMR (DMSOC-d 6 ): δ 2.87 (dt, J=5.6, 5.6 Hz, 2H), 3.17 (s, 3H), 3.33-3.38 (m, 4H), 3.38-3.47 (m, 10H), 7.10 (d, J=8.3 Hz, 1H), 7.58 (d, J=8.7 Hz, 2H), 7.63 (t, J=5.7 Hz, 1H), 7.77 (d, J=8.7 Hz, 2H), 7.81 (d, J=8.5 Hz, 1H), 8.06 (br d, J=8.9 Hz, 1i), 9.25 (s, 1H), 10.91 (s, 1H), 11.16 (brd, J=10.8 Hz, 1H); APCI-MS m/z 561 (M−H) − . Anal. Calcd for C 25 H 30 N 4 O 7 S 2 .0.33 H 2 O: C, 52.81; H, 5.43; N, 9.85. Found: C, 52.81; H, 5.29; N, 9.82.
EXAMPLE 86
4-[N′-(5,6-Dimethyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonaimide (Z Isomer)
[0387] The title compound was prepared from 5,6-dimethyl-1H-indole-2,3-dione and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G in 32% yield: 1 H NMR (DMSO-d 6 ): δ 2.22 (s, 3H), 2.24 (s, 3H), 6.72 (s, 1H), 7.23 (s, 2H), 7.36 (s, 1H), 7.52 (d, J=8.8 Hz, 2H), 7.77 (d, J=8.8 Hz, 2H), 10.93 (s, 1H), 12.71 (s, 1H). APCI-MS m/z 343 (M−H) − . Anal. Calcd for C 16 H 16 N 4 O 3 S: C, 55.80, H, 4.68; N, 16.27; S, 9.31. Found C, 55.78, H, 4.74; N, 16.37; S, 9.22.
EXAMPLE 87
N-{6-Hydroxy-3-[(4-methylsulfamoylmethyl-phenyl)-hydrazono]-2-oxo-2,3-dihydro-1H-indol-5-yl}-acetamide (Z Isomer)
[0388] Condensation of N-(6-hydroxy-2,3-dioxo-2,3-dihydro-1H-indol-4-yl)acetamide and 4-hydrazino-N-methyl-benzylsulfonamide hydrochloride according to Procedure G gave the title compound in 4% yield: 1 H NMR (DMSO-d 6 ): δ 2.04 (s, 3H), 2.51 (d, J=4.8 Hz, :3H), 4.24 (s, 2H), 6.45 (s, 1H), 6.84 (t, J=4.8 Hz, I 1H), 7.30 (s, 4H), 7.82 (s, 1H), 9.12 (s, 1H), 10.20 (s, 1H), 10.77 (s, 1H), 12.50 (s, 1H); APCI-MS m/z 416 (M−H) − .
EXAMPLE 88
4-[N′-(6-Chloro-5-methoxy-2-oxo-1,2-dihydro;ndol-3-ylidene)-hydrazino]benzene-sulfonamide (Z-Isomer)
[0389] The title compound was prepared from 6-chloro-5-methoxy-1H-indole-2,3-dione (Pajouhesh et al., Journal of Pharmaceutical Sciences 1983, 72, 318-21) and 4-sulfonamido-phenylhydrazine hydrochloride according to Procedure G: mp >250° C.; 1 H NMR (DMSO-d 6 ): δ 3.88 (s, 3H), 6.93 (s, 1H), 7.25 (s, 2H), 7.35 (s, 1H), 7.59 (d, J=8.8 Hz, 2H), 7.76 (d, J=8.8 Hz, 2H), 10.97 (s, 1H), 12.78 (s, 1H); APCI-MS: m/z 379 (M−H) − . Anal. Calcd for C 15 H 13 N 4 O 4 CIS: C, 47.31; H, 3.44; N, 14.71; Cl, 9.31 S, 8.42. Found: C, 47.57; H, 3.71; N, 14.93; Cl, 9.11 S, 8.17.
EXAMPLE 89
4-[N′-(5-Hydroxy-6-isopropyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z-Isomer)
[0390] 5-Hydroxy-6-isopropyl-1H-indole-2,3-dione was prepared from 3-isopropyl-4-hydroxyaniline according to Procedure A: 1 H NMR (DMSO-d 6 ): δ 1.12 (d, J=6.8 Hz, 6H), 3.21 (septet, J=6.9 Hz, 1H), 6.62 (s, 1H), 6.82 (s, 1H), 9.51 (s, 1H), 10.61 (s, 1H); ESI-MS m/z 204 (M−H) − . The title compound was prepared from 5-hydroxy-6-isopropyl-1H-indole-2,3-dione and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G: mp >250° C.; 1 H NMR (DMSO-d 6 ): δ 1.12 (d, J=7.0 Hz, 6H), 3.21 (septet, J=6.8 Hz, 1H), 6.62 (s, 1H), 6.97 (s, 11H), 7.21 (s, 2H), 7.45 (d, J=8.9 Hz, 2H), 7.75 (d, J=8.7 Hz, 2H), 9.11 (s, 1H), 10.70 (s, 1H), 12.74 (s, 1H); ESI-MS m/z 373 (M−H) − . Anal. Calcd for C 17 H 18 N 4 O 4 S: C, 54.53; H, 4.85; N, 14.96; S, 8.56. Found: C, 54.37; H, 4.95; N, 14.84; S, 8.48.
EXAMPLE 90
4-[N′ -(2-Methyl-6-oxo-5,6-dihydro-3-oxa-1,5-diaza-s-indacen-7-ylidene)-hydrazino]-benzenesulfonamide (Z Isomer)
[0391] N-(6-Hydroxy-2,3-dioxo-2,3-dihydro-1H-indol-4-yl)acetamide was prepared from 6-amino-2-methylbenzoxazole (Heleyova, et al., Collection of Czechoslovakian Chemical Communications 1996, 61, 37180) according to Procedure A in 12% overall yield. Condensation of N-(6-hydroxy-2,3-dioxo-2,3-dihydro-1H-indol-4-yl)acetamide and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G gave the title compound in 6% yield: 1 H NMR (DMSO-d 6 ): δ 2.55 (s, 3,H), 7.13 (s, 1H), 7.23 (s, 2H), 7.57 (d, J=8.8 Hz, 2H), 7.76 (d, J=8.8 Hz, 2H), 7.78 (s, 1H), 11.12 (s, 1H), 12.67 (s, 1H); APCI-MS m/z 370 (M−H) − . Anal. Calcd for C 16 H 15 N 5 O 4 S: C, 51.75, H, 3.53; N, 18.86; S, 8.86. Found C, 51.50, H, 3.61; N, 18.69; S, 8.49.
EXAMPLE 91
4-[N′-(5-Acetyl-2-oxo-2,5,6,7-tetrahydro-1H-pyrrolo[2,3-f]indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z-Isomer)
[0392] 5-Acetyl-1,5,6,7-tetrahydro-pyrrolo[2,3-f]indole-2,3-dione was prepared from 1-acetyl-5-aminoindoline according to Procedure A in 90% yield: mp >250° C.; 1 H NMR (DMSO-d 6 ): δ 2.11 (s,3H), 3.16 (t, J=8.4 Hz, 2H), 4.06 (t, J=8.4 Hz, 2H), 6.78 (s, 1H), 8.02 (s, 1H), 10.87 (s, 1H); APCI-MS: m/z 229 (M−H) − . Anal. Calcd for C 12 H 10 N 2 O 3 .0.3H 2 O: C, 61.17; H, 4.53; N, 11.89. Found: C, 60.91; H, 4.62; N, 12.10. The title compound was prepared from 5-acetyl-1,5,6,7-tetrahydro-pyrrolo[2,3-f]indole-2,3-dione and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G in 53% yield: mp >250° C.; 1 H NMR (DMSO-d 6 ):d2.13 (s,3H), 3.13 (t, J=8.4 Hz, 2H), 4.06 (t, J=8.4 Hz, 2H), 6.79 (s, 1H), 7.22 (s, 2H), 7.48 (d, J=8.7 Hz, 2H), 7.76 (d, J=8.7 Hz, 2H), 8.24 (s, 1H), 10.96 (s, 1H), 12.78 (s, 1H); APCI-MS: m/z 422 (M+Na) + . Anal. Calcd for C 18 H 17 N 5 O 4 S: C, 54.13; H, 4.29; N, 17.53; S, 8.03. Found: C, 53.85; H, 4.23; N, 17.28; S, 7.89.
EXAMPLE 92
4-[N′-(6-Oxo-5,6-dihydro-[1,3]-dioxolo[4,5-f]indol-7-ylidene)-hydrazino]-benzenesulfonamide (Z-Isomer)
[0393] The title compound was prepared from 5H-[1,3]dioxolo[4,5-f]indole-6,7-dione (Lackey and Sternbach, Synthesis 1993, 993-7) and 4-sulfonamidophenylhydrazine hydrochloride in 55% yield as an orange crystalline solid following Procedure G: mp >220° C.; 1 H NMR (DMSO-d 6 ): δ 12.63 (s, 1H), 10.89 (s, 1H), 7.73 (d, J=7 Hz, 2H), 7.50 (d, J=7 Hz, 2H), 7.22 (s, 2H), 7.13 (s, 1H), 6.56 (s, 1H), 6.00 (s, 2H). Anal. Calcd for C 15 H 12 N 4 O 5 S: C, 50.00; H, 3.36; N, 15.55. Found: C, 50.08; H, 3.35; N, 15.49.
EXAMPLE 93
4-[N′-(2-Oxo-2,5,6,7-tetrahydro-1H-pyrrolo[2,3-f]indol-3-ylidene)-hydrazino]-benzenesulfonamide hydrobromide (Z-Isomer)
[0394] A solution of 0.10 g (0.44 mmol) of 5-acetyl-1,5,6,7-tetrahydro-pyrrolo[2,3-f]indole-2,3-dione in 3 mL of conc. HBr was heated to 100° C. for 18 h. The mixture was cooled to ambient temperature, diluted with 10 mL of water and filtered. The filtrate was concentrated in vacuo and added to a solution of 0.05 g (0.2 mmol) 4-sulfonamidophenylhydrazine hydrochloride in 5 mL of EtOH. The mixture was heated to 80° C. for 1 h and cooled to ambient tempurature. The resulting solid was collected by vacuum filtration, washed with water and dried in a vacuum oven at 70° C. to afford the title compound as a tan solid (0.026 g, 17%): mp >250° C.; 1 H NMR (DMSO-d 6 ): δ 3.17 (t, J=7.8 Hz, 2H), 3.69 (t, J=7.8 Hz, 2H), 6.96 (s, 1H), 7.25 (s, 2H), 7.52 (s, 1H), 7.57 (d, J=8.8 Hz, 2H), 7.77 (d, J=8.8 Hz, 2H), 10.65 (bs, 2H), 11.24 (s, 1H), 12.73 (s, 1H); APCI-MS: m/z 356 (M−H) − . Anal. Calcd for C 16 H 15 N 5 O 3 S.0.9HBr 0.5H 2 O: C, 43.75; H, 3.88; N, 15.94; S, 7.30. Found: C, 44.01; H, 4.14; N, 15.70; S, 7.12.
EXAMPLE 94
C-{4-[N′-(4,6-Dichloro-5-methoxy-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-phenyl}-N-methyl-benzenesulfonamide (Z-Isomer)
[0395] 4,6-Dichloro-5-methoxy-1H-indole-2,3-dione was prepared from 3,5-dichloro-4-hydroxyaniline according to Procedure A in 91% yield: 1 H NMR (DMSO-d 6 ): δ 3.81 (s, 3H), 6.98 (s, 1H), 11.26 (s, 1H); APCI-MS m/z 244/246/248 (M−H) − . Condensation of 4,6-dichloro-5-methoxy-1H-indole-2,3-dione with 4-hydrazino-N-methyl-benzylsulfonamide according to Procedure G gave the title compound in 59% yield: 1 H NMR (DMSO-d 6 ): δ 2.58 (d, J=4.7 Hz, 3H), 3.84 (s, 3H), 4.33 (s, 2H), 6.93 (q, J=4.7 Hz, 1H), 6.99 (s, 1H), 7.41 (d, J=8.5 Hz, 2H), 7.51 (d, J=8.5 Hz, 2H), 11.31 (s, 1H), 12.99 (s, 1H); APCI-MS m/z 441/443 (M−H) − . Anal. Calcd for C 17 H 16 Cl 2 N 4 O 4 S: C, 46.06, H, 3.64; Cl, 15.99; N, 12.64; S, 7.23. Found C, 45.80, H, 3.55; Cl, 16.20; N, 12.57; S, 7.11.
EXAMPLE 95
4-[N′-(4-Chloro-1-hydroxy-6-methyl-2-oxo-1,2-dihydro-indol-3ylidene)-hydrazino]-benzenesulfonamide (Z-Isomer)
[0396] 4-Chloro-5-hydroxy-6-methyl-1 1-indole-2,3-dione was prepared from 3-chloro-4-hydroxy-5-methyl aniline according to Procedure A and employing flash chromatography (hexanes:EtOAc 1:1) to isolate the desired isomer: 1 H NMR (DMSO-d 6 ): δ 2.35 (s, 3H), 6.67 (s, 1H), 9.17 (s, 1H), 10.81 (s, 1H); APCI-MS: m/z 210 (M−H) − . Anal. Calcd for C 9 H 6 NO 3 Cl: C, 51.08; H, 2.85; N, 6.62; Cl, 16.75. Found: C, 51.20; H, 2.90; N. 6.67; Cl, 16.85. The title compound was prepared from 4-chloro-5-hydroxy-6-methyl-1H-indole-2,3-dione and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G in 95% yield: mp >250° C.; 1 H NMR (DMSO-d 6 ): δ 2.26 (s, 3H), 6.69 (s, 1H), 7.28 (s, 1H), 7.57 (d, J=8.8 Hz, 2H), 7.82 (d, J=8.8 Hz, 2H), 8.84 (s, 1H), 11.02 (s, 1H), 13.00 (s, 1H); APCI-MS: m/z 379 (M−H) − . Anal. Calcd for C 15 H 13 N 4 O 4 CIS: C, 47.31; H, 3.44; N. 14.71; Cl, 9.31; S, 8.42. Found: C, 47.20; H, 3.47; N, 14.64; Cl, 9.41; S, 8.32.
EXAMPLE 96
4-[N′-(5-Hyoroxy-4,6-dimethyl-2-oxo-1,2-dihydro-indol-3-ylidene)-hydrazino]-benzenesulfonamide (Z-Isomer)
[0397] 5-Hydroxy-4,6-dimethyl-1H-indole-2,3-dione was prepared from 4-hydroxy-3,5-dimethylaniline according to Procedure A. The title compound was prepared from 5-hydroxy-4,6-dimethyl-1H-indole-2,3-dione and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G: mp >250° C.; 1 H NMR (DMSO-d 6 ): δ 2.18 (s, 3H), 2.47 (s, 3H), 6.50 (s, 1H), 7.22 (s, 2H), 7.44 (d, J=8.7 Hz, 2H), 7.77 (d, J=8.7 Hz, 2H), 7.99 (s, 1H), 10.78(s, 1H), 12.98 (s, 1H); APCI-MS: m/z 359 (M−H) − . Anal. Calcd for C 16 H 16 N 4 O 4 S.0.25 H 2 O: C, 52.67; H, 4.56; N, 15.35; S, 8.79. Found: C, 52.69; H, 4.47; N, 15.33; S, 8.87.
EXAMPLE 97
3-(1H-Indazol-5-yl-amino-methylene)-1,3-dihydro-indol-2-one (Z-Isomer)
[0398] The title compound was prepared in 68% yield from 3-hydroxymethylene-1,3-dihydro-indol-2-one and 5-aminoindazole according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 13.1 (s, 1H), 10.8 (d, 1H), 10.4 (s, 1H), 8.6 (d, 1H), 8.0 (s, 1H), 7.8 (s, 1H), 7.6 (m, 2H), 7.4 (,m, 1H), 7.0 (m, 2H), 6.8 (d, 1H); C 16 H 12 N 4 O 2 : ESI-MS m/z 275 (M−H) − .
EXAMPLE 98
3-(1H-Indazol-6-ylimino-methylene)-4,3-dihydro-indol-2-one (Z-Isomer)
[0399] The title compound was prepared in 79% yield from 3-hydroxymethylene-1,3-dihydro-indol-2-one and 6-aminoindazole according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 13.02 (s, 1H), 10.86 (d, 1H), 10.51 (s, 1H), 8.7 (d, 1H), 8.0 (s, 1H), 7.74 (d, 1H), 7.63 (d, 1H), 7.51 (s, 1H), 7.15 (dd, 1H), 7.02 (m, 1H), 6.94 (m, 1H), 6.85 (d, 1H);; ESI-MS m/z 275 (M−H) − .
EXAMPLE 99
See Procedure G
EXAMPLE 100
N-Methyl-4-[(5-oxazol-5-yl-2-oxo-1,2-dihydro-indol-3-ylidenemethyl)-amino]-phenylmethanesulfonamide (Z-Isomer)
[0400] The title compound was prepared in 56% yield from ethoxymethylene-5-oxazol-5-yl-1,3-dihydro-indol-,2-one and N-methyl-4-aminophenylmethanesultonatnide hydrochloride according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 10.72 (d, 1 H), 10.67 (s, 1H), 8.71 (d, 1H), 8.37 (s, 1H), 7.43-7.34 (m, 7H), 6.89 (m. 2H), 4.28 (s, 2H), 2.54 (d, 3H); APCI-MS m/z 409 (MH) − .
EXAMPLE 101
8-(3H-Benzotriazol-5-ylaminomethylene)-6,8-dihydro-1-thia-3,6-diaza-as-indacene-7-one (Z-Isomer)
[0401] The title compound was prepared in 54% yield from 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one and 5-aminobenzotriazole according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 11.18 (d, 1 H), 10.9 (s, 1H), 9.23 (s, 1H), 8.12 (d, 1H), 7.96 (5s 1H), 7.78 (d, 1H), 7.48 (s, 1H), 7.1 (d, 1H); APCI-MS m/z 333 (M−H) − .
EXAMPLE 102
4N′-2-Oxo-2,3-hydropyrrolo[3,2-f]quinolin-1-ylidene)hydrazino]-benzenesulfonamide (Z-Isomer)
[0402] The title compound was prepared in 24% yield from 3-H-pyrrolo[3,2-f]quinoline-1,2-dione and 4-hydrazinobenzene sulfonamide hydrochloride according to Procedure G:
[0403] [0403] 1 H NMR (DMSO-d 6 ) δ 13.12 (s, 1H), 11.64 (s, 11 H), 9.32 (d, 1H) 9.01 (d, 1H), 8.13 (d, 1H), 7.9 (m, 1H), 7.83 (d, 2H), 7.69 (d, 2H), 7.62 (s, 1H), 7.33 (s, 2H).
[0404] APCI-MS m/z 368 (MH) + .
EXAMPLE 103
2-Oxo-344-sulfamoyl-phenylamino-methylene)-2,3-dihydro-1H-indole-5-carboxylic Acid Isobutyl Ester (Z-Isomer)
[0405] 3-Methylthio-2-oxo-2,3-dihydro-1H-indole-5-carboxylic acid isobutyl ester was prepared in 59% yield from isobutyl 4-aminobenzoate according to Procedure D: 1 H NMR (DMSO-d 6 ): S 0.93 (d, J 6.6 Hz, 6H), 1.93 (s, 3H), 1.98 (septet, J=6.6 Hz, 1H), 4.02 (m, 2H), 4.62 (s, 1H), 6.92 (d, J=8.2 Hz, 1H), 7.79 (s, J=1H), 7.86 (d, J=8.2 Hz, 1H), 10.91 (s, 1H); ESI-MS m/z 302 (M+23)-. Zinc reduction of 3-methylthio-2-oxo-2,3-dihydro-1H-indole-5-carboxylic acid isobutyl ester according to Procedure 8 provided 2-oxo-2,3-dihydro-1H-indole-5-carboxylic acid isobutyl ester in 99% yield: 1 H NMR (DMSO-d 6 ): δ 0.93 (d, J=6.6 Hz, 6H), 1.97 (septet, J=6.6 Hz, 1H), 3.53 (s, 2H), 3.99 (d, J=6.6 Hz, 2H), 6.88 (d, J=8.2 Hz, 1H), 7.75 (s, J=1H), 7.82 (d, J=8.2 Hz, 1H), 10.72 (s, 1H); ESI-MS m/z 256 (M+23) + . Conversion of 2-oxo-2,3-dihydro-1H-indole-5-carboxylic acid isobutyl ester to 3-[(dimethylamino)methylene]-2-oxo-2,3-dihydro-1H-indole-5-carboxylic acid isobutyl ester (mixture of E and Z isomers) was accomplished in 75% yield according to Procedure G: 1 H NMR (DMSO-d 6 ): δ 0.94 Z (d, J=8.8 Hz, 6H), 0.94 E (d, J=8.8 Hz, 6t), 1.94-2.01 Z and E (m, 2H), 3.30 Z (s, 6H), 3.32 E (s, 6H), 3.97-3.99 Z and E (m, 4H), 6.75 Z (d, J=8.2 Hz, 1H), 6.83 E (d, J=8.2 Hz, 1H), 7.47 E (s, 1H), 7.53 Z (d, J=0. 8.2 Hz, 1H), 7.59 E (d, J=8.2 Hz, 1H), 7.73 Z (s, 1H), 7.88 Z (s,, 1H), 7.98 E (s, 1H), 10.34 Z (bs, 1H), 10.44 E (bs, 1H); ESI-MS m/z 289 (M+1) + . The title compound was prepared in 66% yield from 3-[(dimethylamino)imethylene]-2-oxo-2,3-dihydro-1H-indole-5-carboxylic acid isobutyl ester and 4-arninobenzenesulfonamide hydrochloride according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 0.96 (d, J=6.6 Hz, 6H), 2.01 (septet, J=6.6 Hz, 1H), 4.04 (d, J=6.6 Hz, 2H), 6.93 (d, J=8.2 Hz, 1H), 7.26 (s, 2H), 7.60 (d, J=8.7 Hz, 2H), 7.71 (dd, J=1.6, 8.2 Hz, 1H), 7.76 (d, J=8.7 Hz, 2H), 8.27 (s, 1H), 8.86 (d, J=12.5 Hz, 1H), 10.83 (d, J=12.5 Hz, 1H), 10.95 (s, 1H); APCI-MS m/z 414 (M−H) − . Anal. Calcd for C 20 H 21 N 3 O 5 S: C, 57.82, H, 5.09; N, 10.11; S, 7.72. Found C, 57.91, H, 5.16; N, 10.02; S. 7.65.
EXAMPLE 104
4-[(7-Oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)amino]-N-pyriddinyl4-yl-methyl benzenesulfonamide (Z-Isomer)
[0406] To a 250 ml round bottom flask was added 50 ml of dry pyridine, 4-(aminomethyl) pyridine (10.4 g, 50.0 mmol) and a magnetic stir bar. The mixture was stirred and cooled to 0° C. under nitrogen followed by the addition of N-acetylsulfanilyl chloride (12.8 g, 55.0 mmol). The resultant mixture was stirred at 0° C. under nitrogen for 5 min, and the reaction was allowed to warm to rt and stirred for 16 h. The reaction mixture was concentrated to a thick residue and poured onto about 500 g of ice and water. The residue in the flask was rinsed into the ice and water with 25 ml of MeOH to precipitate the N-acetyl sulfanilamide. The resultant precipitate was filtered, washed with excess water and dried under vacuum at 50° C. The solid was suspended in 75 ml of 1 N hydrochloric acid and heated to 100° C. until all starting material had been consumed. The reaction mixture was cooled and neutralized with ammonium hydroxide. The precipatate was filtered and dried under vacuum at 50° C. to yield 5.78 g, 43.9% of 4-amino-N-(4-aminomethylpyridinyl)-benzenesulfonamide: 1 H NMR (DMSO-d 6 ): δ 8.42 (d, 2H), 7.76 (t, 1H), 7.39 (d, 2H), 7.22 (d, 2H), 6.56 (d, 2H), 5.91 (s, 2H), 3.89 (d, 2H); APCI-MS m/z 264 (MH) + . The title compound was prepared in 33% yield from 8-ethoxymethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one and 4-amino-N}4-aminomethylpyridinyl)-benzenesulfonamide according to Procedure J: 1 H NMR (DMSO-d 6 ): δ 11.15 (d, 1H), 10.9 (s, 1H), 9.24 (s, 1H), 8.44 (d, 2H), 8.24 (m, 1H), 8.05 (d, 1H), 7.81 (d, 1H), 7.76 (m, 2H), 7.56 (d, 2H), 7.24 (d, 2H), 7.1 (d, 1H), 4.01 (d, 2H); APCI-MS n/z 464 (MH)+
[0407] Pharmaceutical Formulation and Doses
[0408] The compounds of the present invention can be administered in such oral (including buccal and sublingual) dosage forms as tablets, capsules (each including timed release and sustained release formulations), pills, powders, granules, elixirs, tinctures, suspensions, syrups and emulsions. Likewise, they may also be administered in nasal, ophthalmic, otic, rectal, topical, intravenous (both bolus and infusion), intraperitoneal, intraarticular, subcutaneous or intramuscular inhalation or insulation form, all using forms well known to those of ordinary skill in the pharmaceutical arts. The dosage regimen utilizing the compounds of the present invention is selected in accordance with a variety of factors including type, species, age, weight, sex and medical condition of the patient; the severity of the condition to be treated; the route of administration; the renal and hepatic function of the patient; and the particular compound or salt thereof employed. An ordinarily skilled physician or veterinarian can readily determine and prescribe the effective amount of the drug required to prevent, counter or arrest the progress of the condition. Oral dosages of the present invention, when used for the indicated effects, will range between about 0.1 to 100 mg/kg of body weight per day, and particularly 1 to 10 mg/kg of body weight per day. Oral dosage units will generally be administered in the range of from 1 to about 250 mg and more preferably from about 25 to 250 mg. The daily dosage for a 70 kg mammal will generally be in the range of about 70 mg to 7 grams of a compound of formula I or II.
[0409] While the dosage to be administered is based on the usual conditions such as the physical condition of the patient, age, body weight, past medical history, route of administrations, severity of the conditions and the like, it is generally preferred for oral administration to administer to a human. In some cases, a lower dose is sufficient and, in some cases, a higher dose or more doses may be necessary. Topical application similarly may be once or more than once per day depending upon the usual medical considerations. Advantageously, compounds of the present invention may be administered in a single daily dose, or the total daily dosage may be administered in divided doses of two, three or four times daily. The compounds of the invention can be prepared in a range of concentrations for topical use of 0.5 to 5 mg/ml of suitable solvent. A preferred volume for application to the scalp is 2 ml, resulting in an effective dosage delivered to the patient of 1 to 10 mg. For treatment of chemotherapy-induced alopecia, administration 1 to 2 times prior to chemotherapy administration would be preferred, with additional applications administered as needed. A similar regimen can be pursued for treatment of alopecia induced by radiation therapy. Furthermore, preferred compounds for the present invention can be administered in intranasal form via topical use of suitable intranasal vehicles, or via transdermal routes, using those forms of transdermal skin patches well known to those of ordinary skill in that art. To be administered in the form of a transdermal delivery system, the dosage administration will, of course, be continuous rather than intermittent throughout the dosage regimen.
[0410] In the methods of the present invention, the compounds herein described in detail can form the active ingredient, and are typically administered in admixture with suitable pharmaceutical diluents, excipients or carriers (collectively referred to herein as “carrier” materials) suitably selected with respect to the intended form of administration, that is, oral tablets, capsules, elixirs, syrups and the like, and consistent with conventional pharmaceutical practices.
[0411] For instance, for oral administration in the fonm of a tablet or capsule, the active drug component can be combined with an oral, non-toxic pharmaceutically acceptable inert carrier such as ethanol, glycerol, water and the like. Powders are prepared by comminuting the compound to a suitable fine size and mixing with a similarly comminuted pharmaceutical carrier such as an edible carbohydrate, as, for example, starch or mannitol. Flavoring, preservative, dispersing and coloring agent can also be present.
[0412] Capsules are made by preparing a powder mixture as described above, and filling formed gelatin sheaths. Glidants and lubricants such as colloidal silica, talc, magnesium stearate, calcium stearate or solid polyethylene glycol can be added to the powder mixture before the filling operation. A disintegrating or solubilizing agent such as agar-agar, calcium carbonate or sodium carbonate can also be added to improve the availability of the medicament when the capsule is ingested.
[0413] Moreover, when desired or necessary, suitable binders, lubricants, disintegrating agents and coloring agents can also be incorporated into the mixture. Suitable binders include starch, gelatin, natural sugars such as glucose or beta-lactose, corn sweeteners, natural and synthetic gums such as acacia, tragacanth or sodium alginalte, carboxymethylcellulose, polyethylene glycol, waxes and the like. Lubricants used in these dosage forms include sodium oleate, sodium stearate, magnesium stearate, sodium benzoate, sodium acetate, sodium chloride and the like. Disintegrators include, without limitation, starch, methyl cellulose, agar, bentonite, xanthan gum and the like. Tablets are formulated, for example, by preparing a powder mixture, granulating or slugging, adding a lubricant and disintegrant and pressing into tablets. A powder mixture is prepared by mixing the compound, suitably comminuted, with a diluent or base as described above, and optionally, with a binder such as carboxymethyicellulose, an aliginate, gelatin, or polyvinyl pyrrolidone, a solution retardant such as paraffin, a resorption accelerator such as a quatemary salt and/or an absorption agent such as bentonite, kaolin or dicalcium phosphate. The powder mixture can be granulated by wetting with a binder such as syrup, starch paste, acadia mucilage or solutions of cellulosic or polymeric materials and forcing through a screen. As an alternative to granulating, the powder mixture can be run through the tablet machine and the result is imperfectly formed slugs broken into granules. The granules can be lubricated to prevent sticking to the tablet forming dies by means of the addition of stearic acid, a stearate salt, talc or mineral oil. The lubricated mixture is then compressed into tablets. The compounds of the present invention can also be combined with free flowing inert carrier and compressed into tablets directly without going through the granulating or slugging steps. A clear or opaque protective coating cconsisting of a seating coat of shellac, a coating of sugar or polymeric material and a polish coating of wax can be provided. Dyestuffs can be added to these coatings to distinguish different unit dosages. Oral fluids such as solution, syrups and elixirs can be prepared in dosage unit form so that a given quantity contains a predetermined amount of the compound. Syrups can be prepared by dissolving the compound in a suitably flavored aqueous solution, while elixirs are prepared through the use of a non-toxic alcoholic vehicle. Suspensions can be formulated by dispersing the compound in a non-toxic vehicle. Solubilizers and emulsifiers such as ethoxylated isostearyl alcohols and polyoxy ethylene sorbitol ethers, preservatives, flavor additive such as peppermint oil or saccharin, and the like can also be added.
[0414] Where appropriate, dosage unit formulations for oral administration can be microencapsulated. The formulation can also be prepared to prolong or sustain the release as for example lby coating or embedding particulate material in polymers, wax or the like.
[0415] The compounds of the present invention can also be administered in the form of liposome delivery systems, such as small unilamellar vesicles, large unilamellar vesicles and multilamellar vesicles. Liposomes can be formed from a variety of phospholipids, such as cholesterol, stearylamine or phosphatidylcholines.
[0416] Compounds of the present invention may also be delivered by the use of monoclonal antibodies as individual carriers to which the compound molecules are coupled. The compounds of the present invention may also be coupled with soluble polymers as targetable drug carriers. Such polymers can include polyvinylpyrrolidone, pyran copolymer, polyhydroxypropylmethacrylamide-phenol, polyhydroxyethylaspartamidephenol, or polyethyleneoxidepolylysine substituted with palmitoyl residues. Furthermore, the compounds of the present invention may be coupled to a class of biodegradable polymers useful in achieving controlled release of a drug, for example, polylactic acid, polepsilon caprolactone, polyhydroxy butyric acid, polyorthoesters, polyacetals, polydihydropyrans, polycyanoacrylates and cross-linked or amphipathic block copolymers of hydrogels.
[0417] The present invention includes pharmaceutical compositions containing 0.01 to 99.5%, more particularly, 0.5 to 90% of a compound of the formula (II) in combination with a pharmaceutically acceptable carrier.
[0418] Parenteral administration can be effected by utilizing liquid dosage unit forms such as sterile solutions and suspensions intended for subcutaneous, intramuscular or intravenous injection. These are prepared by suspending or dissolving a measured amount of the compound in a non-toxic liquid vehicle suitable for injection such as aqueous oleaginous medium and sterilizing the suspension or solution.
[0419] Alternatively, a measured amount of the compound is placed in a vial and the vial and its contents are sterilized and sealed. An accompanying vial or vehicle can be provided for mixing prior to administration. Non-toxic salts and salt solutions can be added to render the injection isotonic. Stabilizers, preservations and emulsifiers can also be added.
[0420] Rectal administration can be effected utilizing suppositories in which the compound is admixed with low-melting water-soluble or insoluble solids such as polyethylene glycol, cocoa butter, higher ester as for example flavored aqueous solution, while elixirs are prepared through myristyl palmitate or mixtures thereof.
[0421] Topical formulations of the present invention may be presented as, for instance, ointments, creams or lotions, eye ointments and eye or ear drops, impregnated dressings and aerosols, and may contain appropriate conventional additives such as preservatives, solvents to assist drug penetration and emollients in ointments and creams. The formulations may also contain compatible conventional carriers, such as cream or ointment bases and ethanol or oleyl alcohol for lotions. Such carriers may be present as from about 1% up to about 98% of the formulation. More usually they will form up to about 80% of the formulation.
[0422] For administration by inhalation the compounds according to the invention are conveniently delivered in the form of an aerosol spray presentation from pressurized packs or a nebulizer, with the use of a suitable propellant, e.g. dichlorodifluoromethane, trichlorofluoromethane, dichlorotetrafluoroethane, tetrafluoroethane, heptafluoropropane, carbon dioxide or other suitable gas. In the case of a pressurized aerosol the dosage unit may be determined by providing a valve to deliver a metered amount. Capsules and cartridges of e.g. gelatin for use in an inhaler or insufflator may be formulated containing a powder mix of a compound of the invention and a suitable powder base such as lactose or starch.
[0423] The preferred pharmaceutical compositions are those in a form suitable for oral administration, such as tablets and liquids and the like and topical formulations.
[0424] Biological Data
[0425] The compounds of the present invention have valuable pharmacologic properties. Different compounds from this class are particularly effective at inhibiting the CDK1 and CDK2 enzymes at concentrations which range from 0.0001 to 1 μM and additionally show specificity relative to other kinases. Substrate phosphorylation assays were carried out as follows:
[0426] CDK1 and CDK2
[0427] Cyclin dependent protein kinase assays utilized the peptides Biotin-aminohexyl-AAKAKKTPKKAKK and Biofin-aminohexyl-ARRPMSPKKKA-NH 2 as phosphoryl group acceptors. CDK1 and CDK2 were both expressed utilizing a baculovirus expression system and were partially purified to comprise 20-80% of total protein, with no detectable competing reactions present. Typically, assays were performed by incubating either enzyme (0.2-10 nM), with and without inhibitor, one of the two peptide substrates (1-10 nM), [γ- 32 P]ATP (1-20 nM), and 10-20 mM Mg 2+ for periods of time generally within the range 10-120 min. Reactions were terminated with 0.2-2 volumes of either 20% acetic acid or 50-100 mM EDTA buffered to pH 7 (substrate consumption <20%). The buffer employed in enzyme assays was either 30 mM HEPES 7.4 containing 0.15 M NaCl and 5% DMSO, the buffer 50 mM MOPS 7.0 containing 0.15 M NaCl and 5% DMSO, or the buffer 100 nmM HEPES pH 7.5 containing 0.1 mg/mL BSA and 5% DMSO. Inhibitors were diluted in 100% DMSO prior to addition into the assay. Detection of peptide phosphorylation was accomplished by scintillation counting following either collection of peptide onto phosphocellulose filters (for reactions stopped with acetic acid), collection of peptide in wells of 96 well plates coated with Streptavidin (Pierce) (reactions were stopped with EDTA), or addition of Avidin coated Scintillant impregnated beads (Scintillation Proximity Assays from Amersham, reactions were stopped with EDTA). Counts detected by any of these methodologies minus the appropriate background (assays with additional 40 mM EDTA or lacking peptide substrate) were assumed to be proportional to the reaction initial rates, and IC50s were determined by a least squares fit to the equation CPM=V max *(1−([I]/(K+[I])))+nsb, or pIC50s were determined by a fit to the equation CPM=nsb+(V max −nsb)/(1+(x/10 x −pIC50)), where nsb are the backgrounds counts.
[0428] UL97
[0429] UL97 was produced as al GST fusion protein from a baculovirus vector expressed in sf9 cells as described by He (He, et al., Journal of Virology 1997, 71, 405-11). UL97 was assayed as a protein kinase using 32 P transfer from ATP to histone H2B with detection of radiolabeled histone bound to phosphocellulose. Assay mixes for testing inhibitors of UL97 activity contained 2 mM [y32P]-ATP, 15 mM histone H2B, 50 mM sodiumCHES, pH 9.5, 1 M NaCl, 2 mM dithiothreitol and 10 mM MgCl 2 . Inhibitors were dissolved in diluted DMSO to give a final DMSO concentration in the reaction of 1% DMSO. After incubation at 20° C., the reactions were terminated by addition of 10 volumes of 75 mM phosphoric acid, 30 mM ATP, 1 mM EDTA, then were spotted onto phosphocellulose filters and washed four times with 75 mM phosphoric acid. Radioactivity was determined by liquid scintillation counting.
[0430] Src/Lck
[0431] The peptide substrates used in Src and Lck assays were biotin-aminohexyl-EEIYGEF-NH 2 (Src) and biotin-aminohexyl-EAIYGVLFAKKK-NH 2 (Lck). The src and Ick proteins were purified to homogeneity from a baculovirus expression system and preactivated before adding to assay mixtures. The maximum activation was achieved by incubating concentrated enzyme (10-30 mM) on ice for 40 min in the presence of 1 mM ATP and 10 mM MgCl 2 in 100 mM HEPES, pH 7.5. The activated enzyme was diluted to 2 nM into a 50-mL reaction mixture containing 100 mM HEPES, pH 7.5, 5 mM ATP, 10 mM MgCl 2 , 2 mM peptide, 0.05 mg/mL BSA, and an inhibitor at varying concentrations and with or without 8 mCi/mL [γ- 33 P]ATP dependent upon the method of analysis for the extent of reaction. The controls were reactions in the presence (negative controls) or absence (positive controls) of 50 mM EDTA. Reactions were allowed to proceed for 30 min at room temperature and quenched with addition of EDTA to 50 mM in 220 mL. The extent of reactions was analyzed in one of the two ways: an Elisa-based and a radioactive isotope-based. The quenched samples (200 mL) were transferred to a neutravidin coated plate (Perice) and incubated at room temperature for 40 min to allow biotinylated peptide to bind to neutravidin. The unbound peptide and the rest of the solution was washed away using a plate washer. In the Elisa format, a 200 mL HRP-PY20 anti phosphotyrosine antibody conjugate solution was added. After incubation for about 30 min, the plated was washed to remove unbound antibody-HRP conjugate. An Elisa substrate, K-blue (Neogen), was added and the Elisa reaction quenched with Red-stop (Neogen) after 15 min. The plate was read at A 625 in a plate reader. In the isotope-based format, the reactions had been performed in the presence of [γ- 33 P]ATP. 200 mL Scintiverce DB was added to each well of the plate with bound biotin-peptide. The plate was sealed and counted in a micro-b-counter (Wallac). IC 50 values were obtained by fitting raw data to A 625 (cPm)=V max *(1−([I]/(IC 50 +[I])))+b, where b is background.
[0432] VEGFR-2
[0433] The peptide substrate used in the VEGFR-2 assay was biotin-aminohexyl-EEEEYFELVAKKKK-NH 2 . The kinase domain of the enzyme was purified to homogeneity from a baculovirus expression system. The enzyme was preactivated on ice for 15 min in the presence of 100 μM ATP and 20 mM MgCl 2 , and stored at −80° C. until needed for assay. The activated enzyme was diluted to 0.4 nM into a 60 μl reaction containing 100 mM HEPES, pH 7.5, 5 μM ATP, 10 mM MgCl 2 , 5 μM peptide, 0.1 mM DTT, 0.05 mg/ml BSA, and an inhibitor at varying concentrations. The controls were reactions in the presence (negative controls) or absence (positive controls) of 50 mM EDTA. Reactions were incubated for 30 min at room temperature, and then quenched by the addition of EDTA to 60 mM in 210 μl. The quenched samples (190 μl) were transferred to a neutravidin coated plate (Pierce) and incubated at room temperature for 40 min to allow biotinylated peptide to bind to the neutravidin. The unbound components of the reaction were removed by washing with a plate washer, then 200 pi HRP-PY20 anti-phosphotyrosine antibody conjugate was added to each well. After incubation for 40 min, the plate was washed to remove any unbound anitbody. A HRP substrate, K-blue (Neogen) was added and the reaction was quenched with Red Stop (Neogen) after 20 min. The absorbance of the wells was read at A650 in a plate reader. IC 05 values were obtained by fitting raw data to A6=V MAX *(1−[I]/IC 50 +[I])))+b, where b is background.
[0434] The results shown in Table 2 summarise representative data: Table 2 illustrates the inhibitory activity of compounds of the present invention against several different kinases (CDK2, CDK1, cSrc, Lck, UL97, and VEGFR2).
TABLE 2 Kinase inhibition data of representative compounds Compound CDK2 CDK1 cSrc Lck UL97 VEGFR2 Example 72 +++ ++ + + +++ ++ Example 99 ++ + + + ++++ + Example 68 ++++ ++ + +++ Example 77 ++++ ++++ ++++ Example 36 ++++ ++++ + + +++ + Example 101 +++ ++ Example 35 ++++ +++ Example 27 ++++ +++ Example 11 ++++ +++ Example 103 ++++ +++ Example 76 +++ + + + + Example 104 ++++ +++
[0435] As may be expected in light of the specific inhibitory activity of these compounds against several kinases involved in growth regulation, the compounds of this invention have antiproliferative propertieswhich can be directly demonstrated in several cell proliferation assays. The results shown in Table 3 summarise some of these data for three different cell proliferation assays: MTT, FACS and G1-S progression. These assays are described below.
[0436] MUT Assay
[0437] Compounds are tested for their ability to inhibit cell proliferation and cell viability. The metabolic conversion of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MUT, Sigma #M2128) to a reduced form is a commonly used measure of cellular viability. Following is the procedure: Cells are maintained in 75 cm 2 tissue culture flasks until ready for use. The cells are grown and plated for the assay in Dulbecco's modified Eagle's media (DMEM) containing 10% fetal bovine serum. For example, the following cell lines can be used: a) human foreskin fibroblasts (HFF); b) HT29 (human colon carcinoma cell line); c) MDA-MB468 (human breast carcinoma cell line); d) RKO (human colon adenocarcinoma cell line); e) SW620 (human colon carcinoma cell line); f) A549 (human lung carcinoma cell line); and g) MIA PACA (human pancreatic carcinoma cell line). Cells are maintained at 37° C. in 10% C02, 90% humidified air. Cells are plated in 96-well tissue culture plates at the densities listed below. 100 μL of cell suspension is added to each well of the 96-well plate except the top row of the plate which contains no cells and serves as a reference for the spectrophotometer.
cell line density HFF 2500 cells/well HT29 cell lines 2500 cells/well MDA-MB-468 cell line 5000 cells/well RKO cell line 4000 cells/well SW620 4000 cells/well A549 5,500 cells/well MIA PACA 3000 cells/well
[0438] Cells are incubated overnight in DMEM containing 10% fetal bovine serum at 37° C. in 10% CO 2 , 90% humidified air prior to dosing. Cells are dosed in 10 sequential 3-fold dilutions starting at 30 μM depending upon the solubility of the compound. Compounds with solubilities of less than 30 μM are dosed at the highest soluble concentration. Stock solutions of compounds are made in 100% dimethyl sulfoxide (DMSO). Stock solutions are diluted in DMEM containing 100 μg/ml gentamicin and 0.3 to 0.6% DMSO at the twice the highest concentration to be placed on the cells. If compounds have been dissolved in DMSO the final concentration of DMSO on the cells is kept below 0.3%. Three-fold serial dilutions are performed on each compound to prepare 10 concentrations of the compound for dosing. 100 μl of diluted compound is added to the 100 μl of media currently on the dish. For each concentration of compound, 24 replicate wells are prepared.
[0439] Cells are returned to incubator and allowed to proliferate in the presence of compound for 72 h before addition of MTT. MTT is prepared in phosphate buffered saline (Irvine Scientific #9240) at a concentration of 2 mg/ml. 50 μl per well of MUT solution is added to the 200 μl of media to yield a final concentration of 0.4 mg/ml and plates are returned to the incubator for 4 h. After 4 h incubation the media, compound and MTT mixture is aspirated from the plates and 100 μl of 100% DMSO is added to each well in addition to 25 μl of Sorenson's Buffer (0.1M glycine, 0.1M NaCl, pH 10.5). Quantitation of metabolic reduction of MTT in each plate is performed by reading optical density at 570 nm wavelength on a Molecular Devices UVmax microplate reader. Growth inhibition curves and 50% inhibitory concentrations are determined using Microsoft Excel.
[0440] FACS Assay
[0441] The antiproliferative activity of the compounds of the present invention against a variety of normal or tumour cell lines can also be demonstrated by flow cytometry. These assays allow determination of both cell death and changes in cell cycle profile in cells following treatment of the compound. The assay is performend as follows:
[0442] 1. Cells are incubated in DMEM to which 10% FCS has been added in a humidified incubator at 37° C., and 5% by volume of CO 2 in air. The cells are innoculated in 6-well plates at a density of 0.5-5×10 5 cells per well.
[0443] 2. The test compound is added in serial dilutions 24-36 h after plating in 0.5% DMSO. The plates are then incubated a further 72 h in the presence of the compound. During this time, cells in control cultures undergo at least three cell divisions.
[0444] 3. After incubation, the media is collected and cells are harvested by trypsinization. The cells and media are pooled and pelleted by centrifugation.
[0445] 4. The cell pellet is fixed in aE final volume of 3 mL of 50% ice cold MeOH and incubated for a minimum of 30 min at −20° C.
[0446] 5. The cells are pelleted by centrifugation and resuspended in 0.5 mL PBS containing 1%FCS, 10 mg/ml Propidium Iodide (PI) and 5 mg/mL RNase A and incubated 30 min at 37,0 C in the dark.
[0447] 6. The samples are analysed by flow cytometry using the relative incorporation of PI as a measure of DNA content of each cell. The % Dead cells is recorded as % of events with less than 2N DNA. The IC 50 values for the compound are determined as the concentration of compound which results in 50% cell death relative to the control cultures. The compounds of the present invention give IC 50 values from 0.1 to >25 inmol/L. The compounds of the present invention additionally display IC 50 values for cell killing of 5- to 30-fold lower in several tumour cell lines, inducing the RKO and SW620 colon tumours, MDA MB468 breast tumour, H460 lung tumour and MES/.SA ovarian tumour cell lines, as compared to normal epithelial or fibroblast cell lines and therefore discriminate between normal cell lines and tumour derived cell lines for toxicity.
[0448] G1-S Progression Assay
[0449] This assay is designed to determine the ability of compounds to inhibit progression of cells from GI into S-phase. CDK2 has been shown to be required for progression into S-phase in normal fibroblastic cells and therefore inhibition of this activity will prevent progression from G1-S. This assay therefore provides a rapid assessment of activity consistent with the inhibition of CDK2 in a cell-based format. The protocol is as follows: (1) Grow human diploid fibroblasts (HDF-3) in 100 mm tissue culture dish to confluency. (2) Plate 6-7×10 3 cells/well in a 96 well plate in 100 μl of DMEM . (3) After 16-17 h add various dilutions of test compounds (0.045-100 PM). Dilute compound in DMEM containing DMSO and add 100 μl to each well so that the DMSO conc. is 0.6,-0.8% in 200 μl final volume. (4) Two h after addition of compound, add 20 ul of 100 μM Br dU (final conc. 10 μM) Make 100 μM solution in DMEM from 10 mM stock solution. (5) After 4 h, add 200 μl PBS to each well and remove the contents of the wells by inverting the plate and soaking on to the paper towel . Repeat the washing step three times, with 400 ul PBS each time. (6) Fix the cells and denature the DNA by adding 200 pi fixation/denaturation solution to each well for 3040 min. (7) Remove the fixation/denaturation solution by tapping the plate on the paper towel and add 75 ul of anti BrdU peroxidase antibody to each well. (dilute the antibody to 0.1 U/mL from 15 U/mL stock in PBS containing 1% BSA, Fraction V). Incubate the plate O/N at 4° C. (8) Remove the antibody solution and wash wells four times with 400 μl of PBS. Let the wash solution stay for 34 min during each wash. (9) Drain the wells and add 100 μl of chemiluminiscence Elisa reagent (Prepare the reagent 15-20 min before use to bring it to rt by mixing 100 parts of reagent A with I part of reagent B). (10) Read the plate in a luminometer . Take 2-3 readings within 6-7 min. Perform the following controls:
Well contents Blank Background control culture media 200 μl 100 μl cells — 100 μl BrdU 20 μl — AntiBrdU-POD 75 μl 75 μl
[0450] Reagents:
[0451] Deoxybromouridine (BrdU), anti BrdU peroxidase antibodies, fixation/denaturation solution, chemiluminiscence reagent and BSA Fraction V, were obtained from Boehringer Mannheim. The 96-well white plate with clear bottom were purchased from Coming Costar Corporation. Dulbecco's Modified Eagle Medium containing high glucose, Lglutamine and pyridoxine HCl was obtained from GIBCO BRL.
[0452] The compounds of the present invention prevent progression of normal fibroblasts into S-phase with IC 50 values ranging from 0.05-10 μM. This inhibition of G1-S progression is consistent with these compounds acting as inhibitors of CDK2.
[0453] Results of these cell-based assays with representitive compounds are summarized in Table 3. HDF: are normal diploid fibroblast cells. RKO are colon adenocarcinoma cells and MES/SA are ovarian carcinoma cells.
TABLE 3 Cell-based activities of representative compounds MTT G1/S FACS MDA Compound Chkpt HDF RKO MES/SA HDF RKO MB468 Example 72 ++ + ++ + + ++ + Example 99 ++ + ++++ + +++ ++++ ++++ Example 68 ++ + ++ + + + Example 77 ++ + ++ +++ + ++ + Example 36 +++ + +++ ++++ ++ +++ +++ Example 101 + + + + ++ Example 35 + + ++ + + ++ + Example 27 ++ + ++ ++ ++ ++ Example 11 ++ + ++ Example 103 ++ ++ ++ ++ Example 76 ++ + ++ ++ + + + Example 104 ++ ++ ++ ++
[0454] Utility of Invention
[0455] Inhibitors of members of the CDK family of kinases find utility as agents in the treatment of a wide variety of disorders which have a proliferative component or which involve regulation of cyclin dependent linase function. These include cancers, restenosis, psoriasis, and actinic keratosis.
[0456] The tumour inhibitory activity of the compounds. of the present invention can be demonstrated in vivo. The tumour inhibiting activity is determined using Swiss Nu/Nu female mice in which the human RKO colon adenocarcinoma has been implanted subcutaneously. In this assay, the compounds induce a marked reduction in the average tumour volume compared to vehicle treated controls.
[0457] The present invention demonstrates methodologies by which the onset of cell death in normal proliferating cells induced by chemotherapeutic drugs may be prevented by the prior treatment with inhibitors of cyclin dependent kinases. This may be useful to decrease the severity of chemotherapy -induced side effects due to killing of normal cells. These side effects may include, but are not limited to alopecia, mucocitis (nausea and vomiting, diahrea, oral lesions), neutropenia and thrombocytopenia. Inhibitors of cyclin dependent kinases CDK2 and CDK4 prevent the progression of normal cells into both S-phase (DNA synthesis) or M-phase (mitosis), reducing their susceptibility to incur damage by certain chemotherapeutic drugs which act in those phases of the cell cycle.
[0458] When the compounds of the present invention are used in conjunction with chemotherapeutic agents, they reduce the severity of chemotherapy-induced side effects. The protective effects of these compounds can be demonstrated in tissue culture using normal diploid fibroblasts. Cells are plated 36 h prior to the administration of the compounds of the present invention, which are dosed at or above the IC 50 concentrations determined by the GI checkpoint assay. Cells are then treated with cytotoxic compounds anywhere from 0 to 24 h after treatment with the compounds of the present invention. Cells are incubated with the combination of the cytotoxic and the compound of the present invention from 3 to 72 h. Cytotoxic drugs include, but are not limited to taxanes, vinca alkyloids, anthracyclins, etoposide, mitoxantrone, topoisomerase I inhibitors, and Ara C. Cell death may be recorded by morphological observation, or by assessment by MTT or FACS analysis. The compounds of the present invention reduce the amount of cell death when used in combination with cytotoxics, as compared to the cytotoxic alone.
[0459] The chemoprotective activity of these agents has additionally been demonstrated in vivo. Protection from chemotherapy-induced alopecia is determined in 7 day old Sprague-Dawley rat pups. The treatment is carried out by administering the compounds topically to the head of the animal in doses from 0.01 to 10 mg/kg 2 h before and 2 h after the administration of a single dose of 6 mg/kg etoposide intraperitoneally. Six days after dosing, animals are scored visually for hair loss using a grading scale from 1 (complete hair loss) to 4 (no apparent hair loss). In this assay, the prior treatment of the animal with the compound of this invention results in a marked reduction in the severity of alopecia compared to vehicle treated controls. Under the above described conditions of treatment, the compounds of the present invention also protect against other toxicities of etoposide. Animals treated with etoposide alone show a dramatic lack of weight gain compared to untreated animals. Animals treated with the compounds of the present invention in combination with etoposide, in the schedule indicated above, gain weight normally and even exceed the body weight of control, untreated animals.
[0460] The compounds of the present invention additionally show an additive or synergistic effect on cell kill when dosed in combination with cytotoxic drugs in tumour cells (but not normal cells). This can be demonstrated by pretreating normal fibroblasts or RKO colon carcinoma cells with the compounds of the present invention (at concentrations that equals the IC 50 in the GI checkpoint assay) for 4 h prior to the administration of cytotoxic drug. Cytotoxic drugs include, but are not limited to taxanes, vinca alkyloids, anthracyclins, etoposide, mitoxantrone, topoisomerase I inhibitors, and Ara C. This synergistic effect may also be shown in vivo. Neonatal Sprague-Dawley rats bearing WARD syngeneic tumours are dosed with a combination of etoposide with the compound of the present invention as described above for the protection experiments. Animals dosed in such a manner show an increased antitumour effect as compared to animals dosed with etoposide alone. The compounds of the present invention may therefore be administered systemically to animals in combination with cell-cycle specific cytotoxic drugs; to both increase the antitumour effect of the cytotoxic as well as reduce the severtiy of side effects of the cytotoxic drug. This will allow the dose of cytoto:xic to be escalated to further improve antitumor activity without increasing the host toxicity of the cytotoxic.
[0461] The compounds of the present invention may also be used in combination with radiation treatment to show similar protection of normal cells from the effects of radiation and may be used as radiosensitizers to increase the tumour killing by radiation therapy.
[0462] The compounds of the present invention which are inhibitory for CDK4 or CDK6 activity will selectively inhibit cell cycle progression in cells which retain a functional retinoblastoma protein. Thus, it will be expected that inhibition of CDK4 will systemically protect normal dividing cells, including the GI and oral mucosa, hematopoietic cells and cells in the hair follicle, but be unable to protect tumour cells with loss of RB function, either by deletion or mutation. This implies that compounds which inhibit (CDK4 will be useful as systemically administered cytoprotectant drugs in patients with tumours which have lost Rb, with no protective effect on the tumour itself. Such compounds could be expected to allow for increased dosing frequency and dose escalation of the cytotoxic regimens in these patients, improving the outcome of the patient.
[0463] The compounds from the present invention will also have utility in the treatment of viral infections. The antiviral activity of these compounds can be demonstrated in cytomegalovirus (CMV) and human papillomavirus (HPV) replication assays. The IC 50 for inhibition of CMV replication ranges from 0.05 to 5 μM.
[0464] The assay for CMV replication is performed as follows:
[0465] 1. Growth of Human Fibroblast Cells:
[0466] MRC-5 human lung fibroblasts (passage #27-30)were were cultured in minimal essential medium with added 8% v/v fetal calf serum, 2 mM Lglutamine, 100 units/mL penicillin G, and 100 μg/mL streptomycin sulfate, (MEM 8-1-1). Incubation was at 37° C. in air plus 5% CO 2 . Cells were inoculated into 96-well plates at ˜7×10 3 cells/well and incubated a further 3 days to confluence (˜2×10 4 cells/well).
[0467] 2. Infection of Cells:
[0468] Medium is removed frompeach well down to 20 μl and 150 pfu of HCMV (Strain AD169) suspended in 25 μl of medium MEM 2-1-1 (same as MEM 8-1-1 above, but with 2% v/v fetal calf serum) is added. (MOI -0.013). Plates are centrifuged at 1500 rpm for 10 min at 25° C. and incubated 90 min at 37° C. 180 μl of medium MEM 2-1-1 containing compounds is added to give a range of final concentrationsfrom 0.01 to 100 mM. Multiple plates are set up for each combination with one mock-inifected plate for estimation of cytotoxicity. Plates are then incubated at 37° C. in air plus 5% CO 2 for six days (two rounds of viral replication). Cytotoxicity is estimated microscopically on the mock-infected plates, and the infected plates were harvested by decanting the medium from the wells.
[0469] 3. Preparation, Blotting and Quantitative Hybridization of DNA:
[0470] Cells are lysed by adding 50 μl of 0.1 M Tris Cl (pH 8), 50 mM EDTA, 0.2% SDS, and 0.1 mg/mL proteinase K to each well and incubating 1 h at 55° C. The lysates were diluted with 150 μl of water and extracted by mixing with 65 μl phenol saturated with 0.01 M Tris Cl (pH 8) and 1 mM EDTA. The plates were centrifuged at 2200 rpm for 15 min. Next, 50 μl of the aqueous layer was transfered to a new 96-well plate and mixed with 50 μl of 0.5 N NaOH. After incubation at 95° C. for 15 min, the samples were made to 1.5 M Ammonium acetate, 0.15 M Ammonium H 2 phosphate, 5 mM EDTA, pH 6.5 (APE buffer), and blotted onto BRL Supported Nitrocellulose (cat #1465MH) membranes under vacuum Each well was washed with 200 μl APE buffer. The samples were crosslinked to the membrane with UV light.
[0471] 4. Quantitative DNA-DNA Hybridization:
[0472] The hybridization probe was prepared from cosmids pC7S31 & pCS37 (Sullivan, et al., Antimicrobial Agents & Chemotherapy 1993, 37, 19-25). These contain the HCMV AD169 sequences; from nucleotides 102,000 to 143,300 and 51,600 to 92,900, respectively. The probe is a 1:1 mixture of the two cosmids labeled with α-[ 32 P]-dCTP Prehybridization of the membranes is carried out in 6× SSPE, 1% Ficoll, 1% polyvinylpyrrolidine, 1% BSA, 0.5% SDS, and 50 μg/mL salmon sperm DNA at 45° C. for 2 to 12 h. The prehybridization solution was replaced with hybridization solution (6× SSPE, 0.5% SDS, 50 pglmL salmon sperm DNA) containing 1×10 6 cpm/mL of each heat-denatured probe. Hybridization was for 16 h at 65° C. The membranes were then washed as follows: 6× SSPE with 0.5% SDS, room temperature, 2× for 2 min; 1× SSPE with 0.5% SDS, 65° C., 2× for 15 min; 0.1× SSPE with 0.5% SDS, 65” C, once for 1 h. The membranes were blotted dry and wrapped in Saran wrap for quantitation by Phosphorlmager. The counts of the drug dilution wells were compared to the counts of untreated control wells to produce a response curve and were used to calculate the IC 50 values. These IC 50 values were calculated by weighted linear regression according to the Hill equation.
[0473] The compounds of the present invention may also be used for the treament of other conditions mentioned in connection with modulators of QDK activity. In particular for the treatment of diseases that respond to inhibition of CDK activity, including protection of cells from infection by other viruses and treatment of Alzheimers. Furthermore, these compounds will have utility in the specific inhibition of non-human CDK activities, such as the Aspergiflus fumigatus cdc2 homologue and will therefore be useful in the treatment of fungal or other eukaryotic infections.
[0474] The compounds of the present invention also inhibit other kinases. In particular, these compounds show affinity for the Src tyrosine kinase. The Src tyrosine kinase participates in a variety of fundamental processes within the cell, including signal transduction from cell-surface receptors, apoptosis and cell division. Compounds which are able to inhibit the src TK find utility as tumour inhibitory and antiinflammatory agents. These compounds are also useful for the prevention of osteoporosis and bone building by inhibition of src in osteoclasts (Tanaka, et al., Nature 1996, 383, 528-31). In addition, the compounds of this invention are suitable for other utilities mentioned in connection with Src modulators, and they can be used in particular for the treatment of diseases that respond to the inhibition of the Src tyrosine kinase.
[0475] While the invention has been described and illustrated with reference to certain preferred embodiments thereof, those skilled in the art will appreciate that various changes, modifications and substitutions can be made therein without departing from the spirit and scope of the invention. For example, effective dosages other than the preferred dosages as set forth herein above may be applicable as a consequence of variations in the responsiveness of the mammal being treated for cancer conditions, or for other indications for the compounds of the invention as indicated above. Likewise, the specific pharmacologic responses observed may vary according to and depending upon the particular active compound selected or whether there are present certain pharmaceutical carriers, as well as the type of formulation and mode of administration employed, and such expected variations or differences in the results are contemplated in accordance with the objects and practices of the present invenion. It is intended, therefore, that the invention be limited only by the scope of the claims which follow and that such claims be interpreted as broadly as is reasonable.
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Compounds of formula (I): wherein X is N, CH, CCF 3 , or C(C 1-12 aliphatic); R 4 is sulfonic acid, C 1-12 aliphatic-sulfonyl, sulfonyl-C 1-12 aliphatic, C 1-12 aliphatic-sulfonyl-C 1-6 aliphatic, C 1-6 aliphatic-amino, R 7 -sulfonyl, R 7 sulfonyl-C 1-12 aliphatic, R 7 -aminosulfonyl, R 7 -aminosulfonyl-C 1-12 aliphatic, R 7 -sulfonylamino, R 7 -sulfonylamino-C 1-12 aliphatic, aminosulfonylamino, di-C 1-12 aliphatic amino, di-C 1-12 aliphatic aminocarbonyl, di-Cl 1-12 aliphatic aminosulfonyl, di-C 1-12 aliphatic amino, di-C 1-12 aliphatic aminocarbonyl, di-C 1-12 aliphatic aminosulfonyl-C 1-12 aliphatic, (R 8 ) 1-3 -Arylamino, (R 8 ) 1-3 -Arylsulfonyl, (R 8 ) 1-3 -Aryl-aminosulfonyl, (R 8 ) 1-3 -Aryl-sulfonylamino, Het-amino, Het-sulfonyl, Het-aminosulfonyl, aminoiminoamino, or aminoiminoaminosulfonyl, R 5 is hydmogen; and further wherein R 4 and R 5 are optionally joined to form a fused ring, pharmaceutical formulations comprising them and their use in therapy, especially in the treatment of diseases mediated by CDK2 activity, such as alopecia induced by cancer chemotherapy or radiotherapy.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a photographing lens assembly provided with a motor-driven focusing device of the type in which an optical system, especially a focusing optical system, is moved by a motor for focus adjustment.
2. Description of the Prior Art
There is widely known and used such a photographing lens assembly provided with a driving mechanism for automatic focus adjustment. The driving mechanism generally includes a motor the rotation of which is controlled by a focus deviation signal coming from a focus detector for detecting the existing deviation of the image plane from the focal plane of the camera. The deviation of the image plane on which an image of the object is now being formed is detected electrically by the focus detector. In response to the deviation signal issued from the detector, the rotation of the motor is controlled, and in link with the rotation of the motor the driving mechanism moves the focusing optical system.
In this type of photographing lens assembly, the motor-driven focus adjustment mechanism becomes inactive when the power source battery for the motor is consumed or when the object to be taken is a very unique one (such as flat scene or smoke) for which the detection by the focus detector becomes very difficult.
In order to accommodate the lens assembly also to such cases, the applicants of the present patent application has already proposed a photographing lens assembly provided with not only the above-mentioned motor-driven automatic focus adjustment mechanism but also a manually operable focus adjustment mechanism. The user can select any desired one of the automatic focusing mechanism and the manual focusing mechanism independently of each other by a change-over operation. This photographing lens assembly is disclosed in the specification of U.S. patent application Ser. No. 296,142 filed on Aug. 25, 1981.
In general the manual focusing mechanism of photographing lens assembly is constructed in such manner that the moving range of the focusing optical system manually driven is limited between two end points and any further movement of the focusing system beyond the end points can be inhibited by mechanical limiting means. One of the limit end points lies at the position corresponding to the in-focus position to an object at infinity and the other limit end point lies at the position corresponding to the in-focus position to an object at the minimum object distance.
For the motor-driven automatic focus adjustment mechanism also it is desirable that the moving range of the focusing optical system be limited similarly to the above. This may be attained, preferably, by cutting off the power supply to the motor to stop the rotation or by switching over the direction of current flow to the motor to reverse the rotation of the motor when the focusing optical system reaches either limit end of the moving range.
Therefore, in case of the above-mentioned type of photographing lens assembly provided with both of manual and mechanical focusing mechanisms, it is required to provide both of mechanical limiting means and electrical limiting means for limiting the movement of the focusing optical system. This brings about some difficult problems. In particular when the automatic driving mechanism is selected for focus adjustment, both of mechanical limiting means and electrical limiting means are actuated at the same time at each the limit end point of the moving range of the focusing optical system. Consequently, the focusing optical system and its related mechanism being driven by the motor are subjected to impact force by said mechanical limiting means. The impact force causes the focusing optical and its related mechanism to move back and makes it difficult to stop the focusing optical system at the limit end point.
A solution to the problem is disclosed in Japanese Application for Utility Model Patent laid-open No. 51905/1982. According to the solution, a braking means is provided to moderate the shock at stopping. The braking means comprises a leaf spring which is applied to the moving member related to the focusing optical system when the latter comes near the limit end of the moving range so that the moving member can be impacted against the mechanical stopper with a reduced shock.
However, this known solution has some drawbacks.
To further move the moving member against the pressing force of the leaf spring a great deal of energy is required. To maintain the proper operability for focus adjustment the pressing force by the braking leaf spring must be very precisely set and adjusted. In practice it is very difficult to always correctly stop the focusing optical system just at the end point of the moving area without any loss of the easy operability employing this solution.
SUMMARY OF THE INVENTION
Accordingly the object of the present invention is to provide a photographing lens assembly provided with an automatic driving mechanism which assures smooth stop and reversion of the movement of the focusing optical system at each limit end point of its moving range without any loss of the proper operability of the focus adjustment mechanism.
According to the present invention, the above object is attained by the provision of mechanical limiting means and electrical limiting means at different positions in the direction of the moving course of a moving member interlocked with the focusing optical system. Said mechanical limiting means is actuated after the actuation of said electric limiting means. More concretely, on the infinity side, said mechanical limiting means is located at a position beyond the actuation point of said electrical limiting means a further distance toward the infinity side. On the minimum object distance side, said mechanical limiting means is located at a position beyond the actuation point of said electrical limiting means a further distance toward the minimum object distance side. Preferably the distance from the actuation point of said electrical limiting means is so selected that the moving member responsive to said electrical means can come to contact with said mechanical limiting means and stop without any substantial shock or the moving member can stop without contact with said mechanical limiting means.
Other and further objects, features and advantages of the present invention will appear more fully from the following description of preferred embodiments taken in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view of a single lens reflex camera showing an embodiment of the invention;
FIG. 2 is a sectional view taken along the line II--II in FIG. 1;
FIG. 3 is a perspective view of the change-over mechanism in the embodiment;
FIG. 4 is a sectional view taken along the line IV--IV in FIG. 1;
FIG. 5 illustrates the positional relationship between mechanical limiting means and electrical limiting means in which FIG. 5A shows the position within the rotation range, FIGS. 5B and 5D show the positions for actuation of electrical limiting means and FIGS. 5C and 5E show the positions for actuation of mechanical limiting means; and
FIG. 6 is a block diagram showing the connection of electric circuits in the embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1 showing an embodiment of the invention, an auto-focus photographing lens assembly 30 and a single-lens reflex camera body 10 are joined together. The lens assembly 30 includes a photographing lens system comprising lenses 1, 2, 3 held in a stationary tube 32 and focusing lenses 4, 5, 6 held in moving tubes 34, 36. The focusing lenses are moved along the optical axis for focus adjustment. A part of the light transmitted through the optical system is reflected toward a finder optical system by a turn mirror 12 in the camera body 10. Another part of the transmitted light passes through the turn mirror and then it is reflected by a sub-mirror 16 which directs the light to a photo sensor device 16 on the bottom surface of the camera body. The photo sensor device 16 is positioned at a position optically equivalent to the film plane F. The output of the sensor 16 is introduced into a focus detecting circuit 18 which generates a detection signal. The photo sensor device 16 and the detecting circuit 18 constitute a known focus detecting apparatus. The detection signal is a signal informing of the positional relationship of the object image formed by the photographing lens to the film plane. The apparatus for generating such detection signal is well-known to those skilled in the art and consequently will not be described in detail.
The detection signal is transmitted to a drive circuit 38 in the lens assembly through connector contacts 19 and 38 which are provided on the connecting mount of the camera body and on the connecting mount of the lens assembly respectively. In response to the detection signal the drive circuit 38 controls the forward and reverse rotation of the motor 40 and also the stop thereof. The rotation of the motor 40 is transmitted to a rotating member 42 through a gear train. The rotating member 42 is rotatable around the stationary lens tube so that the rotary member 42 is rotated about the optical axis with the rotation of the motor 40.
The rotating member 42 has an arm 44 fixed thereto. Through the arm the rotation of the rotary member 42 is transmitted to the moving lens tube 36. The tube 36 has a projection 36a and a linear cam slot 36b in the direction of the optical axis. Further, the inner circumferential surface of the moving tube 36 is thread-engaged with a helicoid screw on the outer circumferential surface of the stationary tube 32.
The rotation of the moving tube 36 is transmitted to the moving tube 34 through a pin 34a engaged in the above-mentioned cam slot 36b. The moving tube 32 has, on its outer circumferential surface, a thread which is in engagement with a helicoid screw provided on the inner circumferential surface of the stationary tube 32. The inner helicoid screw and the above-mentioned outer helicoid screw of the stationary tube 32 have different leads. Therefore, when the rotation of the rotating member 42 is transmitted through the arm 44, the moving tubes 36 and 34 start a relative movement along the optical axis while rotating. As a result, the image plane of the image-forming optical system is moved. At the time when the image plane comes into coincidence with the film plane F, the focus detector generates an in-focus signal. In response to the signal, the drive circuit 38 stops the rotation of the motor 40. In this manner, an automatic focus adjustment is effected. The rotating member 42 has a display plate 46 fixed thereon. An object distance scale is marked on the display plate so that the user can read the object distance in the state of in-focus through a display window 48.
On the outer circumferential surface of the stationary tube 32 there are provided also a diaphragm setting ring 50 for adjustment of diaphragm mechanism 52, a focusing ring 54 for manual focusing operation and a mode change-over knob 56.
FIGS. 2 and 3 show the detailed structure of a change-over mechanism which includes a transmission gear train 61 to 67 between the motor 40 and the rotating member 42 and the mode change-over knob 56.
The user can select any desired one of automatic driving mechanism and manual driving mechanism by slide-moving the change-over knob 56 in the circumferential direction. When the knob 56 is slide-moved to select the manual driving mechanism, a clutch lever 70 is rotated about a pin 71 through a lever 58. By this rotation of the clutch lever 70 a moving clutch plate 74 is moved along a shaft 72 having a key 73 and disengaged from a rotary clutch plate 75 fixed to the gear 66 as shown in FIG. 3. The gear 66 with the clutch plate 75 is mounted rotatably about the shaft 72. Therefore, after the clutch plate 73 has been disengaged from the clutch plate 75 in the manner described above, the rotation of the gear 66 by the motor 40 is not transmitted to the shaft 72. Consequently, the rotation of the motor can not be transmitted to the rotating member 42 in mesh with a gear fixedly mounted on the shaft 72. Thus, in this position of the mechanism, the automatic focusing operation by the automatic driving mechanism previously described can not be performed at all.
On the other hand, the clutch plate 74 disengaged from the clutch plate 74 is friction-coupled with a gear 77 through a friction spring 76. The gear 77 is mounted on the shaft 72 rotatably about it and is in mesh with an internal gear of the focusing ring 54. Therefore, when the ring is manually rotated for focusing, the rotation of the focusing ring 54 is transmitted to the shaft 72 through gear 77, spring 76 and clutch disc 74. As the shaft 72 is rotated, the rotating member 42 is rotated by it through the gear 67. In this manner, a manual focusing by the manual driving mechanism can be performed.
By turning the mode change-over knob 56 back to its starting position, the clutch lever 70 is rotated in the direction of the arrow in FIG. 3 and at the same time the clutch plate 74 slide-moves on and along the shaft 74 by the biasing force of the friction spring 76 toward the clutch plate 75. Thus, the clutch discs 74 and 75 are coupled together again. In this position, the rotation of the motor can be transmitted to the shaft 72 through the clutch discs 74, 75 to rotate the rotating member 42 through the gear 67. Therefore, the automatic driving mechanism is operable for automatic focusing. Since the friction spring 76 is now in the state of full extension and its biasing force is almost completely lost, the friction coupling between the clutch disc 74 and the gear 77 is dismissed in this position.
As shown in FIG. 4, on the surface of the stationary tube 32 facing the rotating member 42 there are formed two rotation limiting projections 321 and 322 projecting in the direction of the optical axis. On the other hand, the rotating member 42 has two rotation limiting ends 421 and 422 engageable with the projections 321 and 322 on the stationary tube. The rotation of the rotating member 42 is mechanically limited by the engagement of the limiting projections 321, 322 with the limiting ends 421, 422.
The rotating member 42 has a limit signal generating brush 80 fixed thereto. With the rotation of the rotating member 42 the brush 80 slides on a land formed on a flexible print circuit board 82 which is in turn fixed to the stationary tube 32. The brush generates a limit signal according to the pattern of the land on which the brush slides. More concretely, at the limit position on the infinity side of the moving range for the focusing lens, the brush 80 short-circuits the conductor pattern layers 821 and 823. At the limit position on the minimum object distance side the brush short-circuits the conductor pattern layers 822 and 823 on the flexible print board. The pattern layer 823 is connected to the drive circuit 38. The pattern layers 821 and 822 have a certain determined potential applied thereto respectively. Therefore, at the respective limit positions on the infinity side and on the minimum distance side there is generated a signal of the determined potential on the pattern layer 823. In response to the signal the drive circuit 38 reverses or stops the rotation of the motor. In this manner, an electric limiting of rotation is achieved.
FIGS. 5A to 5E illustrate the relationship in position between mechanical rotation limiting and electric rotation limiting.
Referring to FIG. 5A, the rotating member 42 is now rotationally moving toward the infinity side. Before the rotating member runs against the rotation limiting projection 321, the brush 80 comes into contact with the conductor pattern layer 821 as shown in Figure 5B. At this time, therefore, an electric limiting operation is executed. Assuming that the mode change-over knob 56 is now in the position to select the automatic driving mechanism, the drive circuit 38 will operate so as to stop or reverse the rotation of the motor at the time.
Even after the actuation of the electric limiting, the rotating member 42 with the brush 80 continue moving owing to the inertia force of the motor, thus moving the optical system etc. while decreasing the speed rapidly. Nearly at the position shown in FIG. 5C, that is, when the rotating member 42 comes into contact with the projection 321 or immediately before the contact, the rotating member stops.
Similarly, on the minimum object distance side as shown in FIGS. 5D and 5E, the rotating member 42 moves further after the brush 80 has short-circuited the conductor patterns 822 and 823 and stops when or immediately before it comes into contact with the projection 322.
In order to stabilize the generation of the electric limiting signal it is advisable that the width of the conductor pattern layers and the positions of the pattern layers relative to the brush be determined in such manner that in the positions shown in FIGS. 5C and 5E in which the rotating member 42 is in engagement with the projection 321 or 322, the brush 80 still remains in contact with the conductor pattern layer 821 or 822.
As for the position at which the photographing lens is precisely focused to the object at infinity or at the minimum object distance, it is desirable that the position be set to such a position which lies some distance before the engagement of the rotating member 42 with the projection 321 or 322 and at which the electric limiting operation is started. The reason for this is that the optical performance of the optical system is variable depending on temperature change and/or other factors. However, taking the depth of focus into consideration, the position may be set in front of or behind the desirable position.
FIG. 6 diagramatically shows the connection of electrical circuits in the embodiment.
The focus detecting circuit 18 has three output terminals a 1 , a 2 and a 3 . When the object image formed by the image-forming optical system is deviated from the film plane toward one side, the output terminal a 1 has a low level signal and a 2 and a 3 have a high level signal. When the object image is deviated toward the other side, the output terminal a 2 has a low level signal and a 1 and a 3 have a high level signal. When a coincidence is obtained between the formed image and the film plane, the output terminal a 3 has a low level signal.
The drive circuit 38 is constituted of a logical circuit 381 and a motor control circuit 382. Normally the logical circuit 381 outputs from its output terminals c 1 , c 2 and c 3 signals having the same content as the input signals to its input terminals b 1 , b 2 and b 3 have. However, when a limiting signal generated by the above-mentioned brush 80 and print circuit board 82 is introduced into it, the logical circuit 381 inverts some of the input terminals b 1 , b 2 , b 3 in response to the limiting signal and outputs from the output terminals c 1 , c 2 , c 3 such signals partly changed. For example, in response to the limiting signal the logical circuit interchanges the contents of the input terminals b 1 and b 2 and transmits the interchanged contents to the output terminals c 1 and c 2 , or the logical circuit inverts the content of the input terminal b 3 when it is of high level and then transmits the inverted content to the output terminal c 3 .
The motor control circuit 382 drives the motor 40 in forward direction when low, high and high signals appear at the output terminals c 1 , c 2 and c 3 of the logical circuit respectively. When there appear high, low and high signals at the output terminals c 1 , c 2 and c 3 respectively, the control circuit reverses the rotation of the motor 40. When a low level signal is generated at the output terminal c 3 , the control circuit stops the motor 40. Such a circuit which functions in this manner is known, for example, from the specification of U.S. Pat. No. 4,319,171.
While there has been described a preferred embodiment of the invention, obviously modifications and variations 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.
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A photographing lens assembly is provided with a moving lens system which is movable within a given moving range to change the optical characteristics and an electrical driving apparatus for controlling the movement of the moving lens system and comprises a mechanical limiting device and an electrical limiting device. The mechanical limiting device is adapted to act on the moving lens system when this system has been moved up to the limit of the moving range in order to inhibit any further movement of the lens system beyond that limit. The electrical limiting device is adapted to act on the electric driving apparatus when the moving lens system reaches a position a determined amount before the limit of the given moving range in order to inhibit the control for further moving the lens system in the same direction by the electric driving apparatus.
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BACKGROUND OF THE INVENTION
1. Technical Field
The present invention relates to a travelling toy which is started after vibration of a toy body.
2. Description of the Related Art
Some travelling toys of prior art use a motor or a spring as a power source by which the toy is driven to travel straightforwardly or zigzag, wherein the amusingness of a travelling manner itself is pursued. These travelling toys, being immediately started by switch operation, lack the characteristic of actual cars that move after a warm-up operation during a specific period of time after starting.
SUMMARY OF THE INVENTION
An object of the present invention is to solve the above-mentioned problem.
Another object of the present invention is to provide a travelling toy vehicle that makes vibration when stationary and begins to move after the vibration stops like an actual car with the engine idling before moving.
The travelling toy according to the present invention has been developed to attain the aforesaid and other objects. This travelling toy which is run and stopped by switch operation comprises a power source which produces a drive power. A power transmission mechanism including a travelling mechanism runs the travelling toy by driving wheels mounted to the travelling toy with a power from the power transmission mechanism. A vibrating mechanism vibrates the travelling toy to right and left by the power from the power transmission. A power transmission route change mechanism changes, shortly after starting, a power transmission route for transmitting the power from the power transmission mechanism to the travelling mechanism side and changes the power transmission route back to the vibrating mechanism side in interlock with switch operation at the time of stopping.
The travelling toy having the vibrating and travelling mechanism and the power transmission route change mechanism is driven to vibrate for a specific period of time when stationary before moving, and stops vibration after the specific period of time, then moving like an actual car which makes an engine idling operation before moving. Also it is possible to add vibratory operation to the travelling toy which is travelling.
The above-mentioned and other objects and features of the present invention will become apparent from the following description when read in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a travelling toy according to the present invention;
FIG. 2 is a longitudinal sectional view of the travelling toy according to the present invention;
FIG. 3 is a perspective view of a changeover mechanism which constitutes a power transmission route change mechanism;
FIG. 4(a) is a perspective view of a changeover mechanism;
FIG. 4(b) is a side view of the changeover mechanism;
FIG. 5 is a perspective view of a frame containing various mechanisms of the travelling toy 1;
FIG. 6 is a sectional view of the frame taken along line A--A in FIG. 5;
FIG. 7 is a sectional view of the frame taken along line B--B in FIG. 5; and
FIG. 8 is a cross sectional view of the travelling toy.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is a perspective view showing the travelling toy of the present invention. This travelling toy 1 is a toy having an external appearance like a dump truck equipped with front and rear wheels 4 and 5. At the rear of the body 2 a rear body 2a is pivotably mounted. The rear body 2a can be loaded with building block 3 and raised on a shaft 6 (FIG. 2) serving as a body pivot pin. The travelling toy 1 is designed as to operate as follows. When the rear body 2a is pushed down from above, its body 2 vibrates for a specific period of time. After this period of vibration the toy 1 stops vibrating and starts to travel forwardly, and stops when the rear body 2 is pushed again from above during travel.
The body 2, as shown in FIG. 2, consists of a lower case 7 and an upper case 8. In the body 2, a frame 10 (or gearbox) is mounted which houses various kinds of mechanisms. A motor 20 is housed in the frame 10 as a power source to produce drive power. The frame 10 is capable of making a relative motion with respect to the body 2 on the support point where the shaft 9 is supported on a bearing 1.7. The housing 12 also contains a battery 11.
Hereinafter, the various kinds of mechanisms housed in the frame 10 will be explained. A power transmission mechanism is housed in the frame 10 to the power produced by the motor 20. A travelling mechanism II is also housed in the frame 10 to drive the travelling toy by the power from the motor 20 through the power transmission mechanism I. A vibrating mechanism III to vibrate the body 2 with the power coming through the power transmission mechanism I, a power transmission route change mechanism IV to change the route of transmission of the power from the power transmission mechanism I, and a switch mechanism V to operate and stop the travelling toy are also housed in the frame 10.
The switch mechanism V is used to turn on and off the motor 20 by pressing down on the rear body 2a (the rear of body 2) having a switch operating section. This switch mechanism V includes a switch lever 30 which turns in interlock with the pressing of the rear body 2a, a ratchet wheel 31 which, receiving the rotating force from the switch lever 30, turns intermittently every time the switch lever 30 is operated, and a contact tongue 32 which comes in electrical contact with, and is released from, an electrode of the motor 20.
The switch lever 30 is rotatably supported on a shaft 33 which is mounted on the frame 10. One end of this switch lever 30 projects out of an opening 13 of the frame 10 and has a contact section 34 which contacts a switch-actuating projection 14 mounted under the rear body 2a. To the switch lever 30 the return force of a return spring 35 is applied in the reverse direction of pressing.
On the shaft 33, a ratchet gear 36 is mounted which rotates as one body with the switch lever 30. Furthermore, the rachet wheel 31 is on the shaft 33 mounted which can turn idle. On the side of this ratchet wheel 31 another ratchet gear 38 is integrally formed which is engaged with the ratchet gear 36 with the pressure of the spring 37. Then, the ratchet wheel 31 turns intermittently in the same direction by the rotational force of the switch lever 30. Teeth of the ratchet wheel 31 are generated to form one pitch with a switch-off section 31a having a deep tooth surface plus a switch-on section 31b having a shallow tooth surface. Ratchet wheel 31 is designed to turn by a half pitch per rotation of the switch lever 30.
The contact tongue 32 is a nearly V-shaped member produced of an elastic material. The contact tongue 32 is secured at one end of the frame 10; the other end is a movable end which operates into, and out of, an electrical contact with a contact tongue 38 connected with an electrode 21 of the motor 20. When the V-shaped root 32a is in mesh with the switch-on section 31b of the ratchet wheel 31, the other end 32b of the contact tongue 32 comes into electrical contact with the contact tongue 38. When the V-shaped root 32a is in mesh with the switch-off section 31a of the ratchet wheel 31, the other end 32b of the contact tongue 32 is released form the contact tongue 38. The operation of these contact tongues 32 and 38 turns on and off the motor 20.
The power transmission mechanism I is designed to transmit the rotational force of a drive gear 40 of the motor 20 to the travelling mechanism II and the vibrating mechanism III through a spur gear 42 and a pinion 43 mounted on a shaft 41, a spur gear 45 and a long gear 46 mounted on a shaft 44., and a spur gear 48, a clutch 49 and a pinion 50 mounted on a shaft 47. The spur gear 48 can idle and move axially with respect to the shaft 47.
The clutch comprises one clutch jaw 49a, integrally formed with the spur gear 48, and another clutch jaw 49b fixedly mounted on the shaft 47. The clutch jaws 49a and 49b are always kept in mesh with each other by the action of a spring 51.
The travelling mechanism II is secured on an axle 60 supporting rear wheels 5, and includes a spur gear 61 which can mesh with the final pinion 50 of the power transmission mechanism I. The rear wheels 5 are driven to rotate by the power from the power transmission mechanism I, thereby forwardly moving the toy 1.
The vibrating mechanism III is mounted, capable of idling, on the axle 60, and includes a spur gear 70 which can engage with the final pinion 50 of the power transmission mechanism I, thereby vibrating the body 2 to the right and left by the power from the power transmission mechanism I. On both sides of the spur gear 70 four semi-cylindrical cams 70a are disposed in staggered positions. Two cylindrical vibrating force receiving pieces 71, 71 are installed upright in the lower case 7 as if sandwiching the spur gear 70 from both sides. When the spur gear 70 is rotated by the power from the power transmission mechanism I, the cams 70a provided on both sides alternately rub the inner side of each of the vibrating force receiving pieces 71 to push them to the right and left, thus laterally vibrating the lower case 7 and the body 2 on the center of the shaft 9. The two cylindrical vibrating force receiving pieces 71, 71 can be attached directly to the lower case 7 or connected through springs 73 formed in the lower case 7.
The power transmission route change mechanism IV comprises a changeover mechanism 80 for switching the power transmission route from the vibrating mechanism III side to the travelling mechanism II side, and a return mechanism 81 for switching the power transmission route back to the vibrating mechanism III side in interlock with switch operation to stop the forward motion of the toy. The changeover mechanism 80 is of such a design that as a pinion 82 fixedly mounted on the shaft 44 rotates in one body with the long gear 46, a sector gear 86 freely rotatably mounted on the shaft 47 is turned by the rotational force of the pinion 82 for a specific period of time through a crown gear 84 and a worm gear 85. Both the crown gear 84 and the worm gear 85 are secured on a shaft 83 intersecting at right angles with the shaft 44. Then, an unlocking projection 88a releases a locking lever 89. The locking lever 89 is rotatably supported on the shaft 60 and, in normal operation, held in engagement with the slide surface 88 formed on one side of the sector gear 86 by the action of the spring 87. The locking lever 89 moves the shaft 47 in the axial direction thereof by the force of the spring 90 to move the pinion 50 secured on the shaft 47 and in engagement with the spur gear 70 side, into mesh with the spur gear 61 side.
Hereinafter, the relation of the locking lever 89 and the sector gear 86 will be particularly described with reference to FIGS. 4(a) and 4(b). When the sector gear 86 makes a half turn from the initial state shown in FIGS. 4(a) and 4(b), the unlocking projection 88a comes into contact with the upper part of an arm section 89a of the locking lever 89. Furthermore, as the sector gear 86 rotates, the locking lever 89 is pushed downwardly by the unlocking projection 88a against the force of the spring 87. Then, the unlocking projection 88a, when having reached the lower position, snaps off the locking lever 89, which therefore comes off the sliding surface 88 and at the same time the shaft 47 is moved to the right in FIG. 4(a) by the force of the spring 90. Also, in this case, the sector gear 86 comes out of engagement with the worm gear 85, being turned back to the initial position by the return spring 91. Additionally, the distance of axial movement of the shaft 47 is restricted by the contact of its forward end with the side surface of the switch lever 30.
The return mechanism 81 comprises a cam 92 formed on the side surface of the switch lever 30. The cam 92 moves the shaft 47, which is in the travelling position in which the pinion 50 is in mesh with the spur gear 61, back to the vibrating position side with the rotation of the switch lever 30. With this return operation, the shaft 47 moves as far as the vibrating position, in which the worm gear 85 and the sector gear 86 come into mesh with each other, and at the same time the pinion 50 comes into mesh with the spur gear 70. At the same time, the locking lever 89 comes into engagement with the sliding surface 88 of the side surface of the sector gear 86.
Inside the rear end of the upper case 8, a switch operation restricting lever 15 is installed to mechanically prevent the switch mechanism V from being activated when the rear body 2a (rear or body 2) is pushed down. When the switch operation restricting lever 15 is properly set with its top end in contact with a switch operation restricting lever contact section 16, it is possible to play with the toy using one's hands to move the vehicle. Furthermore, if the toy is carelessly put into a toy box, the switch operation restricting lever 15 will prevent the switch lever 30 from electrically activating the motor 20 and running down the battery 11.
A sound producing gear 92, securely mounted on the side of the sector gear 86, has sound-producing pieces 92a arranged intermittently. With the rotation of the sector gear 86, the sound-producing gear 92 produces a sound every time each of them touches a sound-producing tongue 93. Various patterns of sound producing pieces 92a can be placed on the sound producing gear 92 to produce a particular idling or other forward running sound for the vehicle. The length of the sound-producing tongue 93 and the material it is mounted on can be chosen for a desired pitch and depth of sound. Furthermore, on the side of the spur gear 61 is fixedly attached a sound-producing gear 62, which, in contact with a sound-producing tongue 63,/ produces a sound with the rotation of the spur gear 61. The length or mounting material of the sound-producing tongue 63 can likewise be varied.
The travelling toy according to the present embodiment can be played with as follows. For example, when the rear body 2a of the travelling toy 1 which is stopped, is pushed downwardly, the switch lever 30 rotates to turn on the motor 20. The drive power from the motor 20 is transmitted to the vibrating mechanism III through the power transmission mechanism I, thereby vibrating the body 2. At the same time, the power from the motor 20 is transmitted to the power transmission route change mechanism III to turn the sector gear 86. With the rotation of the sector gear 86, the locking lever 89 comes off the unlocking projection 88a, thus releasing the sector gear 86. Accordingly, the shaft 47 moves to the travelling position, changing the power transmission route from the vibrating mechanism III side to the travelling mechanism II side. Consequently, the body 2 stops vibrating, while the power coming through the power transmission mechanism I is transmitted to the travelling mechanism II to turn the rear wheels 5, thus moving the travelling toy forwardly.
When the rear body 2a of the travelling body 1 thus running is pushed downwardly, the switch lever 30 turns to stop the motor 20, and accordingly the travelling toy 1 stops advancing. At the same time, as the switch lever 30 rotates, the return mechanism 81 operates to move the shaft 47 from the travelling position back to the vibrating position. In this state, the power from the power transmission mechanism I is transmitted to the vibrating mechanism III and to the power transmission route change mechanism IV. Thus, the toy body becomes ready for vibrating when the rear body 2a is pushed downwardly again.
According to the travelling toy of the present embodiment described above, the body 2 vibrates to the right and left prior to travelling as if an actual dump truck vibrates during engine warm-up operation. It is, therefore, possible to produce a travelling toy capable of being used just like an actual motor vehicle. Further, it is possible to make a more amusing travelling toy by adding the vibrating mechanism to a conventional travelling toy which otherwise can do nothing but travelling. Furthermore, because the rear body 2a which forms the body of the travelling toy includes a switch operating section, the toy itself has much the same appearance of an actual vehicle motor. It is, therefore, possible to produce travelling toys which work like an actual motor vehicle.
The travelling toy according to the present embodiment has the appearance of a dump truck with a rear body 2a but may be any other kind of travelling toy such as a fire truck, a locomotive, an airplane, and a boat. For example, the fire truck can have an extendably raisable ladder pivotably mounted on a rear upper surface. Furthermore, the vibrating mechanism according to the present embodiment described above is designed to vibrate to the right and left, but may be so designed as to make up-and-down vibration. Also, in the travelling toy according to the present embodiment, a motor is adopted as a power source, but a spring may be used in place of the motor. Additionally, according to the present embodiment, the travelling toy is equipped with a mechanical power transmission route change mechanism, but the change of the power transmission route may be electronically controlled by means of an integrated circuit. Furthermore, the number of the cams 70a on the spur gear 70 according to the present embodiment is not necessarily limited to four on either side, but may be one or more.
According to the present invention, because of the adoption of the vibrating and travelling mechanisms and the power transmission route change mechanism, it is possible to provide a new, amusing travelling toy which vibrates before moving just like an actual motor vehicle with its engine idling before moving. Thus, the travelling toy excites amusement by adding vibration motion.
While the invention has been illustrated and described in detail in the drawings and foregoing description, it will be recognized that many changes and modifications will occur to those skilled in the art. It is therefore intended, by the appended claims, to cover any such changes and modifications as fall within the true spirit and scope of the invention.
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A travelling toy vehicle is provided having an external body in the shape of a dump truck or other vehicle. An internal gear box, or frame, drives two wheels on an axle. The frame contains a vibrating mechanism and rocks left and right by the motion of a spur gear disposed between two cylindrical force receiving pieces attached to the external body of the travelling toy vehicle. A power transmission route change mechanism couples driver power from a motor to the vibrating mechanism for a predetermined period of time to simulate ideling of the vehicle. Thereafter, the drive power is coupled to the travelling mechanism to provide forward movement of the travelling toy vehicle. Electrical power to the motor is switched on and off by pressing down against the rear portion of the travelling toy vehicle. An operation restricting lever mounted at the rear of the vehicle prevents the switching on of electrical power when the toy is being stored and allows manual use of the toy without propulsion by the motor.
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RELATED APPLICATION
[0001] This application claims benefit from Indian Patent Application No. 2366/MUM/2008 filed on Nov. 7, 2008.
TECHNICAL FIELD
[0002] The present invention relates to the novel process for the synthesis of octreotide and derivatives thereof by solid phase peptide synthesis. In particular, the present invention relates to synthesis of protected linear peptides, cleavage from the resin, deprotection followed by cyclization process for the unprotected peptide wherein the preparation process is simple, easy, environment friendly, inexpensive with high yield and purity.
BACKGROUND OF INVENTION
[0003] Octreotide is a highly potent and pharmacologically selective analog of somatostatin. It inhibits growth hormone for long duration and is thereof indicated for acromegaly to control and reduce the plasma level of growth hormone. The presence of D-Phe at the N-terminal and an amino alcohol at the C-terminal, along with D-Tryptophan and a cyclic structure makes it very resistant to metabolic degradation.
[0004] Octreotide comprises 8 amino acids which has the following structural formula:
[0000]
[0005] wherein sulphur atoms of the Cys at the position 2 and of the Cys at the position 7 are mono-cyclic to form an —S—S— bridge.
[0006] A considerable number of known, naturally occurring small and medium-sized cyclic peptides as well as some of their artificial derivatives and analogs possessing desirable pharmacological properties have been synthesized. However, wider medical use is often hampered due to complexity of their synthesis and purification. Therefore, improved methods for making these compounds in simple, lesser steps and at lesser cost are desirable and this is the felt need of the industry and the mankind.
[0007] Conventional synthesis of octreotide may be divided into two main approaches, direct solid-phase synthesis and liquid-phase synthesis. Solution phase synthesis has been described by Bauer et al., (Sandoz) (Eur. Pat. Appl. 29,579 and U.S. Pat. No. 4,395,403). The process comprises: removing protected group from peptide; linking together by an amide bond two peptide unit; converting a function group at the N- or C-terminal; oxidizing a straight chain polypeptide by boron tristrifluoroacetate. This process involves a time-consuming, multi-step synthesis, and it is difficult to separate octreotide from the reaction mixtures since all the synthesis steps are carried out in liquid phase. Another solution phase approach described by Chaturvedi, et al., (Wockhardt) in U.S. Pat. No. 6,987,167 and EP 1506219 A, claims the cyclization of partially deprotected octreotide in the solution phase using iodine under conditions and for a time sufficient to form the octreotide.
[0008] Synthesis in solid phase have been described subsequently (Mergler et al., Alsina et al., Neugebauer). The above prior art for solid phase peptide synthesis cites the octapeptide formation, by starting the synthesis from the threoninol residue which makes it mandatory to protect this residue. Mergler et al., (Peptides: Chemistry and Biology. Proceedings of the 12 th American Peptide Symposium. Smith, J. A. And Rivier J. E. Eds ESCOM, Leiden, Poster 292 Presentation, (1991)) describes a synthetic process, using an aminoethyl resin upon which the Threoninol residue is incorporated with the two alcohol functions protected in acetal form The synthesis is carried out following an Fmoc/tBu protection scheme, forming the disulphide bridge on resin by oxidation of the thiol groups of the previously deprotected cysteine residues and releasing and deprotecting the peptide with a 20% mixture of TFA/DCM.
[0009] In early 1997, Alsina J. et al. (Alsina J., Chiva C., Ortiz M., Rabanal F., Giralt E., and Albericio F., Tetrahedron Letters, 38, 883-886, 1997) described the incorporation, on active carbonate resins, of a Threoninol residue with the amino group protected by the Boc group and the side chain protected by a Bzl group. The synthesis was then continued by Boc/Bzl strategy. Formation of the disulfide bridge was carried out directly on resin using iodine and the peptide was cleaved from the resin and its side chain protecting groups were simultaneously removed with HF/anisole 9/1. At the final stage the formyl group was removed with a piperidine/DMF solution.
[0010] Neugebauer (Neugebauer W., Lefevre M. R., Laprise R, Escher E., Peptides: Chemistry, Structure and Biology, p 1017, Marshal G. R. And Rivier J. E. Eds. ESCOM.Leiden (1990) described a linear synthesis with a yield of only 7%.
[0011] Edwards et al., (Edwards B. W., Fields C. G., Anderson C. J., Pajeau T. S., Welch M. J., Fields G. B., J. Med. Chem. 37, 3749-3757 (1994) carried out another another solid-phase type approximation; they synthesized step-by-step on the resin, the peptide D-Phe-Cys(Acm)-Phe-D-Trp(Boc)-Lys(Boc)-Thr(tBu)-Cys(Acm)-HMP-Resin. Next they proceeded to form the disulfide on resin and then release the peptide from the resin by means of aminolysis with threoninol, with obtaining a total yield of only 14%.
[0012] The solid phase synthesis described by Yao-Tsung Hsieh et. al., in U.S. Pat. No. 6,476,186 involves the synthesis of octreotide by using Thr(ol)(tBu)-2Cl-trityl resin as starting material followed by the cleavage of the straight chain peptide from the resin by using a strong acid and the formation of the intra-molecular disulfide bond on the completely deprotected octreotide by oxidation using charcoal catalyst and a higher yield of >70%.
[0013] Another solid phase synthesis described by Berta Ponsati et.al (Lipotec) in U.S. Pat No. 6,346,601 and EP 0953577 B involve the coupling of threoninol on the protected heptapeptide in solution, after a selective acid cleavage from the chlorotrityl resin without affecting the peptide side-chain protecting groups.
[0014] A hybrid solid phase-liquid phase method for synthesis of octreotide described by Iarov et al., (Dalton Chemical Laboratories) in WO 2005087794 wherein the method comprises liquid phase condensation of two or three peptide blocks in which at least one peptide block is synthesized by solid-phase method.
[0015] EP 1511761 B1 involves cyclization on the semi-protected linear peptide wherein one of the cysteine residue is protected with an orthogonal protecting group.
[0016] The radioactive isotope labeling of octreotide by the coupling of bifunctional chelating agents like DTPA or DOTA to the peptide was described by Te-Wei Lee et al., in U.S. Pat. No. 5,889,146 (Inst. of Nuclear Energy Research)
[0017] The method for cyclization of linear vapreotide by means of intramolecular cysteine formation has been described by Quattrini et. al., (Lonza AG) in WO 2006048144, wherein the process involves the synthesis of linear vapreotide peptide on Sieber-resin (from Novabiochem) by Fmoc standard groups, wherein the side chain protecting groups are D or L-Trp(Boc), Cys(Trt), Lys(Boc), Tyr(tBu). The protected peptide is cleaved off in 5% TFA in dichloromethane and then globally deprotected by acidolysis in a cleavage mix of 300 equivalents of concentrated TFA, 12 equivalents of Dithiothreitol, 12 equivalents of Dichloromethane, 50 equivalents of water for 1 hour at room temperature. The Boc groups are removed. The product was subjected to charcoal method using trace amounts of activated, powdered charcoal wherein a concentration of the linear cysteinyl peptide of 50 mg/ml (1 eq.) in DMF in the presence of 1 eq. Diisopropyl-ethyl-amine and that additionally air was sparged at low pressure into the liquid under stirring. After 15-20 hrs, 100% conversion was achieved with 84% (w/w) analytical yield of 79% vapreotide.
[0018] The formation of intramolecular disulphide formation in a polypeptide by reacting with hydrogen peroxide has been described by Mineo Niwa et al. (Fujisawa Pharmaceutical Co.) in U.S. Pat. No. 5,102,985 wherein the reaction is to be carried out at a pH of about 6 to 11, wherein the molar ratio of H 2 O 2 to polypeptide is within the range of 1:1 to 100:1.
[0019] The above cited prior art mainly carries out the cyclization of the peptide on the resin or on partially protected or protected peptides. The use of partial or minimal protecting group strategies and improvement in the activation methods have considerable effect on limitations of poor solubility and possible danger of racemization due to the overactivation of carboxyl groups. However, these approaches do not overcome the problem of the poor coupling efficiency between large peptide segments, because of the intrinsic difficulty of obtaining effective molar concentrations for high molecular weight molecules.
OBJECT OF INVENTION
[0020] The main object of the present invention is to provide a novel process for synthesis of octreotide and derivatives thereof wherein the process uses mild reagents, isolates protected peptide by simple aqueous precipitation, avoids usage of hazardous thiol scavengers in the cleavage cocktail, achieves effective oxidation of deprotected peptide in the presence of hydrogen peroxde to yield a clean crude cyclic octapeptide at a purity of >70% with an overall yield of 95%.
[0021] Another object of the present invention is to obtain pure octreotide with a purity of >99% with total impurity <1%.
[0022] Still another object of the invention is an improved process for cyclization of octreotide wherein the cyclization is carried out in the presence of hydrogen peroxide on a completely deprotected heptapeptide or octapeptide.
SUMMARY OF INVENTION
[0023] One embodiment of the present invention is an improved process for preparing octreotide of formula
[0000]
[0024] comprising the following steps: p 1 i. using H-Cys (Trt)-2-chlorotrityl resin as the starting material, coupling of various selected amino acid residues using coupling agent in polar aprotic solvent to give the straight chain peptide resin compound of formula 2 Boc-D-Phe-Cys(Trt)-Phe-D-Trp-Lys(Boc)-Thr(OBut)-Cys(Trt)-2-Chlorotrityl resin;
ii. cleaving the product of step i with a solution comprising of TFA in dichloromethane or acetic acid in dichloromethane to give straight chain peptide of formula 3 Boc-D-Phe-Cys(Trt)-Phe-D-Trp-Lys(Boc)-Thr(OBut)-Cys(Trt)-OH; iii. coupling of threoninol to the C-terminal in the presence of benzotriazole to give linear protected octapeptide of the formula 4 Boc-D-Phe-Cys(Trt)-Phe-D-Trp-Lys(Boc)-Thr(OBut)-Cys(Trt)-Thr-OL; iv. deprotecting the product of step iii with TFA, triisopropylsilane and water to give linear deprotected octapeptide of formula 5
[0000]
v. oxidizing the deprotected octapeptide of step iv at an acidic pH in the range of 2.5 to 6.5 in the presence of hydrogen peroxide to yield octreotide of formula 1;
vi. purifying the crude octreotide of step v by chromatography to a purity of ≧99%;
vii. converting the pure octreotide of step vi to acetate salt;
viii. concentrating the acetate salt of octreotide of step vii and lyophilizing the same.
[0032] Second embodiment of the present invention is a process for preparing octreotide of formula
[0000]
[0033] comprising the following steps:
i. using H-Cys (Trt)-2-chlorotrityl resin as the starting material, coupling of various selected amino acid residues using coupling agent in polar aprotic solvent to give the straight chain peptide resin compound of formula 2 Boc-D-Phe-Cys(Trt)-Phe-D-Trp-Lys(Boc)-Thr(OBut)-Cys(Trt)-2-Chlorotrityl resin; ii. cleaving the product of step i with a solution comprising of TFA in dichloromethane or acetic acid in dichloromethane to give straight chain peptide of formula 3 Boc-D-Phe-Cys(Trt)-Phe-D-Trp-Lys(Boc)-Thr(OBut)-Cys(Trt)-OH; iii. deprotecting the product of step ii with TFA, triisopropylsilane and water to give linear deprotected heptapeptide of formula 6
[0000]
iv. oxidizing the deprotected heptapeptide of step iii at an acidic pH in the range of 2.5 to 6.5 in the presence of hydrogen peroxide to yield heptapeptide of formula 7
[0000]
v. coupling of threoninol to the C-terminal in the presence of benzotriazole to yield octreotide of the formula 1;
vi. purifying the crude octreotide of step v by chromatography to a purity of ≧99%;
vii. converting the pure octreotide of step vi to acetate salt;
viii. concentrating the acetate salt of octreotide of step vii and lyophilizing the same.
[0042] Third embodiment of the present invention is Octreotide of formula 1 as claimed, wherein the purification of the crude cyclic octapeptide to a purity of ≧99% is carried by ion exchange chromatography followed by RP-HPLC in gradient mode.
[0043] Fourth embodiment of the present invention is a pharmaceutical composition comprising octreotide of formula I as claimed and at least one pharmaceutically acceptable excipient.
BRIEF DESCRIPTION OF ACCOMPANYING DRAWINGS
[0044] The manner in which the objects and advantages of the invention may be obtained will appear more fully from the detailed description and accompanying drawings, which are as follows:
[0045] FIG. 1 : RP-HPLC profile of crude octreotide using DMSO for oxidation of S—H to S—S.
[0046] FIG. 2 : RP-HPLC profile of crude octreotide using H2O2 for oxidation of S—H to S—S.
[0047] FIG. 3 : RP-HPLC profile of linear protected heptapeptide at 210 nm wavelength.
[0048] FIG. 4 : RP-HPLC profile of protected octapeptide.
[0049] FIG. 5 : RP-HPLC purity profile of pure octreotide.
[0050] FIG. 6 : MS spectrum of pure octreotide with a mass of 1019.9 Da.
DETAILED DESCRIPTION OF THE INVENTION
[0051] Synthesis of peptides on a solid support is a conventional method which has known advantages cited in the prior art. Impurities found with the desired peptide are derived from three sources: namely, coupling of amino acid derivatives to the growing peptide chain, cleavage of the peptide from the solid support, and deprotection of side-chains of the assembled sequence. Impurities often have small differences in structure such as the deletion of one amino acid residue resulting from a slow coupling reaction or a rearranged/derivatized side-chain group formed during the cleavage of the peptide from the solid support. However, in addition to maintaining the purity of the peptide, a major challenge also is to substantially increase the yield or recovery of the peptide synthesized. Complexity increases with the synthesis of cyclic peptides. The preparation of cyclic peptide disulfides from the corresponding SH-precursors and the direct conversion of the cysteine-protected derivatives into cyclic products (deprotection of the -SH groups with simultaneous cyclization) are most widely used among the diversity of methods known for the synthesis of disulfide containing peptides. As a rule, in both cases, the cyclization is carried out in very dilute solutions, with the peptide concentration being of 10 −4 -10 −5 M in order to avoid an intermolecular aggregation and side reactions. The directed formation of S—S bonds in the highly diluted solutions significantly depends on structural peculiarities of a peptide, in particular, on the nature of amino acid residues between Cys residues. The cyclization of free thiols by the air oxygen usually leads to low yields of target products (9-15%). In the air-oxidation process, the proceeding speed of the reaction progress itself is very slow, and especially, it hardly proceeds under denaturing condition, such as in a highly concentrated salt or urea-aqueous solution of polypeptide. The application of potassium ferricyanide or dimethyl sulfoxide usually result in homogeneous reaction mixtures and the yields of cyclic products are considerably higher (from 20 to 60%, and, in some cases, up to 80%, which depends on the peptide structure). However, a multistage purification of product is necessary for the removal of excess of these oxidative agents. Moreover it produces the problem of environmental pollution, since the resultant waste water contains CN − . A very attractive one-step formation of the disulfide bridges by the action of iodine is often accompanied by side reactions and has only a limited use in the case of Trp- and Met-containing peptides. In the iodine-oxidation process, tyrosine residues in a peptide may be disadvantageously iodinated.
[0052] An inherent feature of the present invention is provision of sufficiently homogenous reaction mixture and a simple, preferably one step isolation of octapeptide of >70% purity which on subsequent chromatographic purification yields an octapeptide of >99% purity. More particularly the oxidation process is easily upscaled and is least cost intensive relatively lowering the manufacturing cost.
[0053] Producing cyclized peptides with the correct structure can be achieved readily by either on-resin or post-cleavage techniques. On-resin techniques produce greater yields of the final products, but are more expensive to perform. However, post-cleavage techniques are less expensive and provide reasonable yields of the desired product. Another feature of the present invention is post-cleavage cyclization of the heptapeptide and subsequent coupling of threoninol or direct cyclization of the octapeptide to form cyclic octapeptide.
[0054] The solid-phase synthesis of octreotide had several potential pitfalls that could reduce peptide assembly and cleavage efficiencies and/or resulted in deletereous side reactions. Potential problems included i) racemization of the C-terminal Cys residue, ii) inefficient disulfide bond formation on resin, iii) modification of Trp during disulfide bond formation, and iv) incomplete peptide-resin cleavage. Racemization during the esterification of the C-terminal amino acid or during the chain elongation is suppressed by several alternative techniques. One of the essential feature of the present invention wherein C-terminal Cys peptide is successfully synthesized without racemization by Fmoc based solid phase method using 2-chlorotrityl resin. The use of 2-Chlorotrityl resin circumvents the racemization at the C-terminal cysteine caused by the base treatment, probably due to its high steric hindrance. Another novel feature of the present invention is cyclization of the fully deprotected heptapeptide or octapeptide.
[0055] Iodine, however, is not without drawbacks as a cyclization agent. For instance, tryptophan moieties present in peptide substrates are at risk of being modified, making the balance between full conversion of starting materials and minimizing side reactions a delicate one, which, in turn, impacts product purity. In the present invention this aspect has been rightfully tackled by not opting for Iodine route for oxidative cyclization. Therefore the process of the present invention has a product of enhanced purity and better yield. Another complicating factor in known synthesis routes is the possibility of interaction between the desired cyclic disulfide and inorganic sulfur compounds used for reducing excess iodine at the end of the reaction, such as sodium dithionite or sodium thiosulfate. Such reducing sulfur-containing compounds may interact with the disulfide linkage, which is sensitive to nucleophilic attack in general. As the process of the present invention does not use iodine, the resulting products have high purity and related impurities are undetectable.
[0056] The solution phase route is more cumbersome as after each coupling the peptide has to be isolated, as compare to the solid phase route where the excess reagents and by-products are washed off by simple filtration. In both, the desired peptide compound is created by the step-wise addition of amino acid moieties to a growing peptide chain. As compared to Boc-chemistry, Fmoc-chemistry based synthesis is a mild procedure and because of the base liability of Fmoc group, acid-labile side-chain protecting groups are employed giving an orthogonal protection strategy. The rationale for use of protecting groups is that the energy of breaking a bond of a protecting group is lower than any other group in question. Where appropriate, these are based on the tert-butyl moiety: tert-butyl ethers for Ser, Thr, tert-butyl esters for Asp, Glu and Boc for Lys, His. The trt group has been extensively used for the protection of Cys. Also for Cys, the Acm group is extensively used when a protecting group on the sulfur needs to be maintained after the cleavage of the peptide. The guanidine group of Arg is protected by Mtr, Pmc or Pbf. Most Of the Fmoc-amino acids derivatives are commercially available. However, a problem exists in the art for the preparation of modified amino acid peptides as well as cyclic peptide compounds based on disulfide links because separate operations are required before purifying the end product, which increases expense and may effect final product quality and quantity.
[0057] The purity of a peptide has several aspects. One is purity on the basis of an active-compound concentration scale. This is represented by the relative content of the pharmacologically active compound in the final product, which should be as high as possible. Another aspect is the degree of absence of pharmacologically active impurities, which though present in trace amounts only, may disturb or even render useless the beneficial action of the peptide when used as a therapeutic. In a pharmacological context both aspects have to be considered. As a rule, purification becomes increasingly difficult with larger peptide molecules. In homogeneous phase synthesis (which is the current method of choice for industrial production of larger amounts of peptides) repeated purification required between individual steps provides a purer product but low yield. Thus, improvements in yield and purification techniques at the terminal stages of synthesis are needed. The present invention is an industrially feasible solid phase synthesis and is a novel process to yield a high purity product with greater yields.
[0058] A general outline for the synthesis of octreotide in the present invention is described as follows: The heptapeptide is synthesized as peptide acid by solid phase peptide synthesis technology on 2-Chloro Trityl chloride Resin using Fmoc chemistry.
Instrument: CS936, CS BIO, California; Peptide synthesizer. Resin: H-Cys(Trt)-2Cl Trityl Resin. Activator: HBTU/NMM Solvent: Dimethyl Formamide Deprotection 20% Piperidine in DMF a) The resin H-Cys(Trt)-2Cl Trityl Resin, 10 mmole is transferred to the RV of the CS936 & the linear peptide assembled on it using 1.5-4 times mole excess amino acid derivatives, on the peptide synthesizer. Each coupling is carried out for a time range of 45-90 min. After the couplings are complete, resin is washed with DMF (60-100 ml three washings) followed by 0.2% DIPEA in DCM (60-100 ml six washings) & dried under vacuum. The details of the synthesis are described in the examples. b) cleavage of the peptide from the resin using the cocktail mixture consisting of TFA in DCM or Acetic acid in DCM c) coupling of peptide in formula 3, with Threoninol to give protected octa-peptide of formula 4. d) isolation of peptide post Threoninol coupling by precipitation with water. e) isolation of peptide in step C can also be done by chromatography. f) removal of protecting group by using TFA cocktail mixture from formula 4 followed by oxidation with H 2 O 2 , to give peptide of formula 1. The crude peptide is purified by chromatography.
The abbreviations used in this description have the meanings set forth below:
[0070] Glossary
AA Amino Acid ACT Activator Arg Arginine Asp Aspartic Acid Boc Tert-butyloxycarbonyl Cys Cysteine DCM Dichloromethane DEP Deprotection reagent DMF Dimethyl Formamide DIPEA N,N-diisopropylethylamine DMSO Dimethyl slphoxide Fmoc 9-fluorenylmethyloxycarbonyl Glu Glutamic acid Gly Glycine HBTU 2-(1H-Benzotriazole 1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate HF Hydrogen Fluoride HIC Hydrophobic Interaction Chromatography His Histidine IEC Ion Exchange Chromatography LC-MS Liquid Chromatography-Mass Spectroscopy Lys Lysine Mtr 4-methoxy-2,3,6-trimethylbenzenesulfonyl MeOH Methanol NMM N-methyl morpholine Obut O-t-butyl Pbf 2,2,4,6,7-pentamethyldihydrobenzofuran-5-sulfonyl Phe Phenyl alanine Pmc 2,2,5,7,8-pentamethylchroman-6-sulfonyl Pro Proline RP-HPLC Reverse Phase High Performance Liquid Chromatography. RV Reaction Vessel Ser Serine SOLV Solvent SP Synthetic Peptide TEA Triethylamine TFA Trifluoroacetic acid Thr Threonine TIS Triisopropylsilane Trp Tryptophan Trt Trityl
EXAMPLES
Example 1
[0111] Attachment of First Amino Acid Cys(Trt) to 2-Chlorotrityl Chloride Resin to give H-Cys(Trt)-2-Chlorotrityl resin:
[0112] Fmoc-Cys(Trt)-OH (52.6 gm, 90 mmol) was suspended in 500 ml dichloromethane. DIPEA (47.12 ml, 270 mmole) was added to it. The mixture was stirred for 10 minutes. While under stirring, 2-ChloroTrityl chloride resin(1.13 mmoles/gm, 22.73 g; 30 mmole) was added. The resulting mixture was continuously stirred for one hour under nitrogen atmosphere. The resin was filtered and washed with DMF (80 ml×6 washings for 3 min) followed by 0.2% DIPEA in DCM (60 ml-100 ml×6 washing for 5 min).
[0113] The resin was capped with MeOH:DCM:DIPEA 200 ml×3, for 5 min each after swelling in DCM. The resin was swelled again in DMF. 20% piperidine in DMF (100 ml×3) was used for deprotection (Fmoc removal) for 5 minutes each. The resin was washed with DMF (60 ml-100 ml×6) for 3 minutes each. The resin was washed with 0.2% DIPEA in DCM (100 ml×3 times) for 3 minutes each time. The resin was dried for 12-15 hours under high vacuum.
[0114] Yield >90% Substitution: 0.6 mmoles/gm.
Example 2
[0115] Chemical Synthesis of Protected (1-7) Fragment of Octreotide (heptapeptide):
[0000] Boc-D-Phe-Cys(Trt)-Phe-(D)Trp-Lys(Boc)-Thr(OBut)-Cys(Trt)-2-ChloroTrityl resin Formula 2
[0116] The peptide was synthesized as peptide acid by solid phase peptide synthesis technology on H-Cys(Trt)-2-chlorotrityl resin using Fmoc chemistry.
[0000]
Instrument
CS-BIO-936,
Resin
Peptide synthesizer
H-Cys(Trt)-2-ChloroTrityl resin
(0.6 mmoles/gm).
Side chain protecting groups
Thr: OBut; Cys: Trt; Lys: Boc.
Activator
HBTU/NMM
Solvent
Dimethyl Formamide.
[0117] The H-Cys(Trt)-2-Chlorotrityl resin (16.666 g, 10 mmole) was transferred into the RV of the CS 936. The assembly of the remaining amino acids was carried out using side chain protected Fmoc derivatives of Thr, Lys, (D)Trp, Phe, Cys, and BOC protected (D)Phe with HBTU (2 times excess; 20 mmole) on the peptide synthesizer. Each coupling was carried out for 60 minutes. The completion of coupling was monitored by Kaiser test, which indicated the completeness of coupling reaction (>99%), when negative. After the couplings were complete, resin was washed with 0.2% DIPEA in DCM (100 ml×6) and product was dried under high vacuum over drying agents like calcium chloride.
[0118] Yield: >90%.
Example 3
[0119] Cleavage of Protected Heptapeptide Fragment of Octreotide:
[0000] Boc-(D)Phe-Cys(Trt)-Phe-(D)Trp-Lys(Boc)-Thr(OBut)-Cys(Trt))-OH. Formula 3
[0120] The dried peptidyl-resin(40 gm) was treated with 500 ml of 0.1% TFA v/v in dichloromethane for 5 minutes and filtered. The process was repeated for six times. The filtrate was concentrated under vacuum on rotavap & cold ether was added (300 ml) to precipitate the protected heptapeptide. The precipitate was triturated with spatula and kept in cold followed by filteration through G-4 sintered funnel. The precipitate was washed with 100 ml of ether twice and dried under vacuum. The RP-HPLC profile of linear protected heptapeptide is depicted in FIG. 3 .
[0121] Yield: >95%
[0122] Purity by RP-HPLC=88.64%
Example 4
[0123] Deprotection of Protected Heptapeptide, to get SH-heptapeptide:
[0000]
[0124] Cleavage cocktail mixture TFA:TIS:WATER (95:2.5:2.5) was prepared & kept at 4° C. 60 ml of cocktail was added to protected-heptapeptide (3 gm) slowly under stirring and nitrogen atmosphere. Stirring was continued for 2 hours and 45 minutes.
[0125] The reaction mixture was concentrated. To the concentrate, cold DIPE (600 ml) was added to precipitate the crude ACM-heptapeptide & kept at −20° C. overnight. The precipitate was filtered, followed by DIPE wash and the precipitate dried under vacuum for 18 hours at room temperature.
[0126] Oxidation of heptapeptide using H2O2:
[0000]
[0127] The heptapeptide was oxidised to form disulfide as in Example 7.
[0128] Coupling of Threoninol to the deprotected disulfide heptapeptide:
[0129] The deprotected disulfide heptapeptide (300 mg w/w, 0.259 mmole) was dissolved in hydroxy benzotriazole (159 mg, 1.036 mmole), in dimethylacetamide (1 ml) followed by addition of & threoninol (108 mg, 1.036 mmole).The reaction mixture was cooled to 15° C. DCC(60 mg, 0.285 mmole) solution (0.2 ml) was added to the reaction mixture and stirred at 15° C. for 1 hour. Additional stirring was carried out at room temperature for 60 hours. The reaction was monitrored by HPLC. After 20 hours, 70% of the reaction was completed. Further monitored coupling after 60 hours, 85 to 90% of the coupling was completed. The peptide was precipitated from reaction mixture by addition of 40 ml of ethyl acetate followed by stirring at room for 2 hours. The product was filtered on whatman filter paper and dried under vacuum for 20 hours.
[0130] Purity: 50%
Example 5
[0131] Coupling of Threoninol to Protected Heptapeptide to Give Protected Octapeptide:
[0000] Boc-(D)Phe-Cys(Trt)-Phe-(D)Trp-Lys(Boc)-Thr(OBut)-Cys(Trt))-Thr-OL. Formula 4
[0132] The protected heptapeptide (24 gm) and hydroxy benzotriazole (6.26 gm) was dissolved in dimethylacetamide (100 ml) followed by addition of threoninol (4.2 gm). The reaction mixture was cooled to 15° C.-20° C. DCC (3.069 gm) was added to the reaction mixture and stirred at 15° C. for 1 hour. Additional stirring was carried out at room temperature for 24 to 72 hours. After the reaction was completed, the urea was filtered on sinter funnel. The urea was washed with 5 ml of DMAC twice. The filtrate fractions were pooled and dropwise added to 0.5% solution of sodium bicarbonate in 1 L of water under stirring at 20° C., further after 15 minutes 500 ml of water was added at 20° C. The stirring was continued for another 1 hour. The precipitate was filtered and washed with 100 ml of water five times. The RP-HPLC profile of linear protected octapeptide is depicted in FIG. 4 .
[0133] Dried under vacuum for 30 hours
[0134] Yield: >95%
[0135] Purity by RP-HPLC=81.38%
Example 6
[0136] Deprotection of Protected Octapeptide to Give SH-Octapeptide:
[0000]
[0137] The protected octapeptide (23 gm) was treated with TFA/TIS/Water (1150 ml) for 2 hours and 45 minutes for the removal of side chain protecting groups. TFA was evaporated, and peptide precipitated by addition of cold DIPE(500 ml). The solution was filtered and washed with DIPE(100 ml×3) and the precipitate dried.
[0138] Yield: >95%
Example 7
[0139] Hydrogen Peroxide Oxidation of S—H Octapeptide:
[0000]
[0140] S—H Octapeptide(15 gm) was dissolved in water at a concentration of 2 mg/ml and pH adjusted to 6.5 to 7 with ammonium hydroxide solution. Hydrogen peroxide solution(450 ml) was added in three parts over a period of half hour and allowed to stir at RT over a period of one hour and then acidified to pH <3 with acetic acid. The crude disulfide looped peptide was filtered and solution was taken for IEC purification. The purity was estimated by RP-HPLC ( FIG. 2 ).
[0141] Purity: 70.5%
Example 8
[0142] Oxidation of S—H Peptide with DMSO-HCl to Get S—S Peptide:
[0000]
[0143] S—H peptide (9 g) was dissolved in 6.5 L DMSO and under ice-cooling 6.5 L 1M HCl was added slowly so that temperature is below 26° C. Stirring was continued for 6 hours. At room temperature after six hours reaction mixture was diluted with 13 L of water and filtered through Whatman no. 41 through Celite bed. The filtrate was loaded on C-18 column for concentration. The compound was eluted with 100% acetonitrile. The eluant was concentrated on rotavap and then the concentrated solution was centri-evaporated to dryness. The RP-HPLC profile of crude octreotide is depicted in FIG. 1 .
[0144] Weight of crude peptide=3.9g.(45%)
[0145] Purity: 44.25%
Example 9
[0146] Purification of Crude Octreotide:
[0147] The crude octreotide was loaded on to cation ion exchange column and eluted using a salt gradient using a Akta Purifier (by Amersham, Sweden) low pressure chromatography system. The IEX fractions of purity >70% were further loaded for RP-HPLC purification on Kromacil C-18 column of (250×50 mm, 100 A 0 .) The peptide was purified by using aqueous TFA(0-0.5%) and methanol/ethanol and/or Acetonitrile in a gradient program on a Shimadzu preparative HPLC System consisting of a controller, 2 LC8A pumps, and UV-Vis detector. The purified peptide was analysed by analytical RP-HPLC ( FIG. 5 ). Fractions of >99% purity were subjected either by RP-HPLC or IEX to salt exchange and concentrated to remove organic solvent either by rota or reverse osmosis and subsequently lyophilized to get final API with purification step yield of 70% or above.The MS spectrum of octreotide is depicted in FIG. 6 .
[0148] While the present invention is described above in connection with preferred or illustrative embodiments, these embodiments are not intended to be exhaustive or limiting of the invention. Rather, the invention is intended to cover all alternatives, modifications and equivalents included within its spirit and scope, as defined by the appended claims.
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This invention relates a process for preparing octreotide and derivatives thereof. The starting material, Cys(Trt)-2-Chlorotrityl resin is coupled with various amino acids to obtain a protected heptapeptide of formula (2): Boc-D-Phe-Cys(Trt)-Phe-D-Trp-Lys(Boc)-Thr(OBut)-Cys(Trt)-2-Chlorotrityl resin. The linear protected peptide of formula (2) is cleaved from the support using TFA5TIS and water to yield linear protected peptide of formula (3) Boc-D-Phe-Cys(Trt)-Phe-D-Trp-Lys(Boc)-Thr(OBut)-Cys(Trt)-OH Linear protected heptapeptide of formula (3) is deprotected to yield heptapeptide of formula (6): D-Phe-Cys-Phe-D-Tip-Lys-Thr-Cys-OH; which is cyclized using hydrogen peroxide and to the cyclic peptide of formula (7) D-Phe-Cys-Phe-D-Trp-Lys-Thr-Cys-OH; threoninol is coupled at C terminal to yield octreotide. Alternatively threoninol is coupled to the heptapeptide of formula (3) to yield protected octapeptide of formula (4) Boc-D-Phe-Cys(Trt)-Phe-D-Trp-Lys(Boc)-Thr(OBut)-Cys(Trt)-Thr-OL which is subsequently deprotected to yield linear octapeptide of formula (5) D-Phe-Cys-Phe-D-Trp-Lys-Thr-Cys-Thr-OL and cyclized with hydrogen peroxide to yield cyclic octreotide with a yield of >95%.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a division of U.S. application Ser. No. 10/262,249, filed on Sep. 30, 2002, to be issued as U.S. Pat. No. 6,747,084 on Jun. 8, 2004.
BACKGROUND OF THE INVENTION
[0002] Pressure-sensitive adhesives (sometimes referred to as PSA) which are permanently tacky in dry form at room temperature are widely used for making labels and tapes which can be applied to a variety of substrates and adhere on application of slight pressure. They are also used for laminating polymeric films such as poly(vinyl chloride) and polyester Mylar, silicone coated papers, and film release liners for forming decals and other related products.
[0003] Water based pressure-sensitive adhesives are of interest because of their low VOC emissions. Although the performance is not equivalent to solvent based pressure-sensitive adhesives, they satisfy emission standards and are easy to process. Common types of pressure-sensitive adhesives, both water based and solvent based, are derived from acrylic ester based copolymers, such as alkyl acrylate and alkyl methacrylate copolymers.
[0004] The following patents and articles are representative of acrylic based pressure-sensitive adhesives:
[0005] Hidalgo, et al. “Polystyrene(1)/poly(butyl acrylate-methacrylic acid)(2) core-shell emulsion polymers. Part Il: Thermomechanical properties of latex films,” Colloid and Polymer Science, 1992, Vol. 270, pages 1208-1221, disclose the formation of polystyrene/poly(butyl acrylate-methacrylic acid) latexes by a two stage process. Initially, a polystyrene seed is prepared and then the butyl acrylate and methacrylic acid polymerized in the presence of the seed forming a core/shell polymer in a ratio of ⅔.
[0006] EP 0 593231 A1 discloses the formation of pressure-sensitive acrylic adhesives by the addition of low molecular weight (<7,000) ethylene oxide-block-propylene oxide copolymer surfactants to acrylic pressure-sensitive adhesives for the purpose of improving low temperature adhesion. These pressure-sensitive adhesives are based upon 2-ethylhexyl acrylate and acrylic and methacrylic esters of C 4-12 alkanols, such as butyl acrylate.
[0007] U.S. Pat. No. 6,225,401 discloses filterable aqueous dispersions of pressure-sensitive adhesive suited for labels formed by copolymerizing acrylic or methacrylic esters in the presence of an inhibitor. A wide variety of hardening comonomers can be included in the emulsion polymerization process and these include the styrenes, acrylonitrile, vinyl esters, and so forth.
[0008] U.S. Pat. No. 6,254,985 discloses aqueous emulsions of pressure-sensitive adhesives base upon esters of acrylic and methacrylic acid. The patentees disclose the use of an emulsifier consisting of at least 5% by weight of aromatic carbon atoms, typically including at least two sulfonate groups to improve adhesion and cohesion.
BRIEF SUMMARY OF THE INVENTION
[0009] The present invention is directed to an improvement in a process for preparing an aqueous emulsion of a pressure-sensitive adhesive based upon acrylic esters which have a good balance of adhesive and cohesive properties and to the resulting emulsion. In the basic process, a pressure-sensitive adhesive formulation comprised of at least one ester of acrylic or methacrylic acid is polymerized in the presence of water and an emulsifier thereby forming an emulsion polymerized pressure-sensitive adhesive polymer. The improvement resides in effecting the polymerization of said pressure-sensitive adhesive formulation comprised of an ester of acrylic or methacrylic acid and a styrene containing polymer containing at least 80 percent by weight styrene, said styrene containing polymer present in an amount of from 5 to 30 percent by weight of the pressure-sensitive adhesive formulation.
[0010] Significant advantages of the process and product can be realized and they include:
[0011] an ability to include a small proportion of a low cost filler polymer into an aqueous pressure-sensitive adhesive based upon acrylic and methacrylic esters without adversely affecting the adhesive properties;
[0012] an ability to overcome deficiencies in film formation from blends of polymers, e.g., blends of polystyrene and acrylic and methacrylic copolymers;
[0013] an ability to include a low cost “filler” into a pressure-sensitive adhesive by a simple method without the need for special equipment;
[0014] an ability to prepare a pressure-sensitive adhesive with high Tg polystyrene filler in one reaction, and in a single reactor, while maintaining the performance advantages of the pressure-sensitive adhesive including those formed by the blend method; and,
[0015] an ability to eliminate the need for the high Tg polystyrene latex to be of a specific particle size, expensive macromers, and minimum amounts of surfactants.
DETAILED DESCRIPTION OF THE INVENTION
[0016] Emulsion polymerization of a pressure-sensitive adhesive formulation comprised of esters of acrylic and methacrylic acid including ethylenically unsaturated monomers to produce aqueous based pressure-sensitive adhesive polymer emulsions is well known. A representative pressure-sensitive adhesive formulation is comprised of an aqueous polymer dispersion wherein the polymer is comprised of polymerized units, based on the total weight of units, of (a) from 60 to 95% by weight of at least one C 6-12 alkyl acrylate; (b) from 0 to 10% by weight of an ethylenically unsaturated compound having a glass transition temperature of above 0° C. and contain no functional groups other than ethylenically unsaturated group; (c) from 0 to 10% by weight of an ethylenically unsaturated compound having at least one acid or acid anhydride group; and (d) from 0 to 20% by weight of a further ethylenically unsaturated compound; the weight percentages based on the total weight of polymer. Typically, unsaturated compounds in group (c) and (d) are included at less than 5% each, when used. Thus, compounds in group (c) and (d) comprise a small proportion of the pressure-sensitive adhesive.
[0017] Particularly suitable alkyl acrylates in group (a) are 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate or dodecyl acrylate.
[0018] Monomers in group (b) can include methyl methacrylate, methyl acrylate, n-butyl acrylate and tert-butyl acrylate; vinyl esters of C 1-20 carboxylic acids such as vinyl laurate, stearate, propionate, the vinyl ester of Versatic acid, and vinyl acetate; vinyl aromatics such as styrene, and so forth. Methyl methacrylate is preferred.
[0019] Examples of group (c) monomers can include acrylic and methacrylic acid, maleic acid, or maleic anhydride. Group (d) monomers can include C, to C 10 hydroxyalkyl (meth)acrylates.
[0020] There are two mechanisms in the process for forming the pressure-sensitive adhesive including the styrene containing polymer, e.g., polystyrene filler. In one mechanism, a styrene containing polymer is dissolved in a pressure-sensitive adhesive formulation comprised of a mixture of monomers. The resulting solution, then, is emulsified with surfactants and water and, with the aid of energy supplied by high shear mixing, converted to a stable emulsion of relatively small particle size particles. The resulting emulsion is polymerized by emulsion polymerization. In a second method, a seed latex of styrene polymer is prepared by emulsion polymerization and the pressure-sensitive adhesive formulation emulsion polymerized in the presence of the seed latex. The second method has the advantage of allowing for reduced emulsifier in the final product, elimination of high shear mixing and allowing the reaction to be carried out in a single reactor.
[0021] The styrene containing polymer is one containing at least 80% by weight styrene and typically one containing 100% styrene by weight. Optional monomers that may be included in producing styrene containing polymers are α-methyl styrene, ρ-methylstyrene, acrylonitrile, methacrylonitrile, methacrylonitrile, methyl methacrylate and trace levels of other monomers leading to a high Tg polymer, at least 80° C.
[0022] The styrene copolymer is incorporated into the pressure-sensitive adhesive in an amount from 5 to 30% by weight, which includes the base pressure-sensitive adhesive polymer and the styrene containing polymer. Levels above about 30% by weight detract from the performance of the pressure-sensitive adhesive. Levels below about 5% by weight, although not adversely affecting the properties of the pressure-sensitive adhesive, do not afford the low cost advantages. Preferably, the level of styrene copolymer is from 10 to 20% by weight.
[0023] Many of the pressure-sensitive adhesive formulations include styrene as a comonomer. Usually, styrene is included at low levels, e.g., below 5% by weight. High levels of styrene in the pressure-sensitive adhesive formulation lead to unacceptably high Tg of the pressure-sensitive adhesive polymer. Such high levels of styrene adversely affect loop tack in the PSA. Accordingly, the ability to incorporate an amount of styrene via copolymerization into the pressure-sensitive adhesive polymer equal to that where the pressure-sensitive adhesive formulation is polymerized in the presence of styrene containing polymer as in the hybrid composite is not an acceptable option.
[0024] The pressure-sensitive adhesive formulation is designed to lead to a hybrid composite having a Tg of −25° C. to −90° C., preferably 40° C. to −75° C. and a loop tack adhesion value greater than 1 pound per linear inch (pli); preferably greater than 1.5 pli, according to Pressure-sensitive Test Council (PSTC) test method PSTC-5, tested on stainless steel panel. Even though the Tg is not as well defined as in a single polymer, the Tg of the composite affords an approximation.
[0025] Polymerization of the seed latex, as well as the pressure-sensitive adhesive formulation can be initiated by thermal initiators or by a redox system. A thermal initiator is typically used at temperatures at or above about 70° C. and redox systems are preferred at temperatures below about 70° C. The amount of thermal initiator used in the process is 0.1 to 3 wt %, preferably not more than about 0.5 wt %, based on total monomers. Thermal initiators are well known in the emulsion polymer art and include, for example, ammonium persulfate, sodium persulfate, and the like. The amount of oxidizing and reducing agent in the redox system is about 0.1 to 3 wt %. Any suitable redox system known in the art can be used; for example, the reducing agent can be a bisulfite, a sulfoxylate, ascorbic acid, erythorbic acid, and the like. The oxidizing agent can include hydrogen peroxide, organic peroxide such as t-butyl peroxide, persulfates, and the like.
[0026] Chain transfer agents, well known in the aqueous emulsion polymerization art; are typically used but are not required. Examples include dodecyl mercaptan, mercaptocarboxylic acids, and esters of mercaptocarboxylic acid. The chain transfer agent is added at levels of about 0.01 to 0.5 wt %, preferably 0.02 to 0.15 wt %, based on the weight of monomers.
[0027] Effective emulsion polymerization reaction temperatures range from about 50 to about 100° C. depending on whether the initiator is a thermal or redox system.
[0028] The emulsifying agents which are suitably used are typically anionic, nonionic or blends thereof. Suitable nonionic emulsifying agents include polyoxyethylene condensates. Polyoxyethylene condensates may be represented by the general formula: R—(CH 2 CH 2 O—) n H where R is the residue of a fatty alcohol containing 10 to 18 carbon atoms, an alkylphenol, a fatty acid containing 10 to 18 carbon atoms, an amide, an amine, or a mercaptan, and where n is an integer of 1 or above. The Igepal surfactants are members of a series of alkylphenoxy-poly(ethyleneoxy)ethanols having alkyl groups containing from about 7-18 carbon atoms, and having from about 4 to 100 ethyleneoxy units, such as the octylphenoxy poly(ethyleneoxy)ethanols, nonylphenoxy poly(ethyleneoxy)ethanols, and dodecylphenoxy poly(ethyleneoxy)ethanols. Examples of nonionic surfactants include polyoxyalkylene derivatives of hexitol (including sorbitans, sorbides, mannitans, and mannides) anhydride, partial long-chain fatty acid esters, such as polyoxyalkylene derivatives of sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate and sorbitan trioleate.
[0029] Suitable anionic emulsifying agents include the monovalent salts of the sulfates of the above mentioned nonionics, mono or disodium salts of sulfosuccinates half esters or diesters, sodium salts of alkylbenzene sulfonates. A single emulsifying agent can be used, or the emulsifying agents can be used in combination. When combinations of emulsifying agents are used, it is advantageous to use a relatively hydrophobic emulsifying agent in combination with a relatively hydrophilic agent. A relatively hydrophobic agent is one having a cloud point in 1% aqueous solution below 190° F. (88° C.) and a relatively hydrophilic agent is one having a cloud point in 1% aqueous solution of 190° F. (88° C.) or above. The concentration range of the total amount of emulsifying agents useful is from 0.5 to 5% based on the aqueous phase of the latex regardless of the solids content. The surfactant package is typically used in an amount of from 2 to 7 wt % of the emulsions.
[0030] An alkaline buffering agent of any convenient type that is compatible with the stabilizing agent may be used if it is desired to maintain the pH of the system at a desired value. The amount of buffer is generally about 0.1 to 0.5 wt % based on the monomers.
[0031] The following examples are intended to illustrate embodiments or the invention and are not intended to restrict the scope thereof.
EXAMPLE 1
PRESSURE-SENSITIVE ACRYLIC WITH 20% POLYSTYRENE DISSOLVED AND THEN EMULSIFIED
Polymerization Procedure
[0032] Emulsion polymerization of a pressure-sensitive adhesive was carried out in conventional manner. More specifically, a 1 gallon reactor was purged with nitrogen and then an “Initial Charge” including a fraction of the monomers employed in the pressure-sensitive adhesive was added. The contents were heated to 80° C. Polymerization of the monomers in the initial charge were effected by the addition of a 2.73% solution of sodium persulfate (1.75 ml) over 10 minutes at a rate of 0.175 g/min.
[0033] A polymerizable emulsion mix was formed by mixing the “Pressure-Sensitive Adhesive Formulation” with the “Emulsifier” in a high shear mixer. After initiation, the initiator, polymerizable emulsion mix, and buffer were added over a period of about 4 hours. After addition of the initiator and polymerizable emulsion mix, the reaction was maintained for an additional 15 min at 80° C. The reaction contents were cooled to 75° C. and 2 ml of 1% iron was added. To finish the reaction, redox delays were added, initially 4 ml of each was added, and the reaction held for 30 min. This procedure was repeated as necessary until the free monomer was reduced to below 0.1%.
Initial Charge Component Amount (g) 1. DI water 44.3 2. Sodium pyrophosphate 3% 42.3 3. Emulsifier K30 (29.9%) 0.317 4. Aerosol A102 (32%) 2.45 5. 2-Ethylhexyl acrylate 28.05 6. Acrylic acid 0.15 7. Styrene 0.68 8. Methyl methacrylate 2.8
[0034] Pressure-Sensitive Adhesive Formulation
Component % Component Amount (g) Methyl methacrylate 1.74 10.45 2-Ethylhexyl acrylate 72.7 436.25 Acrylic acid 97% 0.39 2.34 Styrene 1.48 8.89 Vinyl acetate 2.08 12.48 Polystyrene 20 120 2-Hydroxypropyl acrylate 1.6 9.59 Total 100 600
[0035] Emulsifier
Component g 1. D.I. water 282 2. Sodium Vinyl Sulfonate. (25% nv) 10.32 3. Aerosol A102 (32% nv) 19.00 Total 311.32
[0036] Initiator
1. DI water 91 g 2. sodium persulfate 9 g Total 100 g
[0037] Buffer
1. di water 38.36 g 2. sodium citrate 11.64 g Total 50 g.
[0038] Redox Delays
1. DI. Water 62.61 g 2. t-BHP (70%) 1.08 g 1. DI water 62.42 g 2. SFS 0.61 g
[0039] Final Properties of Pressure-Sensitive Adhesive
pH 5.0 % solids 55.2 Viscosity at 20 rpm, #2 spindle 170 cps
EXAMPLE 2
PRESSURE-SENSITIVE ADHESIVE FORMULATION POLYMERIZED IN THE PRESENCE OF POLYSTYRENE SEED LATEX
Polymerization Procedure
[0040] The polymerization procedure of Example 1 was followed. In general terms the following steps were implemented:
[0041] 1. Reactor was purged with nitrogen.
[0042] 2. First stage: added initial charge consisting essentially of styrene as the monomer and heated to 78° C. Added initiator (9% solution of sodium persulfate) 4.4 grams. Waited for exotherm. In this first stage, a polystyrene seed latex was formed.
[0043] 3. After the first stage and the formation of polystyrene seed latex, the initiator (3.6%), buffer, and polymerizable emulsion mix were added over about 4 hours.
[0044] 4. After the addition of the polymerizable emulsion mix, the reaction product was heated for an additional hour at 90° C.
[0045] 5. When the reaction was complete, the free monomer was checked. The reaction product was cooled to 75° C. and post-treated with the redox delays to reduce the free monomer to below 0.1%.
Initial Charge: Polystyrene Seed Latex Formation
[0046] [0046] Material g DI water 290 Versene 220 0.768 Emulsifier K30 (29.9%) 1.4 Genopol 1879 (40%) 9.3 Sodium bicarbonate 0.06 Styrene 123.9 Total 425.428
[0047] Pressure-Sensitive Adhesive Formulation
Monomer % Monomer Amount, g Methyl methacrylate 1.78 12.64 2-Ethylhexyl acrylate 81.43 571.72 Acrylic acid 97% 0.51 3.58 Styrene 1.78 12.50 Vinyl acetate 5.29 37.14 2-Hydroxypropyl acrylate 2.03 14.25 Butyl acrylate 7.18 50.41 Total 100 702.24
[0048] Emulsifier
Component Amount, g D.I. water 114.5 Sodium vinyl sulfonate (25% v) 17.53 Disponil FES 32 (30% nv) (30% nv) 32.48 Aerosol A102 (32% nv) 3.03 Total 167.54
[0049] Initiator
1. DI Water 96.4 g 2. Sodium persulfate 3.6 g Total 100 g
[0050] Buffer
1. DI water 46.12 g 2. Sodium citrate 14.0 g Total 60.12 g
[0051] Redox Delays
1. DI. Water 33.9 g 2. t-BHP (70%) 1.08 g 1. DI water 34.39 g 2. SFS 0.61 g 3. Iron (ferrous sulfate) solution; 2 ml of 1% solution; mixed in first
[0052] Final Properties of Pressure-Sensitive Adhesive
pH 4.5 % solids 57.3 Viscosity 20 rpm, #3 spindle 950 cps
EXAMPLE 3
EVALUATION OF PRESSURE-SENSITIVE ADHESIVES
[0053] The emulsions of Examples 1 and 2 were used to form the various test samples and were compared to emulsion blends which consisted of a pressure-sensitive adhesive latex having the formulation of Example 1 or Example 2 (pressure sensitive adhesive formulation only) and a polystyrene latex. The latex samples were adjusted to a pH of 7. The emulsions were directly coated onto 2 ml Mylar at a coat weight of 25 g/m 2 . The resulting tapes were applied to various substrates, e.g., stainless steel (SS) and low density polyethylene (LDPE), and evaluated for peel strength. Some of the samples were evaluated for shear based upon a test where a ½ inch film square was exposed to a 500 gram weight (referred to as ½×½×500) and another where a 1 inch square was exposed to a 1000 gram weight and evaluated (referred to as 1×1×1000). Another test was the measured peel to corrugated cardboard test conducted at 35° F. (2° C.) or 20° F. (−7° C.); referred to as 35 CC and 20 CC, respectively. (The sample preparation and test methods used to evaluate the adhesives or coatings in the examples were based on industry standard tests. They are described in publications of the Pressure Sensitive Tape Council (PSTC), Glenview, Ill.) The results are presented in Tables 1-5.
TABLE 1 Peel Peel Peel Shear SS (pli) LDPE (pli) 35 CC (pli) ½ × ½ × 500 Example 1 2.5 1.25 0.83 2 15% Blend 1.45 0.92 0.92 1 30% Blend 1.36 0.98 0 1.9 Control 2.4 1.15 2.2 0.5
[0054] Table 1 compares the hybrid composite latex of Example 1 with the method of latex blending, i.e., blending of a polystyrene latex with a control pressure-sensitive adhesive (same monomer composition as set forth in the pressure-sensitive adhesive formulation as in Example 1). The pressure-sensitive adhesive formulation alone was referred to as the “control” and blends of 15% and 30% polystyrene by weight were compared. As can be seen from Table 1, the polystyrene, whether as a composite or blend, and even though deemed a filler, maintains pressure-sensitive adhesive performance properties of the control pressure-sensitive adhesive. The Example 1 PSA compares favorably with the control in every area except low temperature peel, i.e., 35 CC. It is substantial equal to 35 CC peel for the 15% blend and significantly better than the 30% blended sample.
[0055] If styrene were copolymerized into the pressure-sensitive adhesive at a 20% level, that would increase the Tg by about 20° C. It would be like raising the Tg of the PSA from −60° C. to −40° C. That result would adversely affect the loop tack and possibly other properties of the pressure-sensitive adhesive.
[0056] Table 2 shows results using three sources of polystyrene. Samples A, B and C were prepared in accordance with Example 1. Sample A used a high molecular weight commercial polystyrene, sample B employed a low molecular weight commercial polystyrene, and Sample C used polystyrene beverage cups dissolved in monomer.
TABLE 2 Shear Peel SS (pli) Peel LDPE (pli) Peel 35 CC (pli) 1 × 1 × 1000 A 2.5 1.25 0.83 25 B 2.4 1.5 0.85 36 C 2.2 1.4 0.85 74
[0057] All samples gave performance properties that were very similar thus illustrating that the performance properties were not greatly influenced by the differing polystyrene polymers employed.
[0058] Table 3 compares results of the hybrid composite of Example 1 including polystyrene, a control of PSA alone, and Example 1 composite with tackifier.
TABLE 3 Peel Peel Peel Shear SS (pli) LDPE (pli) 35 CC (pli) 1 × 1 × 1000 Example 1 2.5 1.25 0.83 25 Example 1 + 4 3 1.1 27 Tackifier A Control 2.4 1.15 2.2 7
[0059] As expected, addition of tackifier resin improved the peel values of the hybrid composite of Example 1 with little effect on shear.
[0060] In summary, the results show that the method of incorporating a styrene containing polymer, e.g., a polystyrene filler into a pressure-sensitive adhesive formulation thereby forming a hybrid composite latex is suitable for PSA applications. Performance is not adversely affected, and cost is reduced.
[0061] In the preferred method of preparation, i.e., polymerizing the pressure-sensitive adhesive formulation in the presence of a polystyrene seed latex, the polymer filler has an overall positive impact on performance properties and cost. Performance results for the latex made by example 2, compared with a PSA control and a blend of PSA with polystyrene latex, are shown in Table 4.
TABLE 4 Peel Peel Peel Shear CC (pli) LDPE (pli) 20 CC (pli) 1 × 1 × 1000 Example 2 1.1 2 1.1 7.9 20% Blend 0.58 1.2 0.95 15.2 Control 1.4 0.9 0.9 6.5
[0062] The preferred example shows some differentiation from the latex blend and is more like the PSA control. As in Table 3, addition of a tackifying resin to the 20% blend will improve peel on LDPE and corrugated, Table 5. In fact, the performance of the example 2 latex compares favorably with both the tackified blend and a tackified general purpose commercial label adhesive, Table 5.
TABLE 5 Peel Peel Peel Shear CC (pli) LDPE (pli) 20 CC (pli) 1 × 1 × 1000 Example 2 1.1 2 1.1 7.9 20% Blend + 1.2 2 1.1 4.9 Tackifier A Tackified 1.0 2.6 0.85 26 Commercial GP
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The invention is directed to an improvement in a process for preparing an aqueous emulsion of pressure-sensitive adhesive based upon acrylic esters having a good balance of adhesive and cohesive properties and to the resulting emulsion. In the basic process, a pressure-sensitive adhesive formulation comprised of at least one ester of acrylic or methacrylic acid is polymerized in the presence of water and an emulsifier thereby forming an emulsion polymerized pressure-sensitive adhesive. The improvement resides in effecting the polymerization of said pressure-sensitive adhesive formulation comprised of at least one ester of acrylic or methacrylic acid in the presence of from 5 to 30 percent by weight of a styrene containing polymer containing at least 80 percent by weight styrene.
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REFERENCE TO RELATED APPLICATIONS
The improved shifting tool of co-pending U.S. application Ser. No. 422,739, filed Sept. 24, 1982, is used as a component of apparatus of this invention. The valve of co-pending U.S. application Ser. No. 368,690, filed Apr. 15, 1982, may be used in the invention system for well producing operations.
FIELD OF THE INVENTION
This invention relates to apparatus useful in well flow control and more particularly to apparatus used in an injection system in dual tubing string wells operated by through flow line (TFL)/pumpdown methods.
DESCRIPTION OF THE PRIOR ART
Water or gas is often injected into hydrocarbon producing formations in wells after the formation pressure decreases and formation hydrocarbons will no longer flow to surface. U.S. Pat. Nos. 3,319,717 and 3,455,382, both to C. V. Chenoweth, show apparatus and systems useful for injecting fluids in multizone wells not operated by TFL/pumpdown methods. The multiple formation system shown in U.S. Pat. No. 3,319,717 is not selective because one formation cannot be opened to injection while others remain closed.
Previous systems for TFL/pumpdown wells using tool strings pumped down for injection often could not be operated because pressured pump out fluid supplied underneath the tool string to move the tool string back to surface would flow into the open formation below the tools at relatively low pressure and not increase tubing pressure sufficiently under the TFL/pumpdown tool strings to move them up the tubing to be pumped out.
SUMMARY OF THE INVENTION
The system and apparatus of this invention provide for injection into a selected formation in each tubing string in a multiple formation dual tubing string well, operable by TFL/pumpdown methods, having two tubing strings and a connecting H-member below the bottom packer, wherein the formation zones are isolated by well packers and there is a sliding sleeve valve between packers in one tubing string running through the isolating packers, selectively openable for tubing-formation flow by a TFL/pumpdown tool string carrying a pressure openable injection valve. If desired, sliding sleeve valves may be used in both tubing strings between packers.
There are two pressure openable injection valves used in this well system, both of which seal across an open sliding sleeve valve and close the open sleeve valve to tubing-formation flow. One embodiment of the injection valve closes to flow through when the valve is pressure opened for injection flow through wall ports into a formation. The other injection valve remains open to flow through when open for injection flow and is closed to flow through by insertion of a closing prong which has a through flow passage.
One formation in the dual tubing well may be opened for injection by installing and pressure opening an injection valve closed to flow through. After completing injection, the valve closed to flow may be pumped out of a pumpdown well conventionally by pumping down the other tubing string across through the H-member and up under the valve closed to flow through to move its tool string up, closing the sliding sleeve valve, which prevents flow into the annulus and formation and directs pumped fluid up tubing pumping the tool string back to surface.
To open two formations in the well for injection, an open to flow through injection valve should be installed first in the higher pressure formation tubing and a closable to flow through injection valve installed second in the low pressure formation tubing. On pressure opening, the injected flow is from tubing through injection valves and open sliding valves into annuli and formations as the low pressure formation injection valve is closed to flow through and the high pressure formation injection valve is open to flow through.
After injection operations are completed, the procedure for closing both formations and retrieving both injection valves by TFL/pumpdown methods would be to pump a tool string carrying a closing prong having a through flow passage down the first tubing and close the open to flow through injection valve to injection flow. Next, pump a tool string down the second tubing for retrieval of the low pressure formation injection valve. Now, with both formations closed to injection flow, the second low pressure formation sliding valve may be closed by pumping down the first string through the closing prong and below to cross over through the H-member and up under the second tool string, moving it up, closing the second formation sliding sleeve and releasing the tool string for retrieval of the injection valve and tool string to surface. Now, pumping down the second string through the H-member over into and up the first string and through the prong moves the tool string up to close the first formation sliding sleeve valve and moves the released tool string, prong and injection valve up the first tubing to surface.
An object of this invention is to provide a well injection system for multiple formation wells.
Another object of this invention is to provide an injection system for wells wherein injection devices may be installed or removed using TFL/pumpdown methods.
Another object of this invention is to provide a well injection system wherein a selected formation in each tubing may be opened for injection flow.
A fourth object of this invention is to provide a well injection system wherein the formations may be opened for injection flow in a predetermined sequence.
Another object of this invention is to provide injection valves which may be opened for injection flow by a predetermined pressure.
Another object of this invention is to provide an injection valve which closes to flow through when opened for injection flow by a predetermined pressure.
Also, an object of this invention is to provide an injection valve which is open to flow through when opened for injection flow by a predetermined pressure.
BRIEF DESCRIPTION OF THE DRAWING FIGURES
FIG. 1 is a schematic representation drawing of a well completed to utilize the system and injection valves of this invention.
FIG. 2 is a schematic drawing of a TFL pumpdown tool string including the injection valves of this invention.
FIGS. 3A and 3B is a half-sectioned elevational drawing of an injection valve of this invention open to flow through and closed to injection flow through wall ports.
FIGS. 4A and 4B is a half-sectioned drawing in elevation of another embodiment of the injection valve of this invention shown open for injection flow through wall ports and closed to flow through.
FIG. 5 is a half-sectioned drawing in elevation of a closing prong useful in operating the invention system.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1, there is shown an earth borehole 10 passing through earth formations 11 having a casing 12 therein, wherein there has been installed an H-member 13 and dual packers 14 with two tubing strings 15 running through each packer. The packers, when installed and set, create tubing-casing annuli 16 and define the formation zones within the casing. Flow between the earth formations and casing annuli may occur through perforations 17. Flow between the tubing and casing annuli may occur through ports 18 in sliding sleeve valves 19 in tubing, which are selectively opened and closed to flow by pumping a tool string 20 down tubing into or up tubing out of each sliding sleeve valve.
The tool string 20, shown in FIG. 2, consists of a lock mandrel section 21, a selective improved shifting tool section 22 (of a related co-pending application), each having a through flow passage, and a flow valve 23 (FIG. 3) of this invention or a flow valve 24 (FIG. 4) of this invention. When a tool string is attached to a pumpdown locomotive and running tool (not shown) and pumped down tubing into a sliding sleeve valve, the improved shifting tool selectively engages and opens the sleeve valve with the closed flow valve positioned and sealing across open sleeve valve ports 18.
FIG. 3 shows the injection valve assembly 23 open to flow through wherein there is provided a connector cap 25 attached to an upper connector 26 by thread 27 and positioned thereon by jam nut 28, for connecting the injection valve to the lower end of an improved shifting tool. The lower end of the upper connector is threadedly connected at 29 to the upper end of body 30 with ports 31 and sealed thereto with resilient seal 32. Mounted on the upper outside of the ported body is a wear ring 33 positioned between an outer body shoulder and ring 34 and retained there by retaining ring 35 housed in a groove on the body. A molded resilient seal ring 36 is positioned on and seals to the body and is retained there by another retaining ring 35a housed in a lower groove on the body. Slidably disposed in body seal bores 30a and 30b is a piston valve 37, sealed to bores 30a and 30b with resilient seals 38 and 39, respectively, to form an annular differential area on the upper end of the piston valve. Positioned below ports 31 on the body is a second seal ring 36a, which also seals on the body, a second ring 34a and a second wear ring 33a . The second wear ring is positioned between a lower shoulder on the body and ring 34a and both rings are retained there by a third retaining ring 35b housed in a groove on the lower body. Second seal ring 36a is retained between third and fourth retaining rings 35c by the fourth retaining ring housed in a body groove below the ports. A spring 40 is disposed around a lower portion of the piston valve and in a bore 30c bored from the lower end of the body. Attached to the lower end of the piston valve with threads 41 is a spring retainer 42 having a groove 43. A shear screw 44, installed in threads 45 near the lower end of the body, protruding into groove 43, releasably positions the spring retainer and attached piston valve in up position, closing the body ports to flow while the compressed spring is biasing the retainer and valve down toward the valve open position. Connected to the lower end of the body 30 by threads 46 is a housing 47. There is a longitudinal flow passage 48 through the injection valve 23.
Referring now to FIG. 4, there is shown another embodiment of the injection valve of this invention open to port flow and closed to flow through. The injection valve assembly 24 of FIG. 4 is identical to the flow valve 23 except connected to the lower end of the piston valve 37 by threads 41 is a lower valve 49 having a groove 43 and spaced apart resilient seals 51 and 51a mounted in grooves thereon. Connected to the lower end of the body 30 in flow valve 24 with threads 46 is a lower valve housing 52, sealed to the body with a resilient seal 53. The lower housing is provided with flow ports 54 and an internal seal bore 55 wherein seals 51a and 51 may seal above and below ports 54 to close off flow through ports 54 into flow passage 48.
FIG. 5 shows a closing prong assembly 56 for valve 23 having a flow passage through. On the upper end of the prong is a thread 57 on rod 58 for attaching the prong assembly to the lower end of a pulling tool (not shown). Attached to the lower end of the rod by thread 59 is a mandrel 60 on which is mounted an upper resilient seal 61 between a lower shoulder on the rod and an upper shoulder on the mandrel. A lower mandrel 62 which carries a lower resilient seal 61 between a lower shoulder on the mandrel and a shoulder on the lower mandrel is connected to the upper mandrel by thread 63 and sealed thereto by resilient seal 64. A longitudinal flow passage 65 is provided in the lower portion of the prong which connects with ports 66 to exit above upper seal 61.
BEST MODE FOR CARRYING OUT THE INVENTION
Install a shear pin 44 which will shear at the desired tubing pressure in first injection valve 23, which is the lower section of tool string 20. Attach the tool string to a running tool with pumpdown locomotives and pump the tool string down the tubing 15 having the highest pressure formation sliding sleeve valve 19 in a well completed for TFL/pumpdown operation as shown in FIG. 1. The shear pin positions the spring retainer 42 and connected piston valve 37 up, and resilient seal 38 seals in seal bore 30a while seal 39 seals on the piston valve closing ports 31 to flow. As this first tool string enters the higher pressure sliding sleeve valve, the improved shifting tool 22 positions seals 36 and 36a, FIG. 3, across sleeve valve ports 18 with closed flow valve ports 31 opposite and opens the sliding sleeve valve for flow through ports 18, annulus 16, perforations 17 to formation 11. The lock mandrel 21 in the tool string locks the injection valve in position in the sliding sleeve valve and also locks the sliding valve open. The released running tool and tool string are now pumped back to the surface.
Next, a shear pin 44 for the second injection valve 24, FIG. 4, should be selected, which will shear at a lower pressure than pin 44 selected for flow valve 23 and installed in flow valve 24. The shear pin positions the piston valve 37 and connected lower valve 49 up closing ports 31 to flow while lower ports 54 are open to flow. A tool string 20, with the closable to flow through flow valve 24 lower section, is pumped down the second tubing. As the tool string 20 enters the lower pressure formation sliding sleeve valve, the improved selective shifting tool 22 engages the sliding valve, positions closed to flow ports 31 opposite sliding valve ports 18 and opens ports 18 to flow. Lock 21 in tool string 20 locks the tool string in the sliding sleeve valve and also locks the sliding valve open. The released running tool and tool string are now pumped back to the surface.
Now, both injection valves installed in tubing may be opened as required for injection flow by applying appropriate pressure at the surface to tubing. Pressure to open the injection valve 24, FIG. 4, in the second tubing sliding sleeve valve for injection flow and close the valve to flow through can be applied down both tubing strings onto the differential sealed area between body bores 30a and 30b on the upper end of piston valve 37, shearing pin 44, forcing piston valve 37 and lower valve 49 down, moving resilient seal 38 from seal bore 30a, opening ports 31 to flow while moving lower resilient seal 51 below ports 54 in seal bore 55 and upper resilient seal 51a into seal bore 55 above ports 54, thus closing ports 54 to flow from flow passage 48.
Injection flow may now occur between second tubing and formation through lock 21, shifting tool 22, closed to flow through flow passage 48 and ports 31 in injection valve 24, ports 18 in low pressure formation sliding valve 19, annulus 16, and perforations 17 and into the lower pressure formation 11.
If desired, the high pressure formation may also be opened for separate injection flow by pressuring the first tubing at surface to a pressure usually about 500 psi greater than the lower pressure formation to act on the differential area on the upper end of piston valve 37 and shear the stronger pin 44 in the injection valve 23 not closable to flow through as shown in FIG. 3. Injection flow may now occur between the high pressure formation and the first tubing string through lock 21, shifting tool 22, open to flow through flow passage 48 and ports 31 in injection valve 23, ports 18 in valve 19, annulus 16 and perforations 17. The higher injection pressures are also transmitted down the tubing, across the H-member and up under the closed to flow through injection valve 24.
After completing well injection operations, the two tool strings with their injection valves may be retrieved and sliding sleeve valves open to each formation closed by pumping a pulling tool string with a closing prong 56 of FIG. 5 attached down the first tubing string in which the open to flow through valve 23 was installed in the higher pressure formation sliding sleeve valve. The closing prong enters and is positioned in the valve 23 when the pulling tool engages the lock 21 of tool string 20 so that upper prong seal 61 seals in the bore of upper connector 26 of valve 23 and lower prong seal 61 seals in the lower bore of piston valve 37 closing ports 31 and the higher pressure formation to injection flow.
A pulling tool may now be pumped down the second tubing string to engage the lock on the tool string with injection valve 24 closed to flow through in the low pressure formation open sleeve valve.
Now, pump past the tool string in the higher pressure formation sliding sleeve valve, through prong ports 66, flow passage 65, down and across H-member 13, up the second tubing string to pump the injection valve 24 and tool string up and out of the lower pressure formation sliding sleeve valve 19, closing the sliding valve ports 18 and the lower pressure formation to flow. Continued pumping will carry the tool string and valve 24 back to surface as the lower pressure formation sliding sleeve valve is closed and pumped fluid cannot enter the formation.
Fluid may now be pumped down the second tubing string through the closed low pressure sliding sleeve valve, through the H-member, up the first tubing string with the open higher pressure sliding sleeve valve with open injection valve 23 that has been closed to formation flow by closing prong 56. Fluid pumped up the tubing through prong flow passage 65 and ports 66 cannot enter the higher pressure formation and lifts the tool string from the higher pressure sliding sleeve valve 19 closing ports 18 to flow. Continued pumping carries the first tool string back to surface.
Both formations are now closed to flow and the well is in condition to selectively reestablish tubing to formation flow for future injection operations as required.
The preceding specification describes the invention system in a two formation well operated by TFL/pumpdown methods. The system may be expanded for multiple formation wells and may be operated by using wireline tools and methods as well.
The valve of the earlier noted co-pending application may be substituted for injection valves 23 and 24 in the TFL/pumpdown tool strings to operate the well system of this invention as a producing well wherein production flow is from formation to tubing and the valve of the co-pending application acts as a tubing standing valve preventing back flow and injection into formations.
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A well system for injection into a selected formation in each tubing string in a multiple formation dual string well completed for through flow line/pumpdown operation, utilizing a string of tools which may be pumped down tubing to open selected tubing sleeve valves between packers. Each tool string includes a pressure openable injection valve which seals across the open sleeve valve and is opened for formation injection flow at preselected pressures by application of tubing pressure at the surface. One type of injection valve closes to flow through when pressure opened for injection flow. The other injection valve is closed to injection flow on insertion of a closing prong having a through flow passage. Both injection valves and their respective tool strings may be individually retrieved closing sleeve valves in each tubing and the formations to injection.
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CROSS REFERENCE TO RELATED APPLICATION
This is a continuation in part of prior application Ser. No. 512,336, filed Apr. 23, 1990, abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to the field of video display terminals, and more particularly to a mechanism for moving the display of a video display terminal periodically along a path which varies the distance from the display to a viewer, thereby contributing to the relief of eyestrain and the like. More particularly, the invention concerns a compact position varying mechanism which can be incorporated into or mounted under a standard display of a video terminal such as a computer work station.
2. Prior Art
Numerous instances of physical complaint including but not limited to eyestrain, muscle strain, mental fatigue, headaches, stress, sore necks and sore backs and even increased spontaneous abortion rates of pregnant females have been reported by viewers who are required by their jobs to maintain a position in front of a display terminal for many hours each day. Typically, the display of a video terminal is placed immediately adjacent the terminal keyboard, which is usually within the user's reach, thus placing the display rather close to the viewer, in a fixed position. Television viewers who intently watch the screen for long periods for business or for pleasure are also potentially subject to such problems; however, television viewers are not limited to a location within reach of the display and typically station themselves farther from the display than do video terminal users. Among those whose occupations require long term close attention to a display screen of a video terminal include, but are not limited to, stock brokers, typists, word processors, scientist, engineers, data entry persons, computer programmers, students, traffic controllers, telephone order takers, etc.
Long term focusing of the eyes at a fixed, relatively close location may tire the focusing muscles in the viewer's eyes and can cause conditions of myopia (nearsightedness), hyperopia (farsightedness), amblyopia (lazy eye), presbyopia (aging process or eyestrain), learning disabilities from poor vision perception, accomodation (focussing), convergence (centering), strabismus (wandering eye), monocular/binocular vision imbalances, muscle and nerve imbalances or inability of the eye to focus effectively at near and far distances. In order to rest the eye muscles, persons will frequently look away from the screen to focus at some more distant point. With age, many persons find it difficult to change focus rapidly between a distant point and a nearby point, requiring correction via bifocal lenses. However, it is widely accepted that individuals subject to such problems can improve their vision by exercising the eye muscles, i.e., by focusing sequentially at different distances. An optical instrument to carry out this type of exercise is disclosed in U.S. Pat. No. 4,294,522--Jacobs. An instrument to relieve eyestrain in television viewers is disclosed in U.S. Pat. No. 3,813,419--Pennar. Pennar teaches a linearly movable television platform which is supported on a pair of parallel axles extending transversely to the direction of movement. Pennar provides a drive motor connected for rotating one of the axles.
Users of video display terminals can benefit from a device which requires them to exercise the focusing muscles of their eyes during periods of display terminal observation. Moreover, the users will be more comfortable if they are not fixed physically in a particular body position for long periods. Eye exercise and the ability to shift in position comfortably can be obtained by changing the distance and direction of the display terminal from the viewer, particularly in connection with a work station which permits the user to vary the position of the keyboard as well. However, there are certain practical problems encountered in the design and configuration of an apparatus to accomplish these objectives. The apparatus must be compact, and have a relatively low profile, such that the display can be located in an optimal beneficial position. Whereas at least a motor is required in a linear actuator for moving the display, and a typical motor and the mounting means therefor require several inches of height, as shown by Pennar, it is difficult to conceive of a practical device which can move the display without occupying undue space. Furthermore, the mechanism must be extremely smooth and quiet, because any noticeable vibration or movement of the display or noise is irritating and distracting. In short, the mechanism must be all but invisible or transparent to the user, occupying minimal space and operating such that the changing position of the display occurs substantially without the user even noticing that this has occurred.
The present invention provides a mechanism for moving a video display terminal in a periodic path with respect to the viewer, thereby requiring the viewer's eyes to focus at varying distances as the display is moved. The mechanism preferably comprises a base and relatively movable platform, with a motor disposed at the rear of the base, coupled to the shaft of a linear actuator having a low pitch bidirectional helical path for carrying a follower linked to the platform. The height of the apparatus is minimal (e.g., hardly more than the diameter of the actuator shaft plus the thicknesses of the base and platform) and the mechanism is smooth and quiet. The positioning apparatus can be arranged to allow the viewer to select certain parameters of operation, such as the period of displacement or the amplitude of the displacement. The entire package is arranged for minimal effect on the configuration and operation of the video display terminal, while achieving the desired periodic or cyclical displacement of display position.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a means for varying the distance between the display portion of the terminal and a viewer thereof.
It is another object of the invention to provide a means for a viewer to exercise his or her eyes during observation of the display, while permitting the viewer to rearrange body position in a comfortable manner, for minimizing eye and muscle strain.
It is a further object of the invention to improve computer work stations and the like having keyboards associated with a display, by providing a position-varying actuator in or under the display, while minimizing usage of space, noise and vibration such that the actuator is substantially unnoticeable.
These and other objects are accomplished by a display terminal displacement device (integral to or separate from the VDT) comprising a base, and a platform movably supported on the base. A shaft defining a longitudinal axis and an outer surface is mounted for rotation about the longitudinal axis. The shaft has a bidirectional helical groove in the outer surface, with a length which spans at least a portion of the length of the shaft and provides a span of displacement. The shaft is coupled to a motor for rotating the shaft about the longitudinal axis. A movable follower means is received within the groove and coupled for transmitting motion to the display as the shaft rotates. Preferably, the shaft and motor are mounted on the base and the follower is mounted on the platform or display. The display screen can be supported on the platform as it moves, thus causing a viewer to continuously change focal length while focusing on the display screen.
The motor is preferably a synchronous motor and gear arrangement having an output shaft displaced laterally from the motor axis such that the actuator shaft can be disposed immediately adjacent the base while the motor protrudes upwardly. The motor is mounted at a rear of the base, enclosed in a cowling, and the platform has a front lip which extends downwardly over the front of the base, such that the overall physical dimensions of the apparatus are minimal to support movement of the VDT, and in particular its height is very small. The apparatus is substantially unnoticeable to the viewer, who unconsciously changes focal length to continue to focus on the display, thereby achieving eye exercise without disrupting user operation of the computer work station or similar video display terminal.
The apparatus is useful in a method of relieving eyestrain for an operator of a video display terminal having a display screen and an operator control station such as a keyboard. The method includes providing a non-rigid communication means between the display screen and the control station, mounting the display screen on a platform, and moving the platform reciprocally with respect to the operator.
BRIEF DESCRIPTION OF THE DRAWINGS
There are shown in the drawings the embodiments of the invention that are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown in the drawings, which are exemplary. In the drawings,
FIG. 1 is a perspective view of the apparatus for periodically displacing a display terminal according to the invention, shown partially cutaway.
FIG. 2 is a side elevation view of the display of a video display terminal to be periodically displaced relative to the viewer;
FIG. 3 is a side elevation view showing the displacement path of the display generated by the mechanism of the invention;
FIG. 4 is a side elevation view, partly in section, showing the mechanism for moving the display according to the invention, including the motor and bidirectional helical actuator shaft;
FIG. 5 is a front elevation view of the apparatus, also partly in section;
FIG. 6 is a perspective view of a guide holder according to the invention, which moves along the actuator shaft; and,
FIG. 7 is a perspective view of the pivoting follower pin carried by the guide holder according to the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIGS. 1-7, wherein like references are used to indicate like elements throughout, a video display 10 associated with a computer work station or the like is to be periodically varied in position relative to the viewer so as to cause the viewer to vary focal length while using the terminal. The display is a typical video display 10 as shown in FIGS. 1 and 3 in solid lines, and is to be periodically moved in a path as suggested by the broken lines in FIG. 2. The invention is also applicable to displays of other types, particularly those located relatively close to the viewer, who focuses on the screen 12 of the display 10 continuously, and can even be applied to supports for books or other reading or study material.
The exemplary display 10 shown in the drawings is based on, but not limited to, a cathode ray tube type of VDT and has a visual display screen 12 mounted within a cabinet 14. The display screen 12 may be surrounded by a bezel 20, and due to the elongation of the tube and deflection apparatus the cabinet 14 is elongated in a direction extending away from the viewer 16. The cabinet 14 has a rear protrusion or extension 21 and houses components such as the power transformer, filter capacitors and other components associated with the power supply and electronic processing circuitry needed to decode and display signals received from the processor disposed for example in computer box 24, which typically includes disk drives and the like which are manually accessible to the user. The computer keyboard 25 is located in front of box 24 and is coupled to the terminal via an extendable coiled cable 26. The display cabinet 14 may be pivotally mounted on a stand 18 via pivoting union 17, whereby the viewer can adjust the display screen 12 to a comfortable viewing angle.
The most common form of terminal display, namely a separate unit with a cathode ray tube, is shown as an example. The present invention works equally well with flat displays of other kinds, whether or not the displays are integrated with the associated electronics since the invention is directed toward the object of moving the display and not necessarily any associated electronics. However, the invention is particularly applicable to the CRT form of display, which is relatively heavy and bulky.
In FIG. 3, eye 16 represents the viewer, disposed at a position wherein the angle of viewing subtends the display screen 12. F1 is the viewing distance between the eye 16 of the viewer and the screen 12 of the display unit. The apparatus of the invention slowly and periodically moves the display unit along a path P1 having near end 21 and far end 23. This is accomplished by relatively moving the platform supporting the display cabinet 14 having display 12, relative to a stationary base. Dotted outline 15 shows the position of cabinet 14 when moved by the mechanism of the invention to the point on path Pl furthest from the viewer's eye 16. F2 is thus the excursion of the display screen 12 over the course of a complete movement cycle. As shown in FIG. 3, the path P1 preferably is substantially linear, the length of the path being equal to the displacement F2. It is also possible that the path is not linear or is linear in a direction which is not parallel to the center axis of the CRT. If the path includes a component lateral to the center axis of the CRT, the length of the path and the focal length displacement F2 will not be the same. It is the user's option as to whether the displacement will include a lateral component, which can be obtained by placing the apparatus of the invention such that the path of displacement is as desired.
An apparatus for moving the display 10 includes a base 51 in the form of a shallow housing for mounting stationary components on its inner surface. The base 51 may be located on a suitable desk, or table top, overhead mount or side wall at a work station for the terminal, or can be placed as shown on the console box 24 of the terminal. The base 51 is preferably formed from a sheet metal plate with upturned edges to define a lower portion of an enclosure for the operating components mounted on base 51, to prevent dust and dirt from accumulating in the operating components, and to provide an overall attractive and compact package for the moving apparatus. The base 51 may be fixed to the console box 24 or to a desk or table top with, for example, threaded fasteners, or may be simply rested thereon, for example, via anti-skid feet in which case the weight of the apparatus and the display unit will prevent unwanted movement.
A platform 42 for carrying the display unit is supported on the base 51, as shown in FIGS. 4 and 5, which are cross sections through the apparatus parallel to the CRT center axis and perpendicular to the center axis, respectively. The platform 42 is movably carried on upper tracks 47 and lower tracks 48. The upper tracks 47 are attached to an underside of the platform 42, and the lower tracks 48 are attached to a top surface of the base 51. Each of the upper and lower tracks has a horizontal and a vertical surface. Opposing pairs of horizontal and vertical surfaces define opposing grooves along a length of each of the surfaces. The opposing grooves between the horizontal surfaces hold a slide apparatus, such as ball bearings 55, and the opposing grooves between the vertical surfaces hold a slide apparatus, such as ball bearings 56. The slide apparatus 55 movably supports a load including the weight of the platform 42 and the weight of the display unit 10. The slide apparatus 56 as supported between the opposed surfaces of the upper and lower tracks 47, 48 resists lateral forces imposed on the platform 42, and resists moment loading of the platform 42 due to an overhung load when the platform 42 is extended beyond an edge of the base 51 as hereinafter described.
The display unit 10 rests on the top surface of the platform 42, which is substantially flat and dimensioned to accommodate the footprint of the display unit 10. The platform 42 is essentially rigid to support the weight of the display unit and like the base is preferably made from metal or from one piece of molded plastic.
The extreme front portion of the platform 42 defines a skirt 45, which extends over the front edge of the base. The skirt 42 conceals the front edge and thereby minimizes the extent to which the relative motion between moving and stationary objects is perceived by the viewer.
A motor 64 drives displacement of the platform 42 relative to the base 51. The motor can be a synchronous motor, including gearing to provide an optional output speed range. It is also possible to provide a motor which is adjustable in output speed, such as a DC motor coupled to a voltage regulator allowing the user to vary the speed or perhaps reverse the motor. The motor 64 is coupled to rotate a shaft 58 which is supported on the base 51 such as by journal mount 49.
The motor is arranged as shown in FIG. 5 such that the axis of the output shaft is displaced laterally outward from the motor and the gearing associated with the motor. Accordingly, the shaft can be placed immediately adjacent the base 51. The motor is preferably placed in an enlarged cowling of the base 51 at the rear, and by virtue of the placement of the shaft adjacent the base, the apparatus only adds minimal height to the position of the display unit. The rear cowling is behind the display unit in use, and thus cannot be seen by the user.
The shaft 58 has a longitudinal axis and an outer surface and is mounted for rotation about the longitudinal axis. The outer surface defines a groove 62, aligned at an angle or pitch relative to the longitudinal axis. The groove 62 has a length which spans at least a portion of the length of the shaft 58 and runs in both directions along the shaft. The groove 62 preferably defines a pair of intersecting helical grooves which are joined by circumferential groove portions at opposite ends of the shaft 58. Thus as the shaft rotates unidirectionally, a follower means received within the groove 62 is linearly displaced with a continuous, reciprocating motion along the length of the shaft 58.
The follower means includes a pivot pin 67, shown in FIG. 7, having a lower end 68 which is generally flat and has an inwardly curved end matched to the radius of shaft 58 at the bottom of the groove 62 such that the lower end 68 slides along the groove. The flat lower end is integrally joined to a cylindrical body portion 53 which fits into a bore in the flanged side of guide holder 71, shown in FIG. 6 such that the pivot pin 67 is captive when the guide holder 71 is attached to the underside of platform 42, for example with screws.
The guide holder 71 and pivot pin 67 transmit the rotary motion of the shaft 58 to a linear motion of platform 42, and the display unit 10 resting on the platform. As shown in FIG. 6, the guide holder 71 defines a bore 75 for receiving the shaft 58 in a slip fit. The guide holder 71 further defines a cavity 69 for slidably and rotatably receiving the body portion 53 of the pivot pin 67. The sidewalls of the cavity 69 maintain the pivot pin 67 perpendicular to the shaft 58. When the pivot pin 67 is received within the cavity 69 and the lower end 68 is received within the groove 62, rotation of the shaft 58 moves the pivot pin linearly due to the helical pitch of the groove 62. The guide holder 71 and platform 42 thus move linearly along the shaft due to force from the wall of the groove 62 acting on the lower end 68 of the pivot pin 67. This movement is transmitted to the platform 42 through the pivot pin holder 71 so that the platform 42 moves along path P1.
At the opposite ends of the grooved span of shaft 58 the oppositely pitched portions of the groove are joined along circumferential end sections of the groove. When the end portion 68 of the pivot pin reaches the end of the groove, the end portion 68 follows the circumferential section to the reversed pitch part of the groove, being thereby rotated in bore 69 from one pitch angle to the opposite pitch angle. In this manner, unidirectional rotation of shaft 58 by motor 64 moves the platform 42 reciprocally with respect to the base 51, causing the display unit to move back and forth along path P1.
In the event the linear actuator according to the invention is arranged with a reversing motor, a single pitch screw thread can be used, with a nut attached to the platform for transmitting linear movement. The dual pitch embodiment shown, however, is preferred because the motion is very smooth through reversing of the direction of displacement of the platform. In order to obtain a similarly smooth motion in a reversing motor embodiment, it is necessary to slow down the motor at the point of reversal and to restart the motor slowly in the opposite direction to avoid vibrating or jerking the display unit as clearance is taken up. With a double pitch shaft as shown, reversing does not noticeably jar the display.
With reference to Figs. I and 2, the apparatus of the invention can be embodied directly in the base 18 of the display unit 10, or can be provided as a separable unit which supports the display unit by its base. In an embodiment wherein the apparatus is included in the base, the motor and shaft are preferably mounted to the upper of the base and platform, and the guide holder is mounted to the lower one. The upper part (or platform) in that case is relatively larger than the lower part (or base), and a skirt extending downwardly all around the base 18 conceals the mechanism.
The invention having been disclosed, a number of alternative variations within the scope of the invention will now become apparent to those skilled in the art. Reference should be made to the appended claims rather than the foregoing disclosure of preferred embodiments in order to assess the scope of the invention in which exclusive rights are claimed.
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A device for slowly and smoothly displacing the display unit of a terminal such as a computer work station has a base and a platform movably supported on the base. The platform supports the display terminal and is oscillated back and forth along a path by a linear actuator disposed in the base. A shaft is mounted for rotation on a longitudinal axis and has a groove along the length of its outer surface helically inclined at an angle to the longitudinal axis. A motor rotates the shaft and a follower rides in the groove on the shaft and is connected for transmitting linear motion to the platform as the shaft rotates. The groove includes bidirectional helices joined at the ends by a circumferential groove section. The motor can be a synchronous motor with a gear arrangement providing an output which is laterally and downwardly displaced relative to the motor, whereby the shaft is compactly located immediately adjacent the base of the device providing the device with a low profile capability.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of International Application No. PCT/US99/28628, filed Dec. 2, 1999, entitled Consumer Profiling and Advertisement Selection System, which claims the benefit of co-pending U.S. patent application Ser. No. 09/204,888, filed Dec. 3, 1998, entitled Subscriber Characterization System; U.S. patent application Ser. No. 09/268,526, filed Mar. 12, 1999, entitled Advertisement Selection System Supporting Discretionary Target Market Characteristics, now U.S. Pat. No. 6,216,129; and U.S. patent application Ser. No. 09/268,519, filed Mar. 12, 1999, entitled Consumer Profiling System, now U.S. Pat. No. 6,298,348.
BACKGROUND OF THE INVENTION
The advent of the Internet has resulted in the ability to communicate data across the globe instantaneously, and will allow for numerous new applications which enhance consumer's lives. One of the enhancements which can occur is the ability for the consumer to receive advertising which is relevant to their lifestyle, rather than a stream of ads determined by the program they are watching. Such “targeted ads” can potentially reduce the amount of unwanted information which consumers receive in the mail, during television programs, and when using the Internet. Examples of editorial targeting can be found on the World Wide Web, where banners are delivered based on the page content. The product literature from DoubleClick, “Dynamic Advertising Reporting and Targeting (DART), printed from the World Wide Web site http://www.doubleclick.net/dart on Jun. 19, 1998 discloses DoubleClick's advertising solution for matching advertiser's selected targeted profiles with individual user profiles and deliver an appropriate banner. The user and advertisements are matched based on geographic location or keywords on the page content. The product literature from Imgis, “Ad Force,” printed from the World Wide Web site http://www.starpt.com/core on Jun. 30, 1998 discloses an ad management system for targeting users and delivering advertisements to them. Users are targeted based on the type of content they are viewing or by keywords.
From an advertiser's perspective the ability to target ads can be beneficial since they have some confidence that their ad will at least be determined relevant by the consumer, and therefore will not be found annoying because it is not applicable to their lifestyle. Different systems for matching a consumer profile to an advertisement have been proposed such as the U.S. Pat. No. 5,774,170, which discloses a system for delivering targeted advertisement to consumers. In this system, a set of advertisements is tagged with commercial identifier (CID) and, from the existing marketing database, a list of prospective viewers is also identified with CID. The commercials are displayed to the consumers when the CIDs match.
Other systems propose methods for delivering programming tailored to subscribers' profile. U.S. Pat. No. 5,446,919 discloses a communication system capable of targeting a demographically or psychographically defined audience. Demographic and psychographic information about audience member are downloaded and stored in the audience member receiver. Media messages are transmitted to audience member along with a selection profile command, which details the demographic/psychographic profile of audience members that are to receive each media message. Audience members which fall within a group identified by the selection profile command are presented with the media message.
U.S. Pat. No. 5,223,924 discloses a system and method for automatically correlating user preferences with a TV program information database. The system includes a processor that performs “free text” search techniques to correlate the downloaded TV program information with the viewer's preferences. U.S. Pat. No. 5,410,344 discloses a method for selecting audiovideo programs based on viewers' preferences, wherein each of the audiovideo programs has a plurality of programs attributes and a corresponding content code representing the program attributes. The method comprises the steps of storing a viewer preference file, which includes attributes ratings, which represents the degree of impact of the programs attributes on the viewer and, in response to the comparison of viewer preference file with the program content codes, a program is selected for presentation to the viewer.
In order to determine the applicability of an advertisement to a consumer, it is necessary to know something about their lifestyle, and in particular to understand their demographics (age, household size and income). In some instances, it is useful to know their particular purchasing habits. Purchasing habits are being used by E-commerce to profile their visitors. As an example, the product literature from Aptex software Inc., “SelectCast for Commerce Servers,” printed from the World Wide Web site http://www.aptex.com/products-selectcast-commerce.htm on Jun. 30, 1998 discloses the product SelectCast for Commerce Servers. The product personalizes online shopping based on observed user behavior. User interests are learned based on the content they browse, the promotions they click and the products they purchase.
Knowledge of the purchasing habits of a consumer can be beneficial to a product vendor in the sense that a vendor of soups would like to know which consumers are buying their competitor's soup, so that they can target ads at those consumers in an effort to convince them to switch brands. That vendor will probably not want to target loyal customers, although for a new product introduction the strategy may be to convince loyal customers to try the new product. In both cases it is extremely useful for the vendor to be able to determine what brand of product the consumer presently purchases.
There are several difficulties associated with the collection, processing, and storage of consumer data. First, collecting consumer data and determining the demographic parameters of the consumer can be difficult. Surveys can be performed, and in some instances the consumer will willingly give access to normally private data including family size, age of family members, and household income. In such circumstances there generally needs to be an agreement with the consumer regarding how the data will be used. If the consumer does not provide this data directly, the information must be “mined” from various pieces of information which are gathered about the consumer, typically from specific purchases.
A relatively intrusive method for collecting consumer information is described in U.S. Pat. No. 4,546,382, which discloses a television and market research data collection system and method. A data collection unit containing a memory, stores data as to which of the plurality of TV modes are in use, which TV channel is being viewed as well as input from a suitable optical scanning device for collecting consumer product purchases.
Once data is collected, usually from one source, some type of processing can be performed to determine a particular aspect of the consumer's life. As an example, processing can be performed on credit data to determine which consumers are a good credit risk and have recently applied for credit. The resulting list of consumers can be solicited, typically by direct mail. Although information such as credit history is stored on multiple databases, storage of other information such as the specifics of grocery purchases is not typically performed. Even if each individual's detailed list of grocery purchases was recorded, the information would be of little use since it would amount to nothing more than unprocessed shopping lists.
Privacy concerns are also an important factor in using consumer purchase information. Consumers will generally find it desirable that advertisements and other information is matched with their interests, but will not allow indiscriminate access to their demographic profile and purchase records.
The Internet has spawned the concept of “negatively priced information” in which consumers can be paid to receive advertising. Paying consumers to watch advertisements can be accomplished interactively over the Internet, with the consumer acknowledging that they will watch an advertisement for a particular price. Previously proposed schemes such as that described in U.S. Pat. No. 5,794,210, entitled “Attention Brokerage,” of which A. Nathaniel Goldhaber and Gary Fitts are the inventors, describe such a system, in which the consumer is presented with a list of advertisements and their corresponding payments. The consumer chooses from the list and is compensated for viewing the advertisement. The system uses also software agents representing consumers to match the consumer interest profiles with advertisements. The matching is done using “relevance indexing” which is based on hierarchical tree structures. The system requires real-time interactivity in that the viewer must select the advertisement from the list of choices presented.
The ability to place ads to consumers and compensate them for viewing the advertisements opens many possibilities for new models of advertising. However, it is important to understand the demographics and product preferences of the consumer in order to be able to determine if an advertisement is appropriate.
Although it is possible to collect statistical information regarding consumers of particular products and compare those profiles against individual demographic data points of consumers, such a methodology only allows for selection of potential consumers based on the demographics of existing customers of the same or similar products.
U.S. Pat. No. 5,515,098, entitled “System and method for selectively distributing commercial messages over a communications network,” of which John B. Carles is the inventor, describes a method in which target household data of actual customers of a product are compared against subscriber household data to determine the applicability of a commercial to a household. Target households for a product or service are characterized by comparing or correlating the profile of the customer household to the profile of all households. A rating is established for each household for each category of goods/services. The households within a predefined percentile of subscribers, as defined by the rating, are targeted by the advertiser of the product or service.
It will also frequently be desirable to target an advertisement to a market having discretionary characteristics and to obtain a measure of the correlation of these discretionary features with probabilistic or deterministic data of the consumer/subscriber, rather than being forced to rely on the characteristics of existing consumers of a product. Such correlation should be possible based both on demographic characteristics and product preferences.
Another previously proposed system, described in U.S. Pat. No. 5,724,521, entitled “Method and apparatus for providing electronic advertisements to end users in a consumer best-fit pricing manner,” of which R. Dedrick is the inventor, utilizes a consumer scale as the mechanism to determine to which group an advertisement is intended. A consumer scale matching process compares the set of characteristics stored in a user profile database to a consumer scale associated with the electronic advertisement. The fee charged to the advertiser is determined by where the set of characteristics fall on the consumer scale. Such a system requires specification of numerous parameters and weighting factors, and requires access to specific and non-statistical personal profile information.
For the foregoing reasons, there is a need for a consumer profiling system which can profile the consumer, provide access to the consumer profile in a secure manner, and return a measurement of the potential applicability of an advertisement. There is also a need for an advertisement selection system which can match an advertisement with discretionary target market characteristics, and which can do so in a manner which protects the privacy of the consumer data and characterizations.
SUMMARY OF THE INVENTION
The present invention supports the receipt of consumer purchase information with which consumer characterization vectors are updated based on product characterization information. The consumer characterization vectors include a consumer demographic vector which provides a probabilistic measure of the demographics of the consumer, and a product preference vector which describes which products the consumer has typically purchased in the past, and therefore is likely to purchase in the future. The product characterization information includes vector information which represents probabilistic determinations of the demographics of purchasers of an item, heuristic rules which can be applied to probabilistically describe the demographics of the consumer based on that purchase, and a vector representation of the purchase itself.
In a preferred embodiment a computer-readable detailed purchase record is received, along with a unique consumer identifier. A demographic characterization vector corresponding to the consumer can be retrieved. In the event that there is no existing demographic characterization vector for that consumer, a new demographic characterization vector can be created. In a preferred embodiment the new demographic characterization vector contains no information. A set of heuristic rules is retrieved and contains a probabilistic measure of the demographic characteristics of a typical purchaser of an item. A new demographic characterization vector is calculated based on the purchase, the existing demographic characterization vector, and the heuristic rules.
In a preferred embodiment the calculation of the demographic characterization vector is performed by calculating a weighted average of a product demographics vector and the existing demographic characterization vector. A weighting factor is used in which the weighting factor is determined based on the ratio of the current product purchase amount to a cumulative product purchase amount. The cumulative product purchase amount can be measured as the amount spent on a particular category of items (e.g. groceries, clothes, accessories) over a given period of time such as one month or one year.
In a preferred embodiment the heuristic rules are in the form of a product demographics vector which states the demographics of known purchasers of an item. Each product can have an associated product demographics vector.
The present invention can be used to develop product preference descriptions of consumers which describe the brand and size product that they purchase, and which provide a probabilistic interpretation of the products they are likely to buy in the future. The product preference description can be generated by creating a weighted average of an existing product preference vector describing the consumer's historical product preferences (type of product, brand, and size) and the characteristics of recent purchases.
The present invention can be realized as a data processing system or computer program which processes consumer purchase records and updates their demographic and product preference profiles based on the use of product characterization information. The data processing system can also be used to receive information regarding an advertisement and to perform a correlation between the advertisement and the consumer's demographic and product preferences.
The present invention can be realized as software resident on one or more computers. The system can be realized on an individual computer which receives information regarding consumer purchases, or can be realized on a network of computers in which portions of the system are resident on different computers.
One advantage of the present invention is that it allows consumer profiles to be updated automatically based on their purchases, and forms a description of the consumer including demographic characteristics and product preferences. This description can be used by advertisers to determine the suitability of advertisements to the consumer. Consumers benefit from the system since they will receive advertisements which are more likely to be applicable to them.
The present invention can be used to profile consumers to support the correlation of an advertisement characterization vector associated with an advertisement with the consumer characterization vector to determine the applicability of the advertisement to the consumer.
Another feature of the present invention is the ability to price access to the consumer based on the degree of correlation of an advertisement with their profile. If an advertisement is found to be very highly correlated with a consumer's demographics and product preferences, a relatively high price can be charged for transmitting the advertisement to the consumer. From the consumer's perspective, if the correlation between the advertisement and the consumer's demographics or product preferences is high the consumer can charge less to view the ad, since it is likely that is will be of interest.
The present invention also describes a system for determining the applicability of an advertisement to a consumer, based on the reception of an ad characterization vector and use of a unique consumer ID. The consumer ID is used to retrieve a consumer characterization vector, and the correlation between the consumer characterization vector and the ad characterization vector is used to determine the applicability of the advertisement to the consumer. The price to be paid for presentation of the advertisement can be determined based on the degree of correlation.
The price to present an advertisement can increase with correlation, as may be typical when the content/opportunity provider is also the profiling entity. The price can decrease with correlation when the consumer is the profiler, and is interested in, and willing to charge less for seeing advertisements which are highly correlated with their demographics, lifestyle, and product preferences.
The present invention can be used to specify purchasers of a specific product. In a preferred embodiment the advertisement characterization vector contains a description of a target market including an indicator of a target product, i.e., purchasers of a particular product type, brand, or product size. The advertisement characterization vector is correlated with a consumer characterization vector which is retrieved based on a unique consumer ID. The correlation factor is determined and indicates if the consumer is a purchaser of the product the advertisement is intended for. This feature can be used to identify purchasers of a particular brand and can be used to target ads at those consumers to lure them away from their present product provider. Similarly, this feature can be used to target ads to loyal consumers to introduce them to a new product in a product family, or different size of product.
One advantage of the present invention is that discretionary target market parameters can be specified and do not necessarily need to correspond to an existing market, but can reflect the various market segments for which the advertisement is targeted. The market segments can be designated by demographic characteristics or by product preferences.
Another advantage of the present invention is that demographic samples of present purchasers of a product are not required to define the target market.
The present invention can be used to determine the applicability of an advertisement to a consumer based on demographics, product preferences, or a combination of both.
In a preferred embodiment of the present invention the correlation is calculated as the scalar product of the ad characterization vector and the consumer characterization vector. The ad characterization vector and consumer characterization vector can be composed of demographic characteristics, product purchase characteristics, or a combination of both.
In a preferred embodiment pricing for the displaying of said advertisement is developed based on the result of the correlation between the ad characterization vector and the consumer characterization vector. In a first embodiment the pricing increases as a function of the correlation. This embodiment can represent the situation in which the party which determines the correlation also controls the ability to display the advertisement.
In an alternate embodiment the price for displaying the advertisement decreases as a function of the degree of correlation. This embodiment can represent the situation in which the consumer controls access to the consumer characterization vector, and charges less to view advertisements which are highly correlated with their interests and demographics. A feature of this embodiment is the ability of the consumer to decrease the number of unwanted advertisements by charging a higher price to view advertisements which are likely to be of less interest.
One advantage of the present invention is that it allows advertisements to be directed to new markets by setting specific parameters in the ad characterization vector, and does not require specific statistical knowledge regarding existing customers of similar products. Another advantage is that the system allows ads to be directed at consumers of a competing brand, or specific targeting at loyal customers. This feature can be useful for the introduction of a new product to an existing customer base.
Another advantage of the present invention is that the correlation can be performed by calculating a simple scalar (dot) product of the ad characterization and consumer characterization vectors. A weighted sum or other statistical analysis is not required to determine the applicability of the advertisement.
The present invention can be realized as a data processing system and as a computer program. The invention can be realized on an individual computer or can be realized using distributed computers with portions of the system operating on various computers.
An advantage of the present invention is the ability to direct advertisements to consumers which will find the advertisements of interest. This eliminates unwanted advertisements. Another advantage is the ability of advertisers to target specific groups of potential customers.
These and other features and objects of the invention will be more fully understood from the following detailed description of the preferred embodiments which should be read in light of the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated in and form a part of the specification, illustrate the embodiments of the present invention and, together with the description serve to explain the principles of the invention.
In the drawings:
FIGS. 1A and 1B show user relationship diagrams for the present invention;
FIGS. 2A , 2 B, 2 C and 2 D illustrate a probabilistic consumer demographic characterization vector, a deterministic consumer demographic characterization vector, a consumer product preference characterization vector, and a storage structure for consumer characterization vectors respectively;
FIGS. 3A and 3B illustrate an advertisement demographic characterization vector and an advertisement product preference characterization vector respectively;
FIG. 4 illustrates a computer system on which the present invention can be realized;
FIG. 5 illustrates a context diagram for the present invention;
FIGS. 6A and 6B illustrate pseudocode updating the characteristics vectors and for a correlation operation respectively;
FIG. 7 illustrates heuristic rules;
FIGS. 8A and 8B illustrate flowcharts for updating consumer characterization vectors and a correlation operation respectively; and
FIG. 9 represents pricing as a function of correlation.
FIG. 10 illustrates a representation of a consumer characterization as a set of basis vectors and an ad characterization vector.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In describing a preferred embodiment of the invention illustrated in the drawings, specific terminology will be used for the sake of clarity. However, the invention is not intended to be limited to the specific terms so selected, and it is to be understood that each specific term includes all technical equivalents which operate in a similar manner to accomplish a similar purpose.
With reference to the drawings, in general, and FIGS. 1 through 10 in particular, the method and apparatus of the present invention is disclosed.
FIG. 1A shows a user relationship diagram which illustrates the relationships between a consumer profiling system and various entities. As can be seen in FIG. 1 , a consumer 100 can receive information and advertisements from a consumer personal computer (PC) 104 , displayed on a television 108 which is connected to a settop 106 , or can receive a mailed ad 182 .
Advertisements and information displayed on consumer PC 104 or television 108 can be received over an Internet 150 , or can be received over the combination of the Internet 150 with another telecommunications access system. The telecommunications access system can include but is not limited to cable TV delivery systems, switched digital video access systems operating over telephone wires, microwave telecommunications systems, or any other medium which provides connectivity between the consumer 100 and a content server 162 and ad server 146 .
A content/opportunity provider 160 maintains the content server 162 which can transmit content including broadcast programming across a network such as the Internet 150 . Other methods of data transport can be used including private data networks and can connect the content sever 160 through an access system to a device owned by consumer 100 .
Content/opportunity provider 160 is termed such since if consumer 100 is receiving a transmission from content server 162 , the content/opportunity provider can insert an advertisement. For video programming, content/opportunity provider is typically the cable network operator or the source of entertainment material, and the opportunity is the ability to transmit an advertisement during a commercial break.
The majority of content that is being transmitted today is done so in broadcast form, such as broadcast television programming (broadcast over the air and via cable TV networks), broadcast radio, and newspapers. Although the interconnectivity provided by the Internet will allow consumer specific programming to be transmitted, there will still be a large amount of broadcast material which can be sponsored in part by advertising. The ability to insert an advertisement in a broadcast stream (video, audio, or mailed) is an opportunity for advertiser 144 . Content can also be broadcast over the Internet and combined with existing video services, in which case opportunities for the insertion of advertisements will be present.
Although FIG. 1A represents content/opportunity provider 160 and content server 162 as being independently connected to Internet 150 , with the consumer's devices being also being directly connected to the Internet 150 , the content/opportunity provider 160 can also control access to the subscriber. This can occur when the content/opportunity provider is also the cable operator or telephone company. In such instances, the cable operator or telephone company can be providing content to consumer 100 over the cable operator/telephone company access network. As an example, if the cable operator has control over the content being transmitted to the consumer 100 , and has programmed times for the insertion of advertisements, the cable operator is considered to be a content/opportunity provider 160 since the cable operator can provide advertisers the opportunity to access consumer 100 by inserting an advertisement at the commercial break.
In a preferred embodiment of the present invention, a pricing policy can be defined. The content/opportunity provider 160 can charge advertiser 144 for access to consumer 100 during an opportunity. In a preferred embodiment the price charged for access to consumer 100 by content/opportunity provider varies as a function of the applicability of the advertisement to consumer 100 . In an alternate embodiment consumer 100 retains control of access to the profile and charges for viewing an advertisement.
The content provider can also be a mailing company or printer which is preparing printed information for consumer 100 . As an example, content server 162 can be connected to a printer 164 which creates a mailed ad 182 for consumer 100 . Alternatively, printer 164 can produce advertisements for insertion into newspapers which are delivered to consumer 100 . Other printed material can be generated by printer 162 and delivered to consumer 100 in a variety of ways.
Advertiser 144 maintains an ad server 146 which contains a variety of advertisements in the form of still video which can be printed, video advertisements, audio advertisements, or combinations thereof.
Profiler 140 maintains a consumer profile server 130 which contains the characterization of consumer 100 . The consumer profiling system is operated by profiler 140 , who can use consumer profile server 130 or another computing device connected to consumer profile server 130 to profile consumer 100 .
Data to perform the consumer profiling is received from a point of purchase 110 . Point of purchase 110 can be a grocery store, department store, other retail outlet, or can be a web site or other location where a purchase request is received and processed. In a preferred embodiment, data from the point of purchase is transferred over a public or private network 120 , such as a local area network within a store or a wide area network which connects a number of department or grocery stores. In an alternate embodiment the data from point of purchase 110 is transmitted over the Internet 150 to profiler 140 .
Profiler 140 may be a retailer who collects data from its stores, but can also be a third party who contracts with consumer 100 and the retailer to receive point of purchase data and profile consumer 100 . Consumer 100 may agree to such an arrangement based on the increased convenience offered by targeted ads, or through a compensation arrangement in which they are paid on a periodic basis for revealing their specific purchase records.
Consumer profile server 130 can contain a consumer profile which is determined from observation of the consumer's viewing habits on television 108 or consumer PC 104 . Determination of demographic and product preference information based on the consumer's use of services such as cable television and Internet access can be performed by monitoring the channel selections that a subscriber makes, and determining household demographics based on the subscriber selections and information associated with the programming being watched.
In one embodiment the channel selections are recorded, and based on the time of day during which the programming is watched and duration of viewing, heuristic rules are applied to make probabilistic determinations regarding the household demographics including age, gender, household size and income, as illustrated in FIG. 2A . This can be accomplished by applying heuristic rules which associate the programming with known and assumed characteristics for viewers of the programming. As an example, it is known that the probability that the viewer of a cartoon in the morning is in the 3–8 year old age group is high, thus if the household viewing habits consistently record viewing of cartoons the probability that the household will contain one or more viewers in the 3–8 year old age group is high.
In one embodiment information regarding the program is extracted from the Electronic Program Guide (EPG) which contains information regarding the scheduled programming. In another embodiment information regarding the programming is retrieved from the closed caption channel transmitted in the broadcast signal.
The volume at which the program is watched can also be stored and forms an additional basis for subscriber characterization, wherein the muting of a channel indicates limited interest in a particular program or advertisement. In the case of an advertisement, muting of the advertisement can be used as a measure of the effectiveness (or ineffectiveness) of the advertisement and can serve as part of the basis for the subscriber characterization. The muting of a program, as well as the duration for which the program is watched, can also be used in the determination of the subscriber characterization vector.
By processing the recorded viewing habits in conjunction with programming related information and heuristic rules similar to those illustrated in FIG. 7 but related to programming rather than purchases, it is possible to construct a subscriber characterization vector which contains a probabilistic demographic profile of the household.
When used herein, the term consumer characterization vector also represents the subscriber characterization vector previously described. Both the consumer characterization vector and the subscriber characterization vector contain demographic and product preference information which is related to consumer 100 .
FIG. 1B illustrates an alternate embodiment of the present invention in which the consumer 100 is also profiler 140 . Consumer 100 maintains consumer profile server 130 which is connected to a network, either directly or through consumer PC 104 or settop 106 . Consumer profile server 130 can contain the consumer profiling system, or the profiling can be performed in conjunction with consumer PC 104 or settop 106 . A subscriber characterization system which monitors the viewing habits of consumer 100 can be used in conjunction with the consumer profiling system to create a more accurate consumer profile.
When the consumer 100 is also the profiler 140 , as shown in FIG. 1B , access to the consumer demographic and product preference characterization is controlled exclusively by consumer 100 , who will grant access to the profile in return for receiving an increased accuracy of ads, for cash compensation, or in return for discounts or coupons on goods and services.
FIG. 2A illustrates an example of a probabilistic demographic characterization vector. The demographic characterization vector is a representation of the probability that a consumer falls within a certain demographic category such as an age group, gender, household size, or income range.
In a preferred embodiment the demographic characterization vector includes interest categories. The interest categories may be organized according to broad areas such as music, travel, and restaurants. Examples of music interest categories include country music, rock, classical, and folk. Examples of travel categories include “travels to another state more than twice a year,” and travels by plane more than twice a year.”
FIG. 2B illustrates a deterministic demographic characterization vector. The deterministic demographic characterization vector is a representation of the consumer profile as determined from deterministic rather than probabilistic data. As an example, if consumer 100 agrees to answer specific questions regarding age, gender, household size, income, and interests the data contained in the consumer characterization vector will be deterministic.
As with probabilistic demographic characterization vectors, the deterministic demographic characterization vector can include interest categories. In a preferred embodiment, consumer 100 answers specific questions in a survey generated by profiler 140 and administered over the phone, in written form, or via the Internet 150 and consumer PC 104 . The survey questions correspond either directly to the elements in the probabilistic demographic characterization vector, or can be processed to obtain the deterministic results for storage in the demographic characterization vector.
FIG. 2C illustrates a product preference vector. The product preference represents the average of the consumer preferences over past purchases. As an example, a consumer who buys the breakfast cereal manufactured by Post under the trademark ALPHABITS about twice as often as purchasing the breakfast cereal manufactured by Kellogg under the trademark CORN FLAKES, but who never purchases breakfast cereal manufactured by General Mills under the trademark WHEATIES, would have a product preference characterization such as that illustrated in FIG. 2C . As shown in FIG. 2C , the preferred size of the consumer purchase of a particular product type can also be represented in the product preference vector.
FIG. 2D represents a data structure for storing the consumer profile, which can be comprised of a consumer ID field 237 , a deterministic demographic data field 239 , a probabilistic demographic data field 241 , and one or more product preference data fields 243 . As shown in FIG. 2D , the product preference data field 243 can be comprised of multiple fields arranged by product categories 253 .
Depending on the data structure used to store the information contained in the vector, any of the previously mentioned vectors may be in the form of a table, record, linked tables in a relational database, series of records, or a software object.
The consumer ID 512 can be any identification value uniquely associated with consumer 100 . In a preferred embodiment consumer ID 512 is a telephone number, while in an alternate embodiment consumer ID 512 is a credit card number. Other unique identifiers include consumer name with middle initial or a unique alphanumeric sequence, the consumer address, social security number.
The vectors described and represented in FIGS. 2A–C form consumer characterization vectors that can be of varying length and dimension, and portions of the characterization vector can be used individually. Vectors can also be concatenated or summed to produce longer vectors which provide a more detailed profile of consumer 100 . A matrix representation of the vectors can be used, in which specific elements, such a product categories 253 , are indexed. Hierarchical structures can be employed to organize the vectors and to allow hierarchical search algorithms to be used to locate specific portions of vectors.
FIGS. 3A and 3B represent an ad demographics vector and an ad product preference vector respectively. The ad demographics vector, similar in structure to the demographic characterization vector, is used to target the ad by setting the demographic parameters in the ad demographics vector to correspond to the targeted demographic group. As an example, if an advertisement is developed for a market which is the 18–24 and 24–32 age brackets, no gender bias, with a typical household size of 2–5, and income typically in the range of $20,000-$50,000, the ad demographics vector would resemble the one shown in FIG. 3A . The ad demographics vector represents a statistical estimate of who the ad is intended for, based on the advertisers belief that the ad will be beneficial to the manufacturer when viewed by individuals in those groups. The benefit will typically be in the form of increased sales of a product or increased brand recognition. As an example, an “image ad” which simply shows an artistic composition but which does not directly sell a product may be very effective for young people, but may be annoying to older individuals. The ad demographics vector can be used to establish the criteria which will direct the ad to the demographic group of 18–24 year olds.
FIG. 3B illustrates an ad product preference vector. The ad product preference vector is used to select consumers which have a particular product preference. In the example illustrated in FIG. 3B , the ad product preference vector is set so that the ad can be directed a purchasers of ALPHABITS and WHEATIES, but not at purchasers of CORN FLAKES. This particular setting would be useful when the advertiser represents Kellogg and is charged with increasing sales of CORN FLAKES. By targeting present purchasers of ALPHABITS and WHEATIES, the advertiser can attempt to sway those purchasers over to the Kellogg brand and in particular convince them to purchase CORN FLAKES. Given that there will be a payment required to present the advertisement, in the form of a payment to the content/opportunity provider 160 or to the consumer 100 , the advertiser 144 desires to target the ad and thereby increase its cost effectiveness.
In the event that advertiser 144 wants to reach only the purchasers of Kellogg's CORN FLAKES, that category would be set at a high value, and in the example shown would be set to 1. As shown in FIG. 3B , product size can also be specified. If there is no preference to size category the values can all be set to be equal. In a preferred embodiment the values of each characteristic including brand and size are individually normalized.
Because advertisements can be targeted based on a set of demographic and product preference considerations which may not be representative of any particular group of present consumers of the product, the ad characterization vector can be set to identify a number of demographic groups which would normally be considered to be uncorrelated. Because the ad characterization vector can have target profiles which are not representative of actual consumers of the product, the ad characterization vector can be considered to have discretionary elements. When used herein the term discretionary refers to a selection of target market characteristics which need not be representative of an actual existing market or single purchasing segment.
In a preferred embodiment the consumer characterization vectors shown in FIGS. 2A–C and the ad characterization vectors represented in FIGS. 3A and 3B have a standardized format, in which each demographic characteristic and product preference is identified by an indexed position. In a preferred embodiment the vectors are singly indexed and thus represent coordinates in n-dimensional space, with each dimension representing a demographic or product preference characteristic. In this embodiment a single value represents one probabilistic or deterministic value (e.g. the probability that the consumer is in the 18–24 year old age group, or the weighting of an advertisement to the age group).
In an alternate embodiment a group of demographic or product characteristics forms an individual vector. As an example, age categories can be considered a vector, with each component of the vector representing the probability that the consumer is in that age group. In this embodiment each vector can be considered to be a basis vector for the description of the consumer or the target ad. The consumer or ad characterization is comprised of a finite set of vectors in a the vector space that describes the consumer or advertisement.
FIG. 4 shows the block diagram of a computer system for a realization of the consumer profiling system. A system bus 422 transports data amongst the CPU 203 , the RAM 204 , Read Only Memory-Basic Input Output System (ROM-BIOS) 406 and other components. The CPU 203 accesses a hard drive 400 through a disk controller 402 . The standard input/output devices are connected to the system bus 422 through the I/O controller 201 . A keyboard is attached to the I/O controller 201 through a keyboard port 416 and the monitor is connected through a monitor port 418 . The serial port device uses a serial port 420 to communicate with the I/O controller 201 . Industry Standard Architecture (ISA) expansion slots 408 and Peripheral Component Interconnect (PCI) expansion slots 410 allow additional cards to be placed into the computer. In a preferred embodiment, a network card is available to interface a local area, wide area, or other network. The computer system shown in FIG. 4 can be part of consumer profile server 130 , or can be a processor present in another element of the network.
FIG. 5 shows a context diagram for the present invention. Context diagrams are useful in illustrating the relationship between a system and external entities. Context diagrams can be especially useful in developing object oriented implementations of a system, although use of a context diagram does not limit implementation of the present invention to any particular programming language. The present invention can be realized in a variety of programming languages including but not limited to C, C++, Smalltalk, Java, Perl, and can be developed as part of a relational database. Other languages and data structures can be utilized to realize the present invention and are known to those skilled in the art.
Referring to FIG. 5 , in a preferred embodiment consumer profiling system 500 is resident on consumer profile server 130 . Point of purchase records 510 are transmitted from point of purchase 110 and stored on consumer profile server 130 . Heuristic rules records 530 , pricing policy 570 , and consumer profile 560 are similarly stored on consumer profile server 130 . In a preferred embodiment advertisement records 540 are stored on ad server 146 and connectivity between advertisement records 540 and consumer profiling system 500 is via the Internet or other network.
In an alternate embodiment the entities represented in FIG. 5 are located on servers which are interconnect via the Internet or other network.
Consumer profiling system 500 receives purchase information from a point of purchase, as represented by point of purchase records 510 . The information contained within the point of purchase records 510 includes a consumer ID 512 , a product ID 514 of the purchased product, the quantity 516 purchased and the price 518 of the product. In a preferred embodiment, the date and time of purchase 520 are transmitted by point of purchase records 510 to consumer profiling system 500 .
The consumer profiling system 500 can access the consumer profile 560 to update the profiles contained in it. Consumer profiling system 500 retrieves a consumer characterization vector 562 and a product preference vector 564 . Subsequent to retrieval one or more data processing algorithms are applied to update the vectors. An algorithm for updating is illustrated in the flowchart in FIG. 8A . The updated vectors termed herein as new demographic characterization vector 566 and new product preference 568 are returned to consumer profile 560 for storage.
Consumer profiling system 500 can determine probabilistic consumer demographic characteristics based on product purchases by applying heuristic rules 519 . Consumer profiling system 500 provides a product ID 514 to heuristic rules records 530 and receives heuristic rules associated with that product. Examples of heuristic rules are illustrated in FIG. 7 .
In a preferred embodiment of the present invention, consumer profiling system 500 can determine the applicability of an advertisement to the consumer 100 . For determination of the applicability of an advertisement, a correlation request 546 is received by consumer profiling system 500 from advertisements records 540 , along with consumer ID 512 . Advertisements records 540 also provides advertisement characteristics including an ad demographic vector 548 , an ad product category 552 and an ad product preference vector 554 .
Application of a correlation process, as will be described in accordance with FIG. 8B , results in a demographic correlation 556 and a product correlation 558 which can be returned to advertisement records 540 . In a preferred embodiment, advertiser 144 uses product correlation 558 and demographic correlation 556 to determine the applicability of the advertisement and to determine if it is worth purchasing the opportunity. In a preferred embodiment, pricing policy 570 is utilized to determine an ad price 572 which can be transmitted from consumer profiling system 500 to advertisement records 540 for use by advertiser 144 .
Pricing policy 570 is accessed by consumer profiling system 500 to obtain ad price 572 . Pricing policy 570 takes into consideration results of the correlation provided by the consumer profiling system 500 . An example of pricing schemes are illustrated in FIG. 9
FIGS. 6A and 6B illustrate pseudocode for the updating process and for a correlation operation respectively. The updating process involves utilizing purchase information in conjunction with heuristic rules to obtain a more accurate representation of consumer 100 , stored in the form of a new demographic characterization vector 562 and a new product preference vector 568 .
As illustrated in the pseudocode in FIG. 6A the point of purchase data are read and the products purchase are integrated into the updating process. Consumer profiling system 500 retrieves a product demographics vector obtained from the set of heuristic rules 519 and applies the product demographics vector to the demographics characterization vector 562 and the product preference vector 564 from the consumer profile 560 .
The updating process as illustrated by the pseudocode in FIG. 6A utilizes a weighting factor which determines the importance of that product purchase with respect to all of the products purchased in a particular product category. In a preferred embodiment the weight is computed as the ratio of the total of products with a particular product ID 514 purchased at that time, to the product total purchase, which is the total quantity of the product identified by its product ID 514 purchased by consumer 100 identified by its consumer ID 512 , purchased over an extended period of time. In a preferred embodiment the extended period of time is one year.
In the preferred embodiment the product category total purchase is determined from a record containing the number of times that consumer 100 has purchased a product identified by a particular product ID.
In an alternate embodiment other types of weighting factors, running averages and statistical filtering techniques can be used to use the purchase data to update the demographic characterization vector. The system can also be reset to clear previous demographic characterization vectors and product preference vectors.
The new demographic characterization vector 566 is obtained as the weighted sum of the product demographics vector the demographic characterization vector 562 . The same procedure is performed to obtain the new product preference vector 568 . Before storing those new vectors, a normalization is performed on the said new vectors. When used herein the term product characterization information refers product demographics vectors, product purchase vectors or heuristic rules, all of which can be used in the updating process. The product purchase vector refers to the vector which represents the purchase of a item represented by a product ID. As an example, a product purchase vector for the purchase of Kellogg's CORN FLAKES in a 32 oz. size has a product purchase vector with a unity value for Kellogg's CORN FLAKES and in the 32 oz. size. In the updating process the weighted sum of the purchase as represented by the product purchase vector is added to the product preference vector to update the product preference vector, increasing the estimated probability that the consumer will purchase Kellogg's CORN FLAKES in the 32 oz. size.
In FIG. 6B the pseudocode for a correlation process is illustrated. Consumer profiling system 500 , after receiving the product characteristics and the consumer ID 512 from the advertisement records retrieves the consumer demographic characterization vector 562 and its product preference vector 564 . The demographic correlation is the correlation between the demographic characterization vector 562 and the ad demographics vector. The product correlation is the correlation between the ad product preference vector 554 and the product preference vector 564 .
In a preferred embodiment the correlation process involves computing the dot product between vectors. The resulting scalar is the correlation between the two vectors.
In an alternate embodiment, as illustrated in FIG. 10 , the basis vectors which describe aspects of the consumer can be used to calculate the projections of the ad vector on those basis vectors. In this embodiment, the result of the ad correlation can itself be in vector form whose components represent the degree of correlation of the advertisement with each consumer demographic or product preference feature. As shown in FIG. 10 the basis vectors are the age of the consumer 1021 , the income of the consumer 1001 , and the family size of the consumer 1031 . The ad characterization vector 1500 represents the desired characteristics of the target audience, and can include product preference as well as demographic characteristics.
In this embodiment the degree of orthogonality of the basis vectors will determine the uniqueness of the answer. The projections on the basis vectors form a set of data which represent the corresponding values for the parameter measured in the basis vector. As an example, if household income is one basis vector, the projection of the ad characterization vector on the household income basis vector will return a result indicative of the target household income for that advertisement.
Because basis vectors cannot be readily created from some product preference categories (e.g. cereal preferences) an alternate representation to that illustrated in FIG. 2C can be utilized in which the product preference vector represents the statistical average of purchases of cereal in increasing size containers. This vector can be interpreted as an average measure of the cereal purchased by the consumer in a given time period.
The individual measurements of correlation as represented by the correlation vector can be utilized in determining the applicability of the advertisement to the subscriber, or a sum of correlations can be generated to represent the overall applicability of the advertisement.
In a preferred embodiment individual measurements of the correlations, or projections of the ad characteristics vector on the consumer basis vectors, are not made available to protect consumer privacy, and only the absolute sum is reported. In geometric terms this can be interpreted as disclosure of the sum of the lengths of the projections rather than the actual projections themselves.
In an alternate embodiment the demographic and product preference parameters are grouped to form sets of paired scores in which elements in the consumer characterization vector are paired with corresponding elements of the ad characteristics vector. A correlation coefficient such as the Pearson product-moment correlation can be calculated. Other methods for correlation can be employed and are well known to those skilled in the art.
When the consumer characterization vector and the ad characterization vector are not in a standardized format, a transformation can be performed to standardize the order of the demographic and product preferences, or the data can be decomposed into sets of basis vectors which indicate particular attributes such as age, income or family size.
FIG. 7 illustrates an example of heuristic rules including rules for defining a product demographics vector. From the product characteristics, a probabilistic determination of household demographics can be generated. Similarly, the monthly quantity purchased can be used to estimate household size. The heuristic rules illustrated in FIG. 7 serve as an example of the types of heuristic rules which can be employed to better characterize consumer 100 as a result of their purchases. The heuristic rules can include any set of logic tests, statistical estimates, or market studies which provide the basis for better estimating the demographics of consumer 100 based on their purchases.
In FIG. 8A the flowchart for updating the consumer characterization vectors is depicted. The system receives data from the point of purchase at receive point of purchase information step 800 . The system performs a test to determine if a deterministic demographic characterization vector is available at deterministic demographic information available step 810 and, if not, proceeds to update the demographic characteristics.
Referring to FIG. 8A , at read purchase ID info step 820 , the product ID 514 is read, and at update consumer demographic characterization vector step 830 , an algorithm such as that represented in FIG. 6A is applied to obtain a new demographic characterization vector 566 , which is stored in the consumer profile 560 at store updated demographic characterization vector step 840 .
The end test step 850 can loop back to the read purchase ID info 820 if all the purchased products are not yet processed for updating, or continue to the branch for updating the product preference vector 564 . In this branch, the purchased product is identified at read purchase ID info step 820 . An algorithm, such as that illustrated in FIG. 6A for updating the product preference vector 564 , is applied in update product preference vector step 870 . The updated vector is stored in consumer profile 560 at store product preference vector step 880 . This process is carried out until all the purchased items are integrated in the updating process.
FIG. 8B shows a flowchart for the correlation process. At step 900 the advertisement characteristics described earlier in accordance with FIG. 5 along with the consumer ID are received by consumer profiling system 500 . At step 910 the demographic correlation 556 is computed and at step 920 the product preference correlation 558 is computed. An illustrative example of an algorithm for correlation is presented in FIG. 6 b . The system returns demographic correlation 556 and product preference correlation 558 to the advertisement records 540 before exiting the procedure at end step 950 .
FIG. 9 illustrates two pricing schemes, one for content/opportunity provider 160 based pricing 970 , which shows increasing cost as a function of correlation. In this pricing scheme, the higher the correlation, the more the content/opportunity provider 160 charges to air the advertisement.
FIG. 9 also illustrates consumer based pricing 960 , which allows a consumer to charge less to receive advertisements which are more highly correlated with their demographics and interests.
As an example of the industrial applicability of the invention, a consumer 100 can purchase items in a grocery store which also acts as a profiler 140 using a consumer profiling system 500 . The purchase record is used by the profiler to update the probabilistic representation of customer 100 , both in terms of their demographics as well as their product preferences. For each item purchased by consumer 100 , product characterization information in the form of a product demographics vector and a product purchase vector is used to update the demographic characterization vector and the product preference vector for consumer 100 .
A content/opportunity provider 160 may subsequently determine that there is an opportunity to present an advertisement to consumer 100 . Content/opportunity provider 160 can announce this opportunity to advertiser 144 by transmitting the details regarding the opportunity and the consumer ID 512 . Advertiser 144 can then query profiler 140 by transmitting consumer ID 512 along with advertisement specific information including the correlation request 546 and ad demographics vector 548 . The consumer profiling system 500 performs a correlation and determines the extent to which the ad target market is correlated with the estimated demographics and product preferences of consumer 100 . Based on this determination advertiser 144 can decide whether to purchase the opportunity or not.
Although this invention has been illustrated by reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications may be made which clearly fall within the scope of the invention. The invention is intended to be protected broadly within the spirit and scope of the appended claims.
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Computer network method and apparatus provides targeting of appropriate audience based on psychographic or behavioral profiles of end users. The psychographic profile is formed by recording computer activity and viewing habits of the end user. Content of categories of interest and display format in each category are revealed by the psychographic profile, based on user viewing of agate information. Using the profile (with or without additional user demographics), advertisements are displayed to appropriately selected users. Based on regression analysis of recorded responses of a first set of users viewing the advertisements, the target user profile is refined. Viewing by and regression analysis of recorded responses of subsequent sets of users continually auto-targets and customizes ads for the optimal end user audience.
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FIELD OF THE INVENTION
The invention relates to a birefringent polymer film having negative optical dispersion, novel polymerisable compounds and liquid crystal (LC) materials for its preparation, and the use of the polymer film and novel compounds and materials in optical, electrooptical, electronic, semiconducting or luminescent components or devices.
BACKGROUND AND PRIOR ART
There is a need for anisotropic optical films that demonstrate negative optical retardation dispersion. For example, a quarter wave film made with negative dispersion birefringent materials will be largely achromatic. Devices such as a reflective LCD that utilises such a quarter wave film will have a dark state that is not coloured. Currently such devices have to use two retarder films to achieve this effect. The dispersive power of such a film can be defined in many ways, however one common way is to measure the optical retardation at 450 nm and divide this by the optical retardation measured at 550 nm (R 450 /R 550 ). If the on-axis retardation of a negative retardation dispersion film at 550 nm is 137.5 nm and the R 450 /R 550 value is 0.82, then such a film will be a largely a quarter wave for all wavelengths of visible light and a liquid crystal display device (LCD) using this film as, for example, a circular polariser would have a substantially black appearance. On the other hand, a film made with an on axis of 137.5 nm which had normal positive dispersion (typically R 450 /R 550 =1.13) would only be a quarter wave for one wavelength (550 nm), and an LCD device using this film as, for example, a circular polariser would have a purple appearance. Another way of representing this information is to plot the change in birefringence as a function of wavelength. FIG. 1 shows a typical birefringence against wavelength plot for a polymerised film made from the commercially available reactive mesogen RM257 (Merck KgaA, Darmstadt, Germany). The R 450 /R 550 for this compound is around 1.115.
In an anisotropic optical film formed by rod-shaped, optically anisotropic molecules, the origin of the retardation dispersion is due to the fact that the two refractive indices n e , n o , of the anisotropic molecules (wherein n e is the “extraordinary refractive index” in the direction parallel to the long molecular axis, and n o is the “ordinary refractive index” in the directions perpendicular to the long molecular axis) are changing with wavelength at different rates, with n e changing more rapidly than n o towards the blue end of the visible wavelength spectrum. One way of preparing material with low or negative retardation dispersion is to design molecules with increased n o dispersion and decreased n e dispersion. This is schematically shown in FIG. 2 . Such an approach has been demonstrated in prior art to give LC's with negative birefringence and positive dispersion as well as compounds with positive birefringence and negative dispersion.
Thus, molecules that can be formed into anisotropic films that demonstrate the property of negative or reverse retardation dispersion have been disclosed in prior art. For example, JP2005-208416 A1 and WO 2006/052001 A1 disclose polymerisable materials based on a “cardo” core group. JP2005-208414 A1 discloses molecules that have covalently bonded discs and rods. JP2005-208415 A1 and JP2002-267838 A1 disclose materials that possess a cross-shape with short high refractive index parts of the molecule crossed with longer lower refractive index parts. WO 2005-085222 A1 discloses molecules that have two lower refractive index parts connected by a higher refractive index bridge part. The bridge is predominantly connected to the rods via a fused five-membered heterocyclic ring. All the above-mentioned documents disclose molecules that not only demonstrate negative dispersion, but also contain at least one polymerisable group and can therefore be polymerised when exposed to either heat or UV irradiation. These materials can be processed either as single materials, or as a mixture to give thin films which under the appropriate conditions can demonstrate uniform anisotropic properties. If photoinitiator is also included in the mixture, the anisotropic properties can be locked in by exposing the film to UV irradiation. This method of preparing optical films is well known. Another class of materials which is claimed to demonstrate negative birefringence is disclosed in U.S. Pat. No. 6,139,771, which describes compounds generally consisting of two rod-shaped LC parts connected by a acetylenic or bis-acetylenic bridging group. The bridging group is connected to the two rod-shaped parts using a benzene ring. However the document does neither disclose nor suggest polymerisable versions of these compounds.
U.S. Pat. No. 6,203,724 discloses molecules generally consisting of two rod-shaped LC parts connected by highly dispersive bridging groups. The bridging group is connected to the rod-shaped parts via the axial position of a cyclohexane ring. However the document does neither disclose nor suggest to use such compounds for the preparation of optical polymer films having negative optical dispersion.
U.S. Pat. No. 5,567,349 discloses dimers (or H-shaped RM's) wherein the bridging group is connected to the rod shaped part of the molecule via a phenyl ring, however, this document does not report that the molecules demonstrate negative dispersion or negative birefringence.
However, the materials already disclosed in the literature have thermal properties that are not suitable for processing under standard industrial processes, or are not soluble in the solvents commonly used in standard industrial processes or are not compatible with host RM materials commonly used in standard industrial processes, or are too expensive to manufacture.
This invention has the aim of providing improved polymer films and compounds and materials for their preparation not having the drawbacks of the prior art materials.
Another aim of the invention is to extend the pool of polymer films and materials having negative dispersion that are available to the expert. Other aims are immediately evident to the expert from the following description.
It has been found that these aims can be achieved by providing polymer films, compounds and materials as claimed in the present invention.
SUMMARY OF THE INVENTION
The invention relates to a birefringent polymer film with R 450 /R 550 <1, wherein R 450 is the optical on-axis retardation at a wavelength of 450 nm and R 550 is the optical on-axis retardation at a wavelength of 550 nm, said film being obtainable by polymerising one or more polymerisable compounds, wherein said polymerisable compounds contain
two mesogenic groups comprising one or more non-aromatic rings, one or more polymerisable groups attached to at least one of the mesogenic groups either directly or via spacer groups, and a bridging group connecting the mesogenic groups, comprising one or more subgroups selected from pi-conjugated linear carbyl or hydrocarbyl groups, aromatic and heteroaromatic groups, and being linked to a sp 3 -hybridised C-atom or Si-atom in a non-aromatic ring of each mesogenic group.
The invention further relates to novel polymerisable compounds as described above and below.
The invention further relates to a polymerisable LC material comprising one or more polymerisable compounds as described above and below and one or more further compounds that are optionally polymerisable and/or mesogenic or liquid crystalline.
The invention further relates to an anisotropic polymer obtainable by polymerising a polymerisable compound or a polymerisable LC material as described above and below, preferably in its LC phase in an oriented state in form of a thin film.
The invention further relates to the use of compounds, materials and polymers as described above and below in optical, electronic and electrooptical components and devices, preferably in optical films, retarders or compensators having negative optical dispersion.
The invention further relates to an optical, electronic or electrooptical component or device, comprising a compound, material or polymer as described above and below.
Said devices and components include, without limitation, electrooptical displays, LCDs, optical films, retarders, compensators, polarisers, beam splitters, reflective films, alignment layers, colour filters, holographic elements, hot stamping foils, coloured images, decorative or security markings, LC pigments, adhesives, non-linear optic (NLO) devices, optical information storage devices, electronic devices, organic semiconductors, organic field effect transistors (OFET), integrated circuits (IC), thin film transistors (TFT), Radio Frequency Identification (RFID) tags, organic light emitting diodes (OLED), organic light emitting transistors (OLET), electroluminescent displays, organic photovoltaic (OPV) devices, organic solar cells (O-SC), organic laser diodes (O-laser), organic integrated circuits (O-IC), lighting devices, sensor devices, electrode materials, photoconductors, photodetectors, electrophotographic recording devices, capacitors, charge injection layers, Schottky diodes, planarising layers, antistatic films, conducting substrates, conducting patterns, photoconductors, electrophotographic applications, electrophotographic recording, organic memory devices, biosensors, biochips.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the birefringence versus wavelength plot for a polymerised film made from a reactive mesogen of prior art.
FIG. 2 shows the refractive index versus wavelength plot of a modelled molecule with low or negative retardation dispersion, showing increased n o dispersion and decreased n e dispersion.
FIG. 3 a and FIG. 3 b do schematically depict a compound according to the present invention.
FIG. 4 a and FIG. 4 b show the birefringence versus wavelength plot for a compound with negative optical dispersion (4a) and positive optical dispersion (4b), respectively.
FIGS. 5-8 show the retardation profile of films of the invention.
TERMS AND DEFINITIONS
The term “liquid crystal or mesogenic compound” means a compound comprising one or more calamitic (rod- or board/lath-shaped) or discotic (disk-shaped) mesogenic groups. The term “mesogenic group” means a group with the ability to induce liquid crystal (LC) phase behaviour. The compounds comprising mesogenic groups do not necessarily have to exhibit an LC phase themselves. It is also possible that they show LC phase behaviour only in mixtures with other compounds, or when the mesogenic compounds or materials, or the mixtures thereof, are polymerised. For the sake of simplicity, the term “liquid crystal” is used hereinafter for both mesogenic and LC materials. For an overview of definitions see C. Tschierske, G. Pelzl and S. Diele, Angew. Chem. 2004, 116, 6340-6368.
A calamitic mesogenic group is usually comprising a mesogenic core consisting of one or more aromatic or non-aromatic cyclic groups connected to each other directly or via linkage groups, optionally comprising terminal groups attached to the ends of the mesogenic core, and optionally comprising one or more lateral groups attached to the long side of the mesogenic core, wherein these terminal and lateral groups are usually selected e.g. from carbyl or hydrocarbyl groups, polar groups like halogen, nitro, hydroxy, etc., or polymerisable groups.
The term “reactive mesogen” (RM) means a polymerisable mesogenic or liquid crystal compound.
Polymerisable compounds with one polymerisable group are also referred to as “monoreactive” compounds, compounds with two polymerisable groups as “direactive” compounds, and compounds with more than two polymerisable groups as “multireactive” compounds. Compounds without a polymerisable group are also referred to as “non-reactive” compounds.
The term “film” includes rigid or flexible, self-supporting or free-standing films with mechanical stability, as well as coatings or layers on a supporting substrate or between two substrates.
The term “pi-conjugated” means a group containing mainly C atoms with sp 2 -hybridisation, or optionally also sp-hybridisation, which may also be replaced by hetero atoms. In the simplest case this is for example a group with alternating C—C single and double bonds, or triple bonds, but does also include groups like 1,3- or 1,4-phenylene. Also included in this meaning are groups like for example aryl amines, aryl phosphines and certain heterocycles (i.e. conjugation via N-, O-, P- or S-atoms).
The term “carbyl group” means any monovalent or multivalent organic radical moiety which comprises at least one carbon atom either without any non-carbon atoms (like for example —C≡C—), or optionally combined with at least one non-carbon atom such as N, O, S, P, Si, Se, As, Te or Ge (for example carbonyl etc.). The term “hydrocarbyl group” denotes a carbyl group that does additionally contain one or more H atoms and optionally contains one or more hetero atoms like for example N, O, S, P, Si, Se, As, Te or Ge. A carbyl or hydrocarbyl group comprising a chain of 3 or more C atoms may also be linear, branched and/or cyclic, including spiro and/or fused rings.
On the molecular level, the birefringence of a liquid crystal depends on the anisotropy of the polarizability (Δα=α ∥ −α⊥). “Polarizability” means the ease with which the electron distribution in the atom or molecule can be distorted. The polarizability increases with greater number of electrons and a more diffuse electron cloud. The polarizability can be calculated using a method described in eg Jap. J. Appl. Phys. 42, (2003) p 3463.
The “optical retardation” at a given wavelength R(λ) (in nm) of a layer of liquid crystalline or birefringent material is defined as the product of birefringence at that wavelength Δn(λ) and layer thickness d (in nm) according to the equation
R (λ)=Δ n (λ)· d
The optical retardation R represents the difference in the optical path lengths in nanometers traveled by S-polarised and P-polarised light whilst passing through the birefringent material. “On-axis” retardation means the retardation at normal incidence to the sample surface.
The term “negative (optical) dispersion” refers to a birefringent or liquid crystalline material or layer that displays reverse birefringence dispersion where the magnitude of the birefringence (Δn) increases with increasing wavelength (λ). i.e |Δn(450)|<|Δn(550)|, or Δn(450)/Δn(550)<1, where Δn(450) and Δn(550) are the birefringence of the material measured at wavelengths of 450 nm and 550 nm respectively. In contrast, positive (optical) dispersion” means a material or layer having |Δn(450)|>|Δn(550)| or Δn(450)/Δn(550)>1. See also for example A. Uchiyama, T. Yatabe “Control of Wavelength Dispersion of Birefringence for Oriented Copolycarbonate Films Containing Positive and Negative Birefringent Units”. J. Appl. Phys. Vol. 42 pp 6941-6945 (2003).
This is shown schematically in FIG. 4 a.
Since the optical retardation at a given wavelength is defined as the product of birefringence and layer thickness as described above [R(λ)=Δn(λ) d], the optical dispersion can be expressed either as the “birefringence dispersion” by the ratio Δn(450)/Δn(550), or as “retardation dispersion” by the ratio R(450)/R(550), wherein R(450) and R(550) are the retardation of the material measured at wavelengths of 450 nm and 550 nm respectively. Since the layer thickness d does not change with the wavelength, R(450)/R(550) is equal to Δn(450)/Δn(550). Thus, a material or layer with negative or reverse dispersion has R(450)/R(550)<1 or |R(450)|<|R(550)|, and a material or layer with positive or normal dispersion has R(450)/R(550)>1 or |R(450)|>|R(550)|.
In the present invention, unless stated otherwise “optical dispersion” means the retardation dispersion i.e. the ratio (R(450)/R(550).
The retardation (R(λ)) of a material can be measured using a spectroscopic ellipsometer, for example the M2000 spectroscopic ellipsometer manufactured by J. A. Woollam Co., This instrument is capable of measuring the optical retardance in nanometers of a birefringent sample e.g. Quartz over a range of wavelengths typically, 370 nm to 2000 nm. From this data it is possible to calculate the dispersion (R(450)/R(550) or Δn(450)/Δn(550)) of a material.
A method for carrying out these measurements was presented at the National Physics Laboratory (London, UK) by N. Singh in October 2006 and entitled “Spectroscopic Ellipsometry, Part 1—Theory and Fundamentals, Part 2 —Practical Examples and Part 3—measurements”. In accordance with the measurement procedures described Retardation Measurement (RetMeas) Manual (2002) and Guide to WVASE (2002) (Woollam Variable Angle Spectroscopic Ellipsometer) published by J. A. Woollam Co. Inc (Lincoln, Nebr., USA). Unless stated otherwise, this method is used to determine the retardation of the materials, films and devices described in this invention.
DETAILED DESCRIPTION OF THE INVENTION
Preferably the birefringent polymer film according to the present invention is prepared by polymerising a formulation comprising one or more polymerisable compounds having the structural features as described above and below, hereinafter referred to as “guest component” or “guest compound”, and an LC material, hereinafter referred to as “host component” or “host mixture”, preferably a polymerisable LC host mixture having a nematic phase. The terms “guest” and “host” do not exclude the possibility that the amount of the guest component in the final LC mixture is >50% by weight, and the amount of the host component in the final LC mixture is <50% by weight.
The birefringent polymer film preferably has positive birefringence and negative (or “reverse”) dispersion.
The host component preferably has positive birefringence and positive (or “normal”) dispersion.
The guest component preferably has
(1) Negative birefringence at 550 nm and normal (positive) birefringence dispersion (e.g. negative calamitic compound) or (2) Positive birefringence at 550 nm and reverse (negative) birefringence dispersion. In this case Δn(450)/Δn(550) can be negative if the guest component has a negative birefringence at 450 nm.
In the guest compounds, the mesogenic groups do preferably exhibit a low polarizability and are preferably calamitic groups, very preferably rod-shaped groups.
The mesogenic groups are preferably comprising mainly non-aromatic, most preferably fully saturated, carbocyclic or heterocyclic groups which are connected directly or via linkage groups, wherein “mainly” means that each mesogenic group comprises more saturated rings than unsaturated or aromatic rings, and very preferably does not comprise more than one unsaturated or aromatic ring.
In the guest compounds, the two mesogenic groups can be identical or different from each other.
The bridging group does preferably exhibit a high polarizability and is preferably consisting mainly, very preferably exclusively, of subgroups selected from pi-conjugated linear groups, aromatic and heteroaromatic groups.
Preferably the bridging group consists, very preferably exclusively, of one or more subgroups selected from groups having a bonding angle of 120° or more, preferably in the range of 180°. Suitable and preferred subgroups include, without limitation, groups comprising sp-hybridised C-atoms, like —C≡C—, or divalent aromatic groups connected to their neighboured groups in para-position, like e.g. 1,4-phenylene, naphthalene-2,6-diyl, indane-2,6-diyl or thieno[3,2-b]thiophene-2,5-diyl.
Preferably the bridging group is connected to an sp 3 -hybridised C-atom or Si-atom located in a non-aromatic ring of the mesogenic group. Very preferably the bridging group is connected in axial position to a cyclohexylene or silanane ring comprised in the mesogenic group, which is optionally substituted and wherein one or more non-adjacent C-atoms are optionally replaced by Si and/or one or more non-adjacent CH 2 groups are optionally replaced by —O— and/or —S—.
FIG. 3 a and FIG. 3 b do schematically illustrate the structure of a guest compound according to the present invention, without limiting its scope. Therein 1 denotes mesogenic calamitic groups, 2 denotes a bridging group, 3 denotes polymerisable groups that are attached to the mesogenic groups 1 via spacer groups, and 4 denotes non-polymerisable terminal groups like carbyl or hydrocarbyl.
The guest compounds according to the present invention are not limited to the structures shown in FIGS. 3 a and 3 b . For example, the compounds may also comprise polymerisable groups in other positions than those shown in FIGS. 3 a and 3 b , or in addition to those shown in FIGS. 3 a and 3 b , e.g. at the end of the terminal groups 4. The polymerisable groups may also be attached directly to the mesogenic groups without spacer groups. The terminal groups 4 may also be omitted.
Since the bridging group is a linear group consisting of subgroups having bonding angles of approx. 180°, and is linked to the mesogenic groups via an sp 3 -hybridised C-atom or Si-atom (i.e. with a bonding angle of approx. 109°), the compounds of the present invention have an H-shaped or L-shaped structure, wherein the mesogenic groups are substantially parallel to each other and substantially perpendicular to the bridging group, as illustrated in FIG. 3 a and FIG. 3 b.
In addition, the bridging group, which essentially consists of subgroups with pi-conjugation, has a high polarizability and a high refractive index, whereas the mesogenic groups, which essentially consist of non-aromatic rings, have a low polarizability and a low refractive index. As a result, the compounds show, depending on their exact structure, either positive birefringence and negative dispersion, as schematically depicted in FIG. 4 a , or negative birefringence with positive dispersion, as schematically depicted in FIG. 4 b.
As a reference normal calamitic materials have positive birefringence and polsitive dispersion. It is desirable to have materials where the magnitude of Δn decreases at shorter wavelength, and compounds with both positive dispersion and negative birefringence can be mixed with a host material to give a mixture which possesses a range of dispersion (depending on the concentration of the dopant and host) varying from positive birefringence with positive dispersion through to positive birefringence with negative dispersion.
Preferably the guest compounds are selected of formula I
wherein
U 1,2 are independently of each other selected from
including their mirror images, wherein the rings U 1 and U 2 are each bonded to the group —(B) q — via the axial bond, and one or two non-adjacent CH 2 groups in these rings are optionally replaced by O and/or S, and the rings U 1 and U 2 are optionally substituted by one or more groups L,
Q 1,2 are independently of each other CH or SiH,
Q 3 is C or Si,
B is in each occurrence independently of one another —C≡C—, —CY 1 ═CY 2 — or an optionally substituted aromatic or heteroaromatic group,
Y 1,2 are independently of each other H, F, Cl, CN or R 0 ,
q is an integer from 1 to 10, preferably 1, 2, 3, 4, 5 or 6,
A 1-4 are independently of each other selected from non-aromatic, aromatic or heteroaromatic carbocylic or heterocyclic groups, which are optionally substituted by one or more groups R 5 , and wherein each of -(A 1 -Z 1 ) m —U 1 —(Z 2 -A 2 ) n - and -(A 3 -Z 3 ) o —U 2 —(Z 4 -A 4 ) p - does not contain more aromatic groups than non-aromatic groups and preferably does not contain more than one aromatic group,
Z 1-4 are independently of each other —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR 0 —, —NR 0 —CO—, —NR 0 —CO—NR 0 —, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH 2 CH 2 —, —(CH 2 ) 3 —, (CH 2 ) 4 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —CH═CH—, —CY 1 ═CY 2 —, —CH═N—, —N═CH—, —N═N—, —CH═CR 0 —, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, CR 0 R 00 or a single bond,
R 0 and R 00 are independently of each other H or alkyl with 1 to 12 C-atoms,
m and n are independently of each other 0, 1, 2, 3 or 4,
o and p are independently of each other 0, 1, 2, 3 or 4,
R 1-5 are independently of each other identical or different groups selected from H, halogen, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(═O)NR 0 R 00 , —C(═O)X 0 , —C(═O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , P-Sp-, optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or denote P or P-Sp-, or are substituted by P or P-Sp-, wherein the compounds comprise at least one group R 1-5 denoting or being substituted by P or P-Sp-,
P is a polymerizable group,
Sp is a spacer group or a single bond.
In the guest compounds of the present invention, the subgroups forming the bridging group, like B in formula I, are preferably selected from groups having a bonding angle of 120° or more, preferably in the range of 180°. Very preferred are —C≡C— groups or divalent aromatic groups connected to their adjacent groups in para-position, like e.g. 1,4-phenylene, naphthalene-2,6-diyl, indane-2,6-diyl or thieno[3,2-b]thiophene-2,5-diyl.
Further possible subgroups include —CH═CH—, —CY 1 ═CY 2 —, —CH═N—, —N═CH—, —N═N— and —CH═CR 0 — wherein Y 1 , Y 2 , R 0 have the meanings given above.
Preferably the bridging group, like —(B) q — in formula I, comprises one or more groups selected from the group consisting of —C≡C—, optionally substituted 1,4-phenylene and optionally substituted 9H-fluorene-2,7-diyl. The subgroups, or B in formula I, are preferably selected from the group consisting of —C≡C—, optionally substituted 1,4-phenylene and optionally substituted 9H-fluorene-2,7-diyl, wherein in the fluorene group the H-atom in 9-position is optionally replaced by a carbyl or hydrocarbyl group.
Very preferably the bridging group, or —(B) q — in formula I, are selected from —C≡C—, —C≡C—C≡C—, —C≡C—C≡C—C≡C—, —C≡C—C≡C—C≡C—C≡C—,
wherein r is 0, 1, 2, 3 or 4 and L has the meaning as described below.
In the guest compounds of the present invention, the non-aromatic rings of the mesogenic groups where the bridging group is attached, like U 1 and U 2 in formula I, are preferably selected from
wherein R 5 is as defined in formula I.
In the guest compounds of the present invention, the aromatic groups, like A 1-4 in formula I, may be mononuclear, i.e. having only one aromatic ring (like for example phenyl or phenylene), or polynuclear, i.e. having two or more fused rings (like for example napthyl or naphthylene). Especially preferred are mono-, bi- or tricyclic aromatic or heteroaromatic groups with up to 25 C atoms that may also comprise fused rings and are optionally substituted.
Preferred aromatic groups include, without limitation, benzene, biphenylene, triphenylene, [1,1′:3′1″]terphenyl-2′-ylene, naphthalene, anthracene, binaphthylene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzpyrene, fluorene, indene, indenofluorene, spirobifluorene, etc.
Preferred heteroaromatic groups include, without limitation, 5-membered rings like pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 6-membered rings like pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, and fused systems like carbazole, indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, dithienopyridine, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene, or combinations thereof.
In the compounds of the present invention, the non-aromatic carbocyclic and heterocyclic rings, like A 1-4 in formula I, include those which are saturated (also referred to as “fully saturated”), i.e. they do only contain C-atoms or hetero atoms connected by single bonds, and those which are unsaturated (also referred to as “partially saturated”), i.e. they also comprise C-atoms or hetero atoms connected by double bonds. The non-aromatic rings may also comprise one or more hetero atoms, preferably selected from Si, O, N and S.
The non-aromatic carbocyclic and heterocyclic groups may be mononuclear, i.e. having only one ring (like for example cyclohexane), or polynuclear, i.e. having two or more fused rings (like for example decahydronaphthalene or bicyclooctane). Especially preferred are fully saturated groups. Further preferred are mono-, bi- or tricyclic non-aromatic groups with up to 25 C atoms that optionally comprise fused rings and are optionally substituted. Very preferred are 5-, 6-, 7- or 8-membered carbocyclic rings wherein one or more non-adjacent C-atoms are optionally replaced by Si and/or one or more non-adjacent CH groups are optionally replaced by N and/or one or more non-adjacent CH 2 groups are optionally replaced by —O— and/or —S—, all of which are optionally substituted.
Preferred non-aromatic groups include, without limitation, 5-membered rings like cyclopentane, tetrahydrofuran, tetrahydrothiofuran, pyrrolidine, 6-membered rings like cyclohexane, silinane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine, 7-membered rings like cycloheptane, and fused systems like bicyclo[2.2.2]octane, tetrahydronaphthalene, decahydronaphthalene, indane, or combinations thereof.
Preferably the non-aromatic and aromatic rings, or A 1-4 in formula I, are selected from trans-1,4-cyclohexylene and 1,4-phenylene that is optionally substituted with one or more groups L.
Preferably the mesogenic groups comprise not more than one, very preferably no aromatic ring, most preferably no aromatic or unsaturated ring.
Very preferred are compounds of formula I wherein m and p are 1 and n and o are 1 or 2. Further preferred are compounds of formula I wherein m and p are 1 or 2 and n and o are 0. Further preferred are compounds wherein m, n, o and p are 2.
In the guest compounds of the present invention, the linkage groups connecting the aromatic and non-aromatic cyclic groups in the mesogenic groups, like Z 1-4 in formula I, are preferably selected from —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR 0 —, —NR 0 —CO—, —NR 0 —CO—NR 0 —, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH 2 CH 2 —, —(CH 2 ) 3 , —(CH 2 ) 4 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —CH═CH—, —CY 1 ═CY 2 —, —CH═N—, —N═CH—, —N═N—, —CH═CR 0 —, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, CR 0 R 00 or a single bond, very preferably from —COO—, —OCO— and a single bond.
In the guest compounds of the present invention, the substituents on the rings, like L in formula I, are preferably selected from P-Sp-, F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O)NR 0 R 00 , —C(═O)X, —C(═O)OR 0 , —C(═O)R 0 , —NR 0 R 0 , —OH, —SF 5 , optionally substituted silyl, aryl or heteroaryl with 1 to 12, preferably 1 to 6 C atoms, and straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12, preferably 1 to 6 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, wherein R 0 and R 00 are as defined in formula I and X is halogen.
Preferred substituents are selected from F, Cl, CN, NO 2 or straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonlyoxy or alkoxycarbonyloxy with 1 to 12 C atoms, wherein the alkyl groups are optionally perfluorinated, or P-Sp-.
Very preferred substituents are selected from F, Cl, CN, NO 2 , CH 3 , C 2 H 5 , C(CH 3 ) 3 , CH(CH 3 ) 2 , CH 2 CH(CH 3 )C 2 H 5 , OCH 3 , OC 2 H 5 , COCH 3 , COC 2 H 5 , COOCH 3 , COOC 2 H 5 , CF 3 , OCF 3 , OCHF 2 , OC 2 F 5 or P-Sp-, in particular F, Cl, CN, CH 3 , C 2 H 5 , C(CH 3 ) 3 , CH(CH 3 ) 2 , OCH 3 , COCH 3 or OCF 3 , most preferably F, Cl, CH 3 , C(CH 3 ) 3 , OCH 3 or COCH 3 , or P-Sp-.
is preferably
with L having each independently one of the meanings given above.
In the guest compounds of the present invention, the carbyl and hydrocarbyl groups, like R 1-5 in formula I, are preferably selected from straight-chain, branched or cyclic alkyl with 1 to 40, preferably 1 to 25 C-atoms, which is unsubstituted, mono- or polysubstituted by F, Cl, Br, I or CN, and wherein one or more non-adjacent CH 2 groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR 0 —, —SiR 0 R 00 —, —CO—, —COO—, —OCO—, —O—CO—O—, —S—CO—, —CO—S—, —SO 2 —, —CO—NR 0 —, —NR 0 —CO—, —NR 0 —CO—NR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, wherein Y 1 and Y 2 are independently of each other H, F, Cl or CN, and R 0 and R 00 are independently of each other H or an optionally substituted aliphatic or aromatic hydrocarbon with 1 to 20 C atoms.
Very preferably the carbyl and hydrocarbyl groups, and R 1-5 in formula I, are selected from, C 1 -C 20 -alkyl, C 1 -C 20 -oxaalkyl, C 1 -C 20 -alkoxy, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 1 -C 20 -thioalkyl, C 1 -C 20 -silyl, C 1 -C 20 -ester, C 1 -C 20 -amino, C 1 -C 20 -fluoroalkyl.
An alkyl or alkoxy radical, i.e. where the terminal CH 2 group is replaced by —O—, can be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6, 7 or 8 carbon atoms and accordingly is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, or octoxy, furthermore methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy, for example.
Oxaalkyl, i.e. where one CH 2 group is replaced by —O—, is preferably straight-chain 2-oxapropyl(=methoxymethyl), 2-(=ethoxymethyl) or 3-oxabutyl(=2-methoxyethyl), 2-, 3-, or 4-oxapentyl, 2-, 3-, 4-, or 5-oxahexyl, 2-, 3-, 4-, 5-, or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl, for example.
An alkyl group wherein one or more CH 2 groups are replaced by —CH═CH— can be straight-chain or branched. It is preferably straight-chain, has 2 to 10 C atoms and accordingly is preferably vinyl, prop-1-, or prop-2-enyl, but-1-, 2- or but-3-enyl, pent-1-, 2-, 3- or pent-4-enyl, hex-1-, 2-, 3-, 4- or hex-5-enyl, hept-1-, 2-, 3-, 4-, 5- or hept-6-enyl, oct-1-, 2-, 3-, 4-, 5-, 6- or oct-7-enyl, non-1-, 2-, 3-, 4-, 5-, 6-, 7- or non-8-enyl, dec-1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or dec-9-enyl.
Especially preferred alkenyl groups are C 2 -C 7 -1E-alkenyl, C 4 -C 7 -3E-alkenyl, C 5 -C 7 -4-alkenyl, C 6 -C 7 -5-alkenyl and C 7 -6-alkenyl, in particular C 2 -C 7 -1 E-alkenyl, C 4 -C 7 -3E-alkenyl and C 5 -C 7 -4-alkenyl. Examples for particularly preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 C atoms are generally preferred.
In an alkyl group wherein one CH 2 group is replaced by —O— and one by —CO—, these radicals are preferably neighboured. Accordingly these radicals together form a carbonyloxy group —CO—O— or an oxycarbonyl group —O—CO—. Preferably this group is straight-chain and has 2 to 6 C atoms. It is accordingly preferably acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxy-carbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxy-carbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl, 4-(methoxycarbonyl)-butyl.
An alkyl group wherein two or more CH 2 groups are replaced by —O— and/or —COO— can be straight-chain or branched. It is preferably straight-chain and has 3 to 12 C atoms. Accordingly it is preferably bis-carboxy-methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy-butyl, 5,5-bis-carboxy-pentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy-heptyl, 8,8-bis-carboxy-octyl, 9,9-bis-carboxy-nonyl, 10,10-bis-carboxy-decyl, bis-(methoxycarbonyl)-methyl, 2,2-bis-(methoxycarbonyl)-ethyl, 3,3-bis-(methoxycarbonyl)-propyl, 4,4-bis-(methoxycarbonyl)-butyl, 5,5-bis-(methoxycarbonyl)-pentyl, 6,6-bis-(methoxycarbonyl)-hexyl, 7,7-bis-(methoxycarbonyl)-heptyl, 8,8-bis-(methoxycarbonyl)-octyl, bis-(ethoxycarbonyl)-methyl, 2,2-bis-(ethoxycarbonyl)-ethyl, 3,3-bis-(ethoxycarbonyl)-propyl, 4,4-bis-(ethoxycarbonyl)-butyl, 5,5-bis-(ethoxycarbonyl)-hexyl.
An alkyl or alkenyl group that is monosubstituted by CN or CF 3 is preferably straight-chain. The substitution by CN or CF 3 can be in any desired position.
An alkyl or alkenyl group that is at least monosubstituted by halogen is preferably straight-chain. Halogen is preferably F or Cl, in case of multiple substitution preferably F. The resulting groups include also perfluorinated groups. In case of monosubstitution the F or Cl substituent can be in any desired position, but is preferably in ω-position. Examples for especially preferred straight-chain groups with a terminal F substituent are fluoromethyl, 2-fluorethyl, 3-fluorpropyl, 4-fluorbutyl, 5-fluorpentyl, 6-fluorhexyl and 7-fluorheptyl. Other positions of F are, however, not excluded.
R 0 and R 00 are preferably selected from H, straight-chain or branched alkyl with 1 to 12 C atoms.
—CY 1 ═CY 2 — is preferably —CH═CH—, —CF═CF— or —CH═C(CN)—.
Halogen is F, Cl, Br or I, preferably F or Cl.
R 1-5 can be an achiral or a chiral group. Particularly preferred chiral groups are 2-butyl(=1-methylpropyl), 2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, in particular 2-methylbutyl, 2-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methylhexoxy, 2-octyloxy, 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 4-methylhexyl, 2-hexyl, 2-octyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methoxyoctoxy, 6-methyloctoxy, 6-methyloctanoyloxy, 5-methylheptyloxycarbonyl, 2-methylbutyryloxy, 3-methylvaleroyloxy, 4-methylhexanoyloxy, 2-chlorpropionyloxy, 2-chloro-3-methylbutyryloxy, 2-chloro-4-methylvaleryloxy, 2-chloro-3-methylvaleryloxy, 2-methyl-3-oxapentyl, 2-methyl-3-oxahexyl, 1-methoxypropyl-2-oxy, 1-ethoxypropyl-2-oxy, 1-propoxypropyl-2-oxy, 1-butoxypropyl-2-oxy, 2-fluorooctyloxy, 2-fluorodecyloxy, 1,1,1-trifluoro-2-octyloxy, 1,1,1-trifluoro-2-octyl, 2-fluoromethyloctyloxy for example. Very preferred are 2-hexyl, 2-octyl, 2-octyloxy, 1,1,1-trifluoro-2-hexyl, 1,1,1-trifluoro-2-octyl and 1,1,1-trifluoro-2-octyloxy.
Preferred achiral branched groups are isopropyl, isobutyl(=methylpropyl), isopentyl(=3-methylbutyl), isopropoxy, 2-methyl-propoxy and 3-methylbutoxy.
In the guest compounds of the present invention, the polymerisable group, like P in formula I, is a group that is capable of participating in a polymerisation reaction, like radical or ionic chain polymerisation, polyaddition or polycondensation, or capable of being grafted, for example by condensation or addition, to a polymer backbone in a polymer analogous reaction. Especially preferred are polymerisable groups for chain polymerisation reactions, like radical, cationic or anionic polymerisation. Very preferred are polymerisable groups comprising a C—C double or triple bond, and polymerisable groups capable of polymerisation by a ring-opening reaction, like oxetanes or epoxides.
Suitable and preferred polymerisable groups include, without limitation, CH 2 ═CW 1 —COO—, CH 2 ═CW 1 —CO—,
CH 2 ═CW 2 —(O) k1 —, CH 3 —CH═CH—O—, (CH 2 ═CH) 2 CH—OCO—, (CH 2 ═CH—CH 2 ) 2 CH—OCO—, (CH 2 ═CH) 2 CH—O—, (CH 2 ═CH—CH 2 ) 2 N—, (CH 2 ═CH—CH 2 ) 2 N—CO—, HO—CW 2 W 3 —, HS—CW 2 W 3 —, HW 2 N—, HO—CW 2 W 3 —NH—, CH 2 ═CW 1 —CO—NH—, CH 2 ═CH—(COO) k1 -Phe-(O) k2 —, CH 2 ═CH—(CO) k1 -Phe-(O) k2 —, Phe-CH═CH—, HOOC—, OCN—, and W 4 W 5 W 6 Si—, with W 1 being H, F, Cl, CN, CF 3 , phenyl or alkyl with 1 to 5 C-atoms, in particular H, F, C 1 or CH 3 , W 2 and W 3 being independently of each other H or alkyl with 1 to 5 C-atoms, in particular H, methyl, ethyl or n-propyl, W 4 , W 5 and W 6 being independently of each other Cl, oxaalkyl or oxacarbonylalkyl with 1 to 5 C-atoms, W 7 and W 8 being independently of each other H, Cl or alkyl with 1 to 5 C-atoms, Phe being 1,4-phenylene that is optionally substituted, preferably by one or more groups L as defined above (except for the meaning P-Sp-), and k 1 and k 2 being independently of each other 0 or 1.
Very preferred polymerisable groups are selected from CH 2 ═CW 1 —COO—, CH 2 ═CW 1 —CO—,
(CH 2 ═CH) 2 CH—OCO—, (CH 2 ═CH—CH 2 ) 2 CH—OCO—, (CH 2 ═CH) 2 CH—O—, (CH 2 ═CH—CH 2 ) 2 N—, (CH 2 ═CH—CH 2 ) 2 N—CO—, HO—CW 2 W 3 —, HS—CW 2 W 3 —, HW 2 N—, HO—CW 2 W 3 —NH—, CH 2 ═CW 1 —CO—NH—, CH 2 ═CH—(COO) k1 -Phe-(O) k2 —, CH 2 ═CH—(CO) k1 -Phe-(O) k2 —, Phe-CH═CH—, HOOC—, OCN—, and W 4 W 5 W 6 Si—, with W 1 being H, F, Cl, CN, CF 3 , phenyl or alkyl with 1 to 5 C-atoms, in particular H, F, C 1 or CH 3 , W 2 and W 3 being independently of each other H or alkyl with 1 to 5 C-atoms, in particular H, methyl, ethyl or n-propyl, W 4 , W 5 and W 6 being independently of each other Cl, oxaalkyl or oxacarbonylalkyl with 1 to 5 C-atoms, W 7 and W 8 being independently of each other H, Cl or alkyl with 1 to 5 C-atoms, Phe being 1,4-phenylene that is optionally substituted preferably by one or more groups L as defined above (except for the meaning P-Sp-), and k 1 and k 2 being independently of each other 0 or 1.
Most preferred polymerisable groups are selected from CH 2 ═CH—COO—, CH 2 ═C(CH 3 )—COO—, CH 2 ═CF—COO—, (CH 2 ═CH) 2 CH—OCO—, (CH 2 ═CH) 2 CH—O—,
Polymerisation can be carried out according to methods that are known to the ordinary expert and described in the literature, for example in D. J. Broer; G. Challa; G. N. Mol, Macromol. Chem., 1991, 192, 59.
The term “spacer group” is known in prior art and suitable spacer groups, like Sp in formula I, are known to the skilled person (see e.g. Pure Appl. Chem. 73(5), 888 (2001). The spacer group is preferably selected of formula Sp′-X′, such that P-Sp- is P-Sp′-X′—, wherein
Sp′ is alkylene with 1 to 20 C atoms, preferably 1 to 12 C-atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I or CN, and wherein one or more non-adjacent CH 2 groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR o —, —SiR 0 R 00 —, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —NR 0 —CO—O—, —O—CO—NR 0 —, —NR 0 —CO—NR 0 —, —CH═CH— or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, X′ is —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR 0 —, —NR 0 —CO—, —NR 0 —CO—NR 0 —, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —CH═N—, —N═CH—, —N═N—, —CH═CR 0 —, —CY 1 ═CY 2 —, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond, R 0 and R 00 are independently of each other H or alkyl with 1 to 12 C-atoms, and Y 1 and Y 2 are independently of each other H, F, Cl or CN. X′ is preferably —O—, —S—CO—, —COO—, —OCO—, —O—COO—, —CO—NR 0 —, —NR 0 —CO—, —NR 0 —CO—NR 0 — or a single bond.
Typical groups Sp′ are, for example, —(CH 2 ) p1 —, —(CH 2 CH 2 O) q1 —CH 2 CH 2 —, —CH 2 CH 2 —S—CH 2 CH 2 — or —CH 2 CH 2 —NH—CH 2 CH 2 — or —(SiR 0 R 00 —O) p1 —, with p1 being an integer from 2 to 12, q1 being an integer from 1 to 3 and R 0 and R 00 having the meanings given above.
Preferred groups Sp′ are ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxy-butylene, ethylene-thioethylene, ethylene-N-methyl-iminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene for example. Further preferred are chiral spacer groups.
Further preferred are compounds wherein the polymerisable group is directly attached to the mesogenic group without a spacer group Sp.
In case of compounds with two or more groups P-Sp-, the polymerisable groups P and the spacer groups Sp can be identical or different.
In another preferred embodiment the guest compounds comprise one or more terminal groups, like R 1-4 , or substituents, like R 5 , that are substituted by two or more polymerisable groups P or P-Sp- (multifunctional polymerisable groups). Suitable multifunctional polymerisable groups of this type are disclosed for example in U.S. Pat. No. 7,060,200 B1 oder US 2006/0172090 A1. Very preferred are compounds comprising one or more multifunctional polymerisable groups selected from the following formulae:
—X-alkyl-CHP 1 —CH 2 —CH 2 P 2 P1
—X′-alkyl-C(CH 2 P 1 )(CH 2 P 2 )—CH 2 P 3 P2
—X′-alkyl-CHP 1 CHP 2 —CH 2 P 3 P3
—X 1 -alkyl-C(CH 2 P 1 )(CH 2 P 2 )—C a H 2a+1 P4
—X′-alkyl-CHP 1 —CH 2 P 2 P5
—X′-alkyl-CHP 1 P 2 P5
—X′-alkyl-CP 1 P 2 —C a H 2a+1 P6
—X′-alkyl-C(CH 2 P 1 )(CH 2 P 2 )—CH 2 OCH 2 —C(CH 2 P 3 )(CH 2 P 4 )CH 2 P 5 P7
—X′-alkyl-CH((CH 2 ) a P 1 )((CH 2 ) b P 2 ) P8
—X′-alkyl-CHP 1 CHP 2 —C a H 2a+1 P9
wherein
alkyl is straight-chain or branched alkylene having 1 to 12 C-atoms which is unsubstituted, mono- or polysubstituted by F, Cl, Br, I or CN, and wherein one or more non-adjacent CH 2 groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR 0 —, —SiR 0 R 00 —, —CO—, —COO—, —OCO —, —O—CO—O—, —S—CO—, —CO—S—, —SO 2 —, —CO—NR 0 —, —NR 0 —CO—, —NR 0 —CO—NR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, with R 0 and R 00 having the meanings given above, or denotes a single bond, a and b are independently of each other 0, 1, 2, 3, 4, 5 or 6, X′ is as defined above, and P 1-5 independently of each other have one of the meanings given for P above.
Very preferred compounds of formula I are those of the following subformulae:
wherein R 1-5 , A 1-4 , Z 1-4 , B, m, n, o, p and q have the meanings given above.
Especially preferred are compounds of the following subformulae:
wherein Z has one of the meanings of Z 1 given above, R has one of the meanings of R 1 as given above that is different from P-Sp-, and P, Sp, L and r are as defined above, and the benzene rings in the mesogenic groups are optionally substituted by one or more groups L as defined above.
P-Sp- in these preferred compounds is preferably P-Sp′-X′, with X′ preferably being —O—, —COO— or —OCOO—. Z is preferably —COO— or —OCO—.
The compounds of formula I can be synthesized according to or in analogy to methods which are known per se and which are described in the literature and in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart. Especially suitable methods are disclosed in U.S. Pat. No. 6,203,724. Further suitable methods of synthesis are also described below and in the examples.
The compounds of formula I can be generally synthesized by initially reacting a suitably substituted acetylene, e.g. (trimethylsilyl)acetylene, with a suitable cyclohexanone in the presence of butyllithium, as described e.g. in ACS Symposium Series (2001), 798 (Anisotropic Organic Materials), 195-205. After separation of the isomers by chromatography, the axial acetylenic substituents can either be homocoupled to form a dimer, (i.e. intermediate 2 in example 1) or coupled to another ring, such as dihalodobenzene, by palladium catalyzed coupling reactions as described e.g. in either J. Org. Chem. 1997, 62, 7471, or Tetrahedron Lett. 1993, 6403. With suitable choice of halo substituted phenyl rings, this can either give the symmetrical dimer or the axial-phenylacetylenic substituted cyclohexanones, which can be further coupled to another axially substituted acetylenic cyclohexanone to give unsymmetrical examples. All the above examples generally give coupled products that are either mono or di-tertiary alcohols. Esterification of the dialcohols with a suitable carboxylic acid yields a diester product.
An alternative synthetic route involves the formation of the axial-substituted cyclohexanone by the methods described above, followed by esterification of the tertiary alcohols with a suitable carboxylic acid. The ester with an axial substituted acetylenic group can be homocoupled to give the diacetylenes, or coupled to a suitably substituted halo benzene via a palladium catalyzed coupling reaction.
The methods of preparing a guest compound as described above and below are another aspect of the invention. Especially preferred is a method comprising the following steps:
a) reacting a suitably substituted acetylene with an optionally substituted cyclohexanone in the presence of butyllithium, b) separating the isomers thereby formed, c) homocoupling an isomer prepared by steps a) and b) via its axial acetylenic substituents to give a dimer, or d) coupling an isomer prepared by steps a) and b) via its axial acetylenic substituent to another optionally substituted cyclohexanone, or e) coupling an isomer prepared by steps a) and b) via its axial acetylenic substituent to an aromatic ring, and coupling the resulting product to an identical or different isomer prepared by steps a+b).
Another aspect of the invention is a polymerisable material, preferably a polymerisable LC material, comprising one or more guest compounds as described above and below, and one or more additional compounds, which are preferably mesogenic or liquid crystalline and/or polymerisable. Very preferably the LC material comprises one or more additional compounds selected from reactive mesogens (RMs), most preferably selected from mono- and direactive RMs. These additional compounds constitute the polymerisable LC host material.
Preferably the polymer films according to the present invention are crosslinked, and the polymerisable guest compounds and/or the polymerisable host materials comprise at least one compound with two or more polymerisable groups (di- or multireactive).
The concentration of the guest compound(s) of the present invention in the polymerisable LC material (including both the guest and the host material) is preferably from 5 to 90 wt. %, very preferably from 30 to 70 wt. %.
The additional RMs of the polymerisable LC host material can be prepared by methods which are known per se and which are described in standard works of organic chemistry like for example Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart. Suitable RMs are disclosed for example in WO 93/22397, EP 0 261 712, DE 195 04 224, WO 95/22586, WO 97/00600, U.S. Pat. No. 5,518,652, U.S. Pat. No. 5,750,051, U.S. Pat. No. 5,770,107 and U.S. Pat. No. 6,514,578. Examples of particularly suitable and preferred RMs are shown in the following list.
wherein
P 0 is, in case of multiple occurrence independently of one another, a polymerisable group, preferably an acryl, methacryl, oxetane, epoxy, vinyl, vinyloxy, propenyl ether or styrene group, A 0 and B 0 are, in case of multiple occurrence independently of one another, 1,4-phenylene that is optionally substituted with 1, 2, 3 or 4 groups L, or trans-1,4-cyclohexylene, Z 0 is, in case of multiple occurrence independently of one another, —COO—, —OCO—, —CH 2 CH 2 —, —C≡C—, —CH═CH—, —CH═CH—COO—, —OCO—CH═CH— or a single bond, R 0 is alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 or more, preferably 1 to 15 C atoms which is optionally fluorinated, or is Y 0 or P—(CH 2 ) y —(O) z —, Y 0 is F, Cl, CN, NO 2 , OCH 3 , OCN, SCN, SF 5 , optionally fluorinated alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 4 C atoms, or mono- oligo- or polyfluorinated alkyl or alkoxy with 1 to 4 C atoms, R 01,02 are independently of each other H, R 0 or Y 0 , R* is a chiral alkyl or alkoxy group with 4 or more, preferably 4 to 12 C atoms, like 2-methylbutyl, 2-methyloctyl, 2-methylbutoxy or 2-methyloctoxy, Ch is a chiral group selected from cholesteryl, estradiol, or terpenoid radicals like menthyl or citronellyl, L is, in case of multiple occurrence independently of one another, H, F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 5 C atoms, r is 0, 1, 2, 3 or 4, t is, in case of multiple occurrence independently of one another, 0, 1, 2 or 3, u and v are independently of each other 0, 1 or 2, w is 0 or 1, x and y are independently of each other 0 or identical or different integers from 1 to 12, z is 0 or 1, with z being 0 if the adjacent x or y is 0,
and wherein the benzene and napthalene rings can additionally be substituted with one or more identical or different groups L.
Especially preferably the polymerisable LC host material contains only achiral compounds and no chiral compounds.
Further preferably the polymerisable LC host material comprises one or more compounds selected from formula MR3, MR4, MR7, MR8, MR9, MR10, MR18, DR6, DR7 and DR8, furthermore DR1 and DR5.
Further preferably the polymerisable LC host material comprises one or more compounds selected from the following formulae:
wherein P 0 , R 0 , x, y, and z are as defined above.
Further preferably the polymerisable LC host material comprises one or more compounds selected from the following formulae:
Preferably the polymerisable compounds of the polymerisable LC host material are selected from compounds, very preferably mono- or direactive RMs, having low birefringence.
Especially preferred is a polymerisable host material having an absolute value of the birefringence from 0.01 to 0.2, very preferably from 0.04 to 0.16.
The general preparation of polymer LC films according to this invention is known to the ordinary expert and described in the literature, for example in D. J. Broer; G. Challa; G. N. Mol, Macromol. Chem., 1991, 192, 59. Typically a polymerisable LC material is coated or otherwise applied onto a substrate where it aligns into uniform orientation, and polymerised in situ in its LC phase at a selected temperature for example by exposure to heat or actinic radiation, preferably by photo-polymerisation, very preferably by UV-photopolymerisation, to fix the alignment of the LC molecules. If necessary, uniform alignment can promoted by additional means like shearing or annealing the LC material, surface treatment of the substrate, or adding surfactants to the LC material.
As substrate for example glass or quartz sheets or plastic films can be used. It is also possible to put a second substrate on top of the coated material prior to and/or during and/or after polymerisation. The substrates can be removed after polymerisation or not. When using two substrates in case of curing by actinic radiation, at least one substrate has to be transmissive for the actinic radiation used for the polymerisation. Isotropic or birefringent substrates can be used. In case the substrate is not removed from the polymerised film after polymerisation, preferably isotropic substrates are used.
Suitable and preferred plastic substrates are for example films of polyester such as polyethyleneterephthalate (PET) or polyethylene-naphthalate (PEN), polyvinylalcohol (PVA), polycarbonate (PC) or triacetylcellulose (TAC), very preferably PET or TAC films. As birefringent substrates for example uniaxially stretched plastics film can be used. PET films are commercially available for example from DuPont Teijin Films under the trade name Melinex®.
The polymerisable material can be applied onto the substrate by conventional coating techniques like spin-coating or blade coating. It can also be applied to the substrate by conventional printing techniques which are known to the expert, like for example screen printing, offset printing, reel-to-reel printing, letter press printing, gravure printing, rotogravure printing, flexographic printing, intaglio printing, pad printing, heat-seal printing, ink-jet printing or printing by means of a stamp or printing plate.
It is also possible to dissolve the polymerisable material in a suitable solvent. This solution is then coated or printed onto the substrate, for example by spin-coating or printing or other known techniques, and the solvent is evaporated off before polymerisation. In many cases it is suitable to heat the mixture in order to facilitate the evaporation of the solvent. As solvents for example standard organic solvents can be used. The solvents can be selected for example from ketones such as acetone, methyl ethyl ketone, methyl propyl ketone or cyclohexanone; acetates such as methyl, ethyl or butyl acetate or methyl acetoacetate; alcohols such as methanol, ethanol or isopropyl alcohol; aromatic solvents such as toluene or xylene; halogenated hydrocarbons such as di- or trichloromethane; glycols or their esters such as PGMEA (propyl glycol monomethyl ether acetate), γ-butyrolactone, and the like. It is also possible to use binary, ternary or higher mixtures of the above solvents.
Initial alignment (e.g. planar alignment) of the polymerisable LC material can be achieved for example by rubbing treatment of the substrate, by shearing the material during or after coating, by annealing the material before polymerisation, by application of an alignment layer, by applying a magnetic or electric field to the coated material, or by the addition of surface-active compounds to the material. Reviews of alignment techniques are given for example by I. Sage in “Thermotropic Liquid Crystals”, edited by G. W. Gray, John Wiley & Sons, 1987, pages 75-77; and by T. Uchida and H. Seki in “Liquid Crystals—Applications and Uses Vol. 3”, edited by B. Bahadur, World Scientific Publishing, Singapore 1992, pages 1-63. A review of alignment materials and techniques is given by J. Cognard, Mol. Cryst. Liq. Cryst. 78, Supplement 1 (1981), pages 1-77.
Especially preferred is a polymerisable material comprising one or more surfactants that promote a specific surface alignment of the LC molecules.
Suitable surfactants are described for example in J. Cognard, Mol. Cryst. Liq. Cryst. 78, Supplement 1, 1-77 (1981). Preferred aligning agents for planar alignment are for example non-ionic surfactants, preferably fluorocarbon surfactants such as the commercially available Fluorad FC-171® (from 3M Co.) or Zonyl FSN® (from DuPont), multiblock surfactants as described in GB 2 383 040 or polymerisable surfactants as described in EP 1 256 617.
It is also possible to apply an alignment layer onto the substrate and provide the polymerisable material onto this alignment layer. Suitable alignment layers are known in the art, like for example rubbed polyimide or alignment layers prepared by photoalignment as described in U.S. Pat. No. 5,602,661, U.S. Pat. No. 5,389,698 or U.S. Pat. No. 6,717,644.
It is also possible to induce or improve alignment by annealing the polymerisable LC material at elevated temperature, preferably at its polymerisation temperature, prior to polymerisation.
Polymerisation is achieved for example by exposing the polymerisable material to heat or actinic radiation. Actinic radiation means irradiation with light, like UV light, IR light or visible light, irradiation with X-rays or gamma rays or irradiation with high energy particles, such as ions or electrons. Preferably polymerisation is carried out by UV irradiation. As a source for actinic radiation for example a single UV lamp or a set of UV lamps can be used. When using a high lamp power the curing time can be reduced. Another possible source for actinic radiation is a laser, like for example a UV, IR or visible laser.
Polymerisation is preferably carried out in the presence of an initiator absorbing at the wavelength of the actinic radiation. For this purpose the polymerisable LC material preferably comprises one or more initiators, preferably in a concentration from 0.01 to 10%, very preferably from 0.05 to 5%. For example, when polymerising by means of UV light, a photoinitiator can be used that decomposes under UV irradiation to produce free radicals or ions that start the polymerisation reaction. For polymerising acrylate or methacrylate groups preferably a radical photoinitiator is used. For polymerising vinyl, epoxide or oxetane groups preferably a cationic photoinitiator is used. It is also possible to use a thermal polymerisation initiator that decomposes when heated to produce free radicals or ions that start the polymerisation. Typical radical photoinitiators are for example the commercially available Irgacure® or Darocure® (Ciba Geigy AG, Basel, Switzerland). A typical cationic photoinitiator is for example UVI 6974 (Union Carbide).
The polymerisable material may also comprise one or more stabilizers or inhibitors to prevent undesired spontaneous polymerisation, like for example the commercially available Irganox® (Ciba Geigy AG, Basel, Switzerland).
The curing time depends, inter alia, on the reactivity of the polymerisable material, the thickness of the coated layer, the type of polymerisation initiator and the power of the UV lamp. The curing time is preferably ≦5 minutes, very preferably ≦3 minutes, most preferably ≦1 minute. For mass production short curing times of 30 seconds are preferred.
Preferably polymerisation is carried out in an inert gas atmosphere like nitrogen or argon.
The polymerisable material may also comprise one or more dyes having an absorption maximum adjusted to the wavelength of the radiation used for polymerisation, in particular UV dyes like e.g. 4,4″-azoxy anisole or Tinuvin® dyes (from Ciba AG, Basel, Switzerland).
In another preferred embodiment the polymerisable material comprises one or more monoreactive polymerisable non-mesogenic compounds, preferably in an amount of 0 to 50%, very preferably 0 to 20%. Typical examples are alkylacrylates or alkylmethacrylates.
In another preferred embodiment the polymerisable material comprises one or more di- or multireactive polymerisable non-mesogenic compounds, preferably in an amount of 0 to 50%, very preferably 0 to 20%, alternatively or in addition to the di- or multireactive polymerisable mesogenic compounds. Typical examples of direactive non-mesogenic compounds are alkyldiacrylates or alkyldimethacrylates with alkyl groups of 1 to 20 C atoms. Typical examples of multireactive non-mesogenic compounds are trimethylpropanetrimethacrylate or pentaerythritoltetraacrylate.
It is also possible to add one or more chain transfer agents to the polymerisable material in order to modify the physical properties of the polymer film. Especially preferred are thiol compounds, for example monofunctional thiols like dodecane thiol or multifunctional thiols like trimethylpropane tri(3-mercaptopropionate). Very preferred are mesogenic or LC thiols as disclosed for example in WO 96/12209, WO 96/25470 or U.S. Pat. No. 6,420,001. By using chain transfer agents the length of the free polymer chains and/or the length of the polymer chains between two crosslinks in the polymer film can be controlled. When the amount of the chain transfer agent is increased, the polymer chain length in the polymer film decreases.
The polymerisable material may also comprise a polymeric binder or one or more monomers capable of forming a polymeric binder, and/or one or more dispersion auxiliaries. Suitable binders and dispersion auxiliaries are disclosed for example in WO 96/02597. Preferably, however, the polymerisable material does not contain a binder or dispersion auxiliary.
The polymerisable material can additionally comprise one or more additives like for example catalysts, sensitizers, stabilizers, inhibitors, chain-transfer agents, co-reacting monomers, surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes, pigments or nanoparticles.
The thickness of a polymer film according to the present invention is preferably from 0.3 to 5 microns, very preferably from 0.5 to 3 microns, most preferably from 0.7 to 1.5 microns. For use as alignment layer, thin films with a thickness of 0.05 to 1, preferably 0.1 to 0.4 microns are preferred.
The polymer films and materials of the present invention can be used as retardation or compensation film for example in LCDs to improve the contrast and brightness at large viewing angles and reduce the chromaticity. It can be used outside the switchable LC cell of the LCD or between the substrates, usually glass substrates, forming the switchable LC cell and containing the switchable LC medium (incell application).
The polymer film and materials of the present invention can be used in conventional LC displays, for example displays with vertical alignment like the DAP (deformation of aligned phases), ECB (electrically controlled birefringence), CSH (colour super homeotropic), VA (vertically aligned), VAN or VAC (vertically aligned nematic or cholesteric), MVA (multi-domain vertically aligned), PVA (patterned vertically aligned) or PSVA (polymer stabilised vertically aligned) mode; displays with bend or hybrid alignment like the OCB (optically compensated bend cell or optically compensated birefringence), R—OCB (reflective OCB), HAN (hybrid aligned nematic) or pi-cell (π-cell) mode; displays with twisted alignment like the TN (twisted nematic), HTN (highly twisted nematic), STN (super twisted nematic), AMD-TN (active matrix driven TN) mode; displays of the IPS (in plane switching) mode, or displays with switching in an optically isotropic phase.
The layers, films and materials of the present invention can be used for various types of optical films, preferably selected from optically uniaxial films (A-plate, C-plate, negative C-plate, O-plate), twisted optical retarders, like for example twisted quarter wave foils (QWF), achromatic retarders, achromatic QWFs or half wave foils (HWF), and optically biaxial films. The LC phase structure in the layers and materials can be selected from cholesteric, smectic, nematic and blue phases. The alignment of the LC material in the layer can be selected from homeotropic, splayed, tilted, planar and blue-phase alignment. The layers can be uniformly oriented or exhibit a pattern of different orientations.
The films can be used as optical compensation film for viewing angle enhancement of LCD's or as a component in a brightness enhancement films, furthermore as an achromatic element in reflective or transflective LCD's. Further preferred applications and devices include
retarding components in optoelectronic devices requiring similar phase shift at multiple wavelengths, such as combined CD/DVD/HD-DVD/Blu-Ray, including reading, writing re-writing data storage systems achromatic retarders for optical devices such as cameras achromatic retarders for displays including OLED and LCD's.
The following examples are intended to explain the invention without restricting it. The methods, structures and properties described hereinafter can also be applied or transferred to materials that are claimed in this invention but not explicitly described in the foregoing specification or in the examples.
Above and below, percentages are percent by weight. All temperatures are given in degrees Celsius. m.p. denotes melting point, cl.p. denotes clearing point, T g denotes glass transition temperature. Furthermore, C=crystalline state, N=nematic phase, S=smectic phase and I=isotropic phase. The data between or behind these symbols represent the transition temperatures. Δn denotes the optical anisotropy (Δn=n e −n o , where n o denotes the refractive index parallel to the longitudinal molecular axes and n e denotes the refractive index perpendicular thereto), measured at 589 nm and 20° C. The optical and electrooptical data are measured at 20° C., unless expressly stated otherwise.
Method of measuring the refractive indices of the novel materials:
The refractive indices of a liquid crystal mixture commercially available from Merck KGaA under the product code ZL14792 are measured using an Abbe refractometer at 20° C. and using a light of wavelength 589 nm. This mixture is then doped with 10% w/w of the material under test and the refractive indices are remeasured. Extrapolation to 100% gives the refractive index of the material under test.
Unless stated otherwise, the percentages of components of a polymerisable mixture as given above and below refer to the total amount of solids in the mixture polymerisable mixture, i.e. not including solvents.
EXAMPLE 1
Key intermediates used in the synthesis of many examples are the two intermediates shown below:
The synthetic route used to prepare intermediate 2 is shown below. Intermediate 1 is also prepared via a similar route (shown below)
There are two possible methods of converting the product of stage 2 of the above reaction scheme. The first method uses a THP protecting group to protect the alcohol before the acetylene-containing product is coupled. The second method directly converts the product of stage 2 into intermediate 2 using a method disclosed by Lee et al in Journal of Organic Chemistry (2005) 70, 4393.
The synthetic routes that can be used to synthesise the above examples are shown below. Example 2 can also be prepared via an analogous route. Example 3 is prepared via a similar route to example 1, however in this case, intermediate 2 is used rather than intermediate 1
EXAMPLE 2
Compound (1) is prepared via the following route:
A method of preparing 2-[(1-ethynylcyclohexyl)oxy]tetrahydropyran—a compound similar to the key intermediate, the THP protected acetylene (intermediate 4)- has previously been reported in the literature:
1. Lithium hexafluorophosphate-catalyzed efficient tetrahydropyranylation of tertiary alcohols under mild reaction conditions. Syn. Lett . (2004), (10), 1802-1804. 2. Triphenylphosphine hydrobromide: A mild and efficient catalyst for tetrahydropyranylation of tertiary alcohols. Tetrahedron Letters (1988), 29, (36), 4583-6. 3. Bismuth triflate: An efficient catalyst for the formation and deprotection of tetrahydropyranyl ethers. European Journal of Organic Chemistry (2003), (19), 3827-3831.
EXAMPLE 3
Compound (2) is prepared via the following route:
EXAMPLE 4
The synthetic route to compound (3) involves the synthesis of the saturated acid shown below: The synthetic route to this intermediate has been described in the literature (Lub et al in Recueil des Travaux Chimiques der Pays - Bas , (1996), 115, 321)
EXAMPLE 5
Compounds (4) and (5) are prepared by one of two possible routes. The first route uses intermediate 2 as a key intermediate whilst in the alternative route; the ester is prepared first before being dimerised to form the target diacetylene:
Alternative route (here shown for compound (5)):
EXAMPLE 6
Compound (6) is prepared via the following route:
EXAMPLE 7
Compound (7) is prepared via the following route:
EXAMPLE 8
The 1,4-diethynylbenzene compound (8) is prepared via the route shown below:
EXAMPLE 9
Compound (9) is prepared in analogy to Example 8.
EXAMPLE 10
Compound (10) is prepared in analogy to Example 8.
EXAMPLE 11
Compound (11) is prepared as shown below
Compound (11.1) is prepared by reacting, 4-[3-(3-chloro-1-oxopropoxy)propoxy]benzoic acid with 4-ethynyl-4′-propyl-(trans,trans)-[1,1′-bicyclohexyl]-4-ol. Compound (11) is prepared by reacting compound (11.1) with 1,4-diiodobenzene under Sonogashira conditions.
Compound (11) has the following physical properties:
K-I 155.7° C. n e =1.5759 n o =1.5271 Δn=0.0488
EXAMPLE 12
Compound 12 is prepared by a route similar to that shown for example 11 (compound 11). It has the following properties:
K-I 121.8° C. n e =1.5623 n o =1.5218 Δn=0.0405
EXAMPLE 13
Compound 13 is prepared via a synthetic route similar to that described in example 11, but wherein 4,4′-diiodo-1,1′-biphenyl is used for the final Sonagashira reaction step. Compound 13 has the following properties:
K-I 120.7° C. n e =1.5861 n o =1.5508 Δn=0.0353
EXAMPLE 14
Compound 14 is prepared via a synthetic route similar to that described in example 11, but wherein 4′-Pentylbicyclohexyl-4-one is used as starting material, and 1,1′-(1,2-ethynediyl)bis[4-iodobenzene] is used for the final Sonagashira reaction step. Compound 14 has the following properties:
K-I=95.6° C. ne=1.5840 no=1.5670 Δn=0.0140
EXAMPLE 15
Compound 15 is prepared by the route shown above. 4-ethynyl-4′-propyl-(trans,trans)-[1,1′-bicyclohexyl]-4-ol is prepared via the method shown in Example 1. This tertiary alcohol is reacted with 4-(tert-butyl-(4-iodobutoxy)dimethylsilane and sodium hydride in DMF to give the ether tert-butyl-[4-(4-ethynyl-4′-propylbicyclohexyl-4-yloxy)-butoxy]-dimethyl-silane (compound 15.1). Deprotection of this ether gives the alcohol (15.2) which is subsequently esterified with chloropropionyl chloride to give the ester (compound 15.3). This compound is reacted with diiodobenzene under Sonagashira conditions to give the final product (compound 15). Compound 15 has the following physical properties:
K-I 94.6° C. ne=1.5230 no=1.5292 Δn=−0.0062
EXAMPLE 16
Compound 16 is prepared by the route shown above. 4-ethynyl-4′-propyl-(trans,trans)-[1,1′-bicyclohexyl]-4-ol is prepared via the method shown in Example 1. This tertiary alcohol is reacted with iodobenzene and sodium hydride in DMF to give the ether (compound 16.1). Reaction of this compound with an excess of 1,4-diiodobenzene under Sonagashira conditions gives predominantly the monoreacted product, compound 16.2. Subsequent reaction of this compound with compound (11.1) under Sonagashira conditions gives the final unsymmetrical product (compound 16). Compound 16 has the following properties: K-I 91.8° C.
EXAMPLE 17
Compound 17 is prepared via a synthetic route similar to that described in example 11, but wherein 2,7-diiodo-9H-fluorene is used for the final Sonagashira reaction step. Compound 17 has the following optical properties:
ne=1.5820 no=1.5540 Δn=0.0280
EXAMPLE 18
The following mixture is prepared:
FC 171 ®
0.26%
Irg 651 ®
0.38%
Irg 1076 ®
0.03%
Compound (A)
15.32%
Compound 12
24.01%
Toluene
60.00
FC 171 is a fluorosurfactant commercially available from 3M, Irgacure 651 and 1076 are photoinitiators commercially available from Ciba AG. Compound A is described in the literature (see e.g. D. J. Broer; G. Challa; G. N. Mol, Macromol. Chem., 1991, 192, 59).
The formulation is spin coated at 3000 rpm on to a PI coated glass slide. The samples are annealed at 60° C. for 60 s. After annealing, each sample is polymerised using the EFOS lamp (200 mW/cm2) 365 nm filter, under nitrogen at 60° C. for 60 s. The retardation of each slide is measured using the Ellipsometer and the thickness of each slide is measured using the surface profilometer.
The retardation profile of the film is shown in FIG. 5 , and indicates that it has the optical property of an A-plate, and that the film has positive dispersion with R 450 /R 550 =1.091, but the dispersion is lower than the same mixture which does not contain Compound 12 (see Comparative Example 1).
COMPARATIVE EXAMPLE 1
The following mixture is prepared:
FC 171
0.26%
Irg 651 ®
0.38%
Irg 1076 ®
0.03%
(A)
39.33%
Toluene
60.00%
The formulation is spin coated at 3000 rpm on to a PI coated glass slide. The samples are annealed at 60° C. for 60 s. After annealing, each sample is polymerised using the EFOS lamp (200 mW/cm2) 365 nm filter, under nitrogen at 60° C. for 60 s. The retardation of each slide is measured using the Ellipsometer and the thickness of each slide is measured using the surface profilometer.
The retardation profile of the film is shown in FIG. 6 , and indicates that it has the optical property of an A-plate, and that the film has positive dispersion with R 450 /R 550 =1.112.
EXAMPLE 19
The following mixture is prepared:
Irg 651 ®
0.42
Irg 1076 ®
0.02
(A)
2.82
(B)
7.12
(C)
9.63
Compound 15
19.99
Toluene
60.00
Compounds B and C are described in U.S. Pat. No. 6,183,822.
The formulation is spin coated at 3000 rpm on to a PI coated glass slide. The samples are annealed at 40° C. for 60 s. After annealing, each sample is polymerised using the EFOS lamp (200 mW/cm2) 365 nm filter, under nitrogen at 40° C. for 60 s. The retardation of each slide is measured using the Ellipsometer and the thickness of each slide is measured using the surface profilometer.
The retardation profile of the film is shown in FIG. 7 , and indicates that it has the optical property of an O-plate, and that the film has positive dispersion with R 450 /R 550 =1.00 when measured normal to the plane of the film.
EXAMPLE 20
The following mixture is prepared:
Irgacure 651 ®
0.40
Irganox 1076 ®
0.03
(A)
1.61
(C)
12.36
Compound 15
8.00
Compound 13
17.60
Toluene
60.00
The formulation is spin coated at 3000 rpm on to a PI coated glass slide. The samples are annealed at 50° C. for 30 s. After annealing, each sample is polymerised using the EFOS lamp (200 mW/cm2) 365 nm filter, under nitrogen at 40° C. for 60 s. The retardation of each slide is measured using the Ellipsometer and the thickness of each slide is measured using the surface profilometer.
The retardation profile of the film is shown in FIG. 8 , and indicates that it has the optical property of an +C-plate, and that the film has negative dispersion with R 450 /R 550 =0.96 when measured at an angle of between 20 and 60° out to the plane of the film.
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The invention relates to a polymer film having negative optical dispersion, novel polymerisable compounds and liquid crystal (LC) materials for its preparation, and the use of the polymer film and novel compounds and materials in optical, electrooptical, electronic, semiconducting or luminescent components or devices.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a new and improved propulsion device having an impulse drive using universal joints. As hereinafter described in detail, the invention is employed in a land vehicle but other applications, such as in boats, are contemplated. The device may also be used for such diversified purposes as a pile driver or other hammer or a carpet stretcher. Essentially, the invention takes advantage of the fact that universal joints, when the forks thereof are disposed at obtuse angles, rotate nonuniformly. By accumulating the nonuniform rate of rotation, a weight may be caused to reciprocate longitudinally of the vehicle, the weight velocity being high in one direction and low in the other. The variation in rate causes the device to tend to move in the direction of the high speed movement of the weight. If the device is mounted on wheels, the vehicle travels in the direction of the fast movement.
2. Description of Related Art
U.S. Pat. No. 2,030,511 shows a motion-transmitting mechanism using universal joints, but does not use these joints otherwise than for causing shafts to rotate around angles.
U.S. Pat. No. 4,121,436 shows a drive train employing universal joints, but again does not take advantage of the results obtained in accordance with the present invention. The same is true of U.S. Pat. No. 3,427,824.
U.S. Pat. No. 2,418,368 shows a vehicle which is advanced by an unbalanced force but on quite different principles.
SUMMARY OF THE INVENTION
The invention employs a prime mover, such as a motor or internal combustion engine, which turns one end of a first universal joint. Preferably there are at least four universal joints in a train around a 180 degree angle. Each joint speeds up and slows down twice per revolution, and the effect of the plural joints is cumulative. Since it is desired that there be only one acceleration per cycle, a one-to-two speed-up gear is used at the end of the chain, and this gear drives a crank which revolves twice per complete revolution of the U-joints. The crank causes a weight to reciprocate parallel to the direction of movement of the vehicle. The effect of the arrangement is that the weight is moved rapidly in the forward direction of the vehicle and slowly in the return direction. This causes the vehicle to move forwardly.
In most usages, universal joints are connected in pairs to prevent cogging--the nonconstant rate of rotation. In the present invention, the cogging is multiplied by the arrangement of the universal joints.
Other objects of the present invention will become apparent upon reading the following specification and referring to the accompanying drawings in which similar characters of reference represent corresponding parts in each of the several views.
In the drawings:
FIG. 1 is a side elevational view of a vehicle employing the present invention.
FIG. 2 is a top plan view thereof.
FIG. 3 is a sectional view taken substantially along line 3--3 of FIG. 1.
DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention is shown incorporated in a vehicle having a chassis 11 provided with a horizontally disposed base 12 having ground support wheels 13 and a superstructure 14.
Mounted on the superstructure 14 is a prime mover 16, here shown to be an electric motor. It will be understood that an internal combustion engine may be substituted. The shaft of motor 16 drives a flywheel 17. The shaft also drives a reduction gear system 21 mounted on support 19. Thus, assuming that the motor turns at 3600 rpm, the gear system 21 reduces the speed of its shaft to 60 rpm.
The output shaft 23 of reduction gear 21 is connected to the first universal joint 26, here shown only partially, the structure of such universal joints being well understood in the machinery art. Thus there is a first fork 27 fixed to shaft 23 which is connected by pin 29 to a cross (not shown) which is connected by another pin to a second fork 28, the forks 27 and 28 being turned 90 degrees relative to each other and disposed so that the input shaft 23 and output shaft 31 (fixed to fork 28) are disposed at an obtuse angle of 135 degrees. Shaft 31 is connected to second universal joint 32, the first fork 33 of which is fixed to shaft 31. The fork 28 is turned 90° relative to fork 33. Each fork hereinafter mentioned is likewise turned 90° relative to the adjacent fork. Pin 35 attaches fork 33 to the cross (not shown) and another pin fixes the cross to the second fork 34 which is, in turn, fixed to shaft 38. Shaft 38 is received in a bearing 36 attached by mount 37 to the support 19.
Below bearing 36 is third universal joint 41. The fork 42 thereof is fixed to shaft 38 and attached by pin 44 to the cross (not shown) which is also attached by a pin (not shown) to the second fork 43 fixed to one end of shaft 46. The opposite end of shaft 46 is attached to fourth universal joint 47. Thus the fork 48 is fixed to shaft 46 and attached by pin 50 to the cross (not shown) which is attached by another pin (not shown) to the second fork 49. Fork 49 is fixed to shaft 51.
Shaft 51 is journalled in third bearing 52 fixed to the gearbox 54. Shaft 51 is part of a one-to-two right-angle gear box 54, also mounted on chassis 11. The output shaft of box 54 extends transversely across chassis 11. On either side of the chassis is a crank 57 fixed to shaft 56 connected by crank pin 58 to one end of connecting rod 59. The opposite end of rod 59 is connected by wrist pin 61 to weight 62 which reciprocates in ways on the base 12. Weight 62 is preferably in the shape of an inverted T (see FIG. 3) having lateral extensions 60 which fit under crosshead guide members 66 fixed to base 12 on either side. A cover 63 is provided having longitudinal slots 64 on either side for extension of wrist pin 61.
In operation, as the weight 62 reciprocates, it has a high speed in one direction (i.e., to the left, as viewed in FIGS. 1 and 2) and a slow speed in the opposite direction. This causes the vehicle to move toward the left. It is the theory of the inventor that the invention uses centrifugal inertia force to move the vehicle along in one direction. The connecting rod 59 changes the rotational force to a bi-directional force. The movement of the weight 62 between a rapid movement in the one direction and a slow movement in the opposite direction, is done by using the universal joints connected in series to give a ratio of about 8 to 1. The nonconstant velocity effect of the universal joint occurs twice each revolution. In order to change this to a single change, the 1 to 2 gear box 54 is used. Thus the crank shaft 56 speeds up and slows down only once each revolution.
It is true that, although the weight has more force in one direction than in the opposite direction, the momentum is equal in both directions. Therefore the machine will not start by itself. The momentum balance is disrupted by an outside force or by a one-way clutch or brake (not shown) to prevent backward motion. Once forward momentum is established, the outside force is no longer needed. The starting force may be a slope (as little as 1/8 of an inch per foot) or any other source.
Thus the prime mover 16 turns flywheel 17. The four universal joints rotate at a nonconstant rate. Each joint increases its shaft speed 2 to 1 during the fast cycle for a total of 8 to 1 for the four joints. During the slow cycle, shaft speed is reduced eight times.
Universal joints speed up or slow down twice per revolution. This can be overcome by using a 1 to 2 speed-up gear so that the crank 57 performs two complete revolutions per revolution of the universal joints.
As the crank 57 rotates, the weight 62 is moved to the right. The high kinetic energy of the weight pulls the machine along with it. The arm then moves the weight slowly back to the left and the cycle repeats.
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A prime mover is connected by a series of universal joints to a crank which reciprocates a weight. The joints are arranged in such manner that the weight moves substantially faster in one direction than in the opposite direction causing a force to be applied to the structure in the first direction. When the structure is mounted on a vehicle the vehicle is caused to move in the first direction.
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BACKGROUND OF THE INVENTION
This invention relates to optical communication systems and more particularly to optical communication systems that transmit bipolar digital signals by translating each digital level in the bipolar signal into two bits of a binary signal.
Large numbers of messages are now transmitted over the telephone plant by means of T1 and T2 Carrier Systems. In these systems speech signals are converted into bipolar electrical signals which are essentially binary in nature but the adjacent logic "1s" are caused to alternate in polarity. This alteration in polarity was deemed necessary in order to insure that a sufficient number of transitions would be available in the signal in order to permit the repeaters to derive timing information and to provide dc balance to preclude baseline wander in the ac coupled receiver. In addition, violations in the alternating polarity, known to those in the art as "bipolar violations", are inserted in order to stress receivers by introducing known amounts of baseline wander. The medium used for connecting the terminal stations and repeaters is wire pair cable. A large number of wire pair cables utilized to transmit both 1 and T2 carrier signals have already been installed in the major cities. These cables are physically positioned within ducts beneath the surface of the streets of the cities. Many of the ducts have already been loaded with wire pair cables to their full capacity. Expansion of the telephone plant in these areas, if that expansion is to take place with similar T Carrier Systems will require the installation of additional ducts. It would be advantageous if the existing wire pair cables in these ducts could be replaced by optical fibers inasmuch as each fiber is smaller than a wire and, in addition, may allow larger bandwidths to be transmitted.
In the period of transition when wire pair cables are being replaced by optical fibers, many electrical bipolar signals of the type generated in the T1 Digital Transmission System will have to be converted into optical signals in order to permit them to be transmitted over optical fibers. Inasmuch as there is no straightforward equivalent of two polarities in the optical signal, some sort of conversion is necessary. It would also be advantageous if the resulting optical signal were simply of the binary type as opposed to a multilevel optical signal, in order to simplify the repeater units which will be necessary in the optical transmission system. Finally, it is desirable to maintain the polarity information present in the bipolar signal of the T Carrier System inasmuch as polarity transitions and bipolar violations will continue to provide information to T carrier type equipment operating at the receiving end of the optical transmission system.
One such encoding which will both develop a binary signal in an optical transmission system and preserve the bipolar information is disclosed in a copending application by Messrs. J. S. Cook and S. D. Personick entitled, "Optical Communication System with Bipolar Input Signal" filed Aug. 1, 1975, Serial No. 601,049. In accordance with the Cook-Personick invention, each pulse of the bipolar signal is converted into two binary digits which are then utilized to modulate an optical signal source. Each positive pulse of the bipolar signal is converted into two equal binary digits of a first logic state and each negative pulse of bipolar signal is converted into two equal binary digits of the opposite logic state. Each digital zero or zero voltage level in the bipolar signal is converted into two binary digits of opposite logic states. One feature of this type of conversion is that the two opposite binary digits that are not utilized to represent the digital zero are not generated as a pair in the conversion process. This particular pair of binary digits is in essence a forbidden word with respect to the conversion. In the decoder apparatus disclosed in the Cook-Personick application the binary signal after being detected at the receiving location is stored in a 3-cell shift register. The logic apparatus connected to this shift register is designed to detect the presence of the forbidden code in each of the two pairs of adjacent cells in the 3-cell shift register. The remainder of the decoding apparatus is connected to decode two of the three bits present in the 3-cell shift register. Upon detection of the forbidden word in the two cells being utilized for decoding, the decoding apparatus is switched to the other pair of cells in the 3-cell register. In this way no information is lost as a result of the detection of an out-of-frame condition. Unfortunately, the Cook-Personick approach to word synchronization or framing has the potential shortcoming that an error in the data can be interpreted as an out-of-frame condition thereby causing a reframing which in turn leads to detection on the wrong pair of bits and the introduction of additional errors. In short, this prior art technique of reframing has been determined to be much too sensitive to single transmission errors.
SUMMARY OF THE INVENTION
In accordance with the present invention, apparatus at the receiving location of an optical communication system wherein a bipolar signal has been converted to a binary signal detects the presence of the forbidden word in the received binary pulse stream and in response to this detection generates an energizing pulse. This energizing pulse is caused to trigger a clock circuit whose tank circuit derives its energy from the developed energizing pulse. A voltage waveform developed by the clock circuit is then utilized to drive decoder apparatus which in turn translates the binary signal into a bipolar signal. It is a feature of the present invention that the apparatus utilized to detect the presence of the forbidden word in the binary pulse stream consists of a single cell in a shift register and a logic gate having one input connected to receive the bit stored in the shift register and a second input connected to receive the bit presented to an input of the cell.
BRIEF DESCRIPTION OF THE DRAWING
The present invention will be more readily understood after reading the following detailed description with the accompanying drawing in which:
FIG. 1 is a schematic block diagram of an optical communication system including a decoder apparatus constructed in accordance with the present invention;
FIG. 2 is a detailed schematic block diagram of the framing circuit, clock circuit and decoder circuit shown as blocks in FIG. 1; and
FIG. 3 is a family of voltage waveforms useful in describing the operation of the apparatus shown in FIG. 2.
DETAILED DESCRIPTION
In FIG. 1 a source of bipolar signal 10 provides bipolar data of the type utilized in the T1 digital transmission system. In the T1 system the bipolar pulse repetition frequency, f 1 , is equal to 1.544 megabits/sec. In this bipolar signal digital "1s" are represented by positive and negative voltage levels and the digital "0s" are represented by zero voltage. In normal operation, digital 1s are caused to alternate in polarity so that a constant dc value of zero is maintained in the bipolar signal. The bipolar signal provided by source 10 is coupled to the input of a coder 11 which develops two binary digits for each one of the three levels in the bipolar signal. A desirable encoding of the type disclosed in the above-identified Cook-Personick application is to translate each positive voltage level into two digital 1s, each negative voltage level into two digital 0s and finally each zero voltage level into two binary digits of opposite value. In accordance with the Cook-Personick invention the positive voltage level may also be transmitted as two digital 0 s and the negative voltage level as two digital 1s. The only important characteristic is that both positive and negative voltage levels of the bipolar signal be transmitted as two identical binary digits. In this way the dc balance present in the original bipolar signal is maintained. The zero voltage level (the digital 0 in the bipolar signal) may be transmitted as either 01 or 10, and the binary pair that is not utilized is identified as the forbidden word.
Coder 11 also includes a source of optical signals which is modulated by the developed binary signal such that each digital 1 appears as an optical pulse of predetermined magnitude at the output of coder 11 and each digital 0 is translated into the absence of an optical pulse at the output of coder 11. As will be apparent to those skilled in the art, the digital 0 need not be represented by the total absence of an optical pulse. In fact, if a laser is used as the optical source (rather than a light emitting diode) the digital 0 is more likely to be represented by a pulse with approximately 10 percent of the power present in the pulse representing the digital 1. This binary unipolar data stream present at the output of coder 11 with a pulse repetition frequency of f 2 is coupled by way of an optical transmission medium 12 to a receiving terminal regenerator 13. In receiving terminal regenerator 13 the incoming optical binary signal is translated into an electrical binary signal on line 14. Receiving terminal regenerator 13 also provides a clock signal on line 15 having transitions with the same repetition frequency as the data bits present on line 14. The optical communication system described thus far is identical to apparatus disclosed in the above-identified Cook-Personick application which is utilized to convert a bipolar data stream of the type available from a T1 Digital Transmission System into a unipolar data stream at a receiving location.
The present invention is based on the discovery of a characteristic found in encodings of the type discussed hereinabove in connection with the Cook-Personick application. This characteristic is illustrated in the following table:
______________________________________Bipolar Level Encoding Formats______________________________________+ 11 11 00 000 01 10 01 10- 00 00 11 11Forbidden Words = 10 01 10 01Possible Sequences Resulting Binary Digits______________________________________ +0 ##STR1## 1110 0001 ##STR2## +- ##STR3## 1100 0011 ##STR4## -+ 0011 ##STR5## ##STR6## 1100 -0 0001 ##STR7## ##STR8## 1110 0+ 0111 ##STR9## ##STR10## 1000 0- ##STR11## 1000 0111 ##STR12## 00 ##STR13## ##STR14## ##STR15## ##STR16##______________________________________
From the above table it can be seen that in the type of encodings under consideration, the forbidden word occurs as the last digit of a 2-digit word and the first digit of the next 2-digit word for four out of the seven possible sequences of two digits in the bipolar signal. In view of this characteristic it is feasible to utilize the forbidden word as a means of word synchronizing or framing the decoding which takes place at the receiving location.
The unipolar data present on line 14 is coupled to the input of a 2-cell shift register 21. Each bit present in the binary signal on line 14 is caused to be read into the first cell of the shift register in response to a positive going transition in the clock signal on line 15. The output of each cell in the shift register and the complementary outputs of both cells are coupled by way of lines 25 through 28 to the input of a 2-to-1 decoder 22. The term 2-to-1 is applied to this decoder inasmuch as two bits of the binary signal are converted into one level in the reconstructed bipolar signal. One output from each of the two cells in the shift register is also coupled by way of lines 25 and 27 to the input of a data modifier 23. This data modifier 23 utilizes the binary information present in both cells of the shift register to develop an energizing pulse on line 29 when cells of the shift register contain the forbidden word. The energizing pulses on line 29 are in essence a modified version of the unipolar data. Each energizing pulse on line 29 is caused to trigger a tank circuit present in the f 1 clock extraction circuit 24. A square voltage waveform is developed by clock circuit 24 and coupled to an input of decoder apparatus 22 in order to serve as a timing function for the translation of the binary data into bipolar form.
A detailed schematic block diagram of shift register 21, decoder apparatus 22, clock circuit 24 and data modifier 23 is disclosed in FIG. 2 of the drawing. The particular embodiment of the apparatus disclosed in FIG. 2 is the one which will respond to a forbidden word of 10 in the binary pulse stream. In FIG. 2 unipolar binary data present on line 14 is coupled to the D input of a D-type flip-flop circuit 201. A typical sequence of binary digits which would be present on line 14 is shown as waveform A in FIG. 3. The clocking signal available on line 15 from the receiving terminal regenerator 13 is coupled in FIG. 2 to the clock input of flip-flop circuit 201. A typical clocking signal of the type present on line 15 is shown as waveform B in FIG. 3. Each positive-going transition in waveform B occurs approximately in the middle of the binary digit present on line 14. Upon the occurrence of each positive-going transition, flip-flop circuit 201 is caused to switch to a state dictated by the binary digit present on line 14. The resulting waveforms available at the Q output and Q output of flip-flop circuit 201 in response to the binary digits shown in waveform A are shown as waveforms C and E, respectively.
In FIG. 2 the Q output of flip-flop 201 is coupled by way of line 25 both to the input of decoder apparatus 22 and to the D input of a second flip-flop circuit 202. Flip-flop circuit 202 also responds to the clocking pulses present on line 15, and in response to each positive-going transition in the clocking signal, flip-flop circuit 202 switches its state to one which is dictated by the binary state available at the Q output of flip-flop 201. The voltage waveforms developed by flip-flop 202 at its Q and Q outputs are illustrated as waveforms D and F, respectively, in FIG. 3 for the typical binary digits shown as waveform A. As indicated in waveforms C through F of FIG. 3, flip-flop 202 provides the same outputs as flip-flop 201 but it does so at a later time interval. Specifically, the outputs from flip-flop 202 are delayed in time by one binary digit interval from the outputs of flip-flop 201.
The Q output of flip-flop 201 and the Q output of flip-flop 202 are coupled by way of lines 25 and 27 to a NOR gate 231. NOR gate 231 develops an energizing pulse at its output on line 29 whenever each of the inputs is presented with a digital 0. A digital 0 is present on both lines 25 and 27 when the forbidden word 10 is stored in shift registers 201 and 202. Hence, with a digital 1 stored in flip-flop 202 and a digital 0 stored in flip-flop 201 NOR gate 231 develops a digital 1 on line 29, thereby providing an energizing pulse to the clock circuit 24. For the waveforms developed in FIG. 3 corresponding to the digital bit stream illustrated as waveform A, the data modifier consisting of NOR gate 231 develops the pulse stream shown as waveform G in FIG. 3. As indicated in waveform G a digital 1 or energizing pulse is present on line 29 during each instance that a digital 1 is present in flip-flop 202 and a digital 0 is present in flip-flop 201.
As this point in the specification, it should be readily apparent to those skilled in the art that flip-flop 202 provides the only storage that is necessary to a development of the energizing pulses by NOR gate 231. In fact, the unipolar data on line 14 could be directly coupled to the D input of flip-flop 202 and the information on line 28 could be provided by an inhibit gate with an input connected to line 25 or line 25 could be directly connected to an inhibit input of NAND gate 222 (to be discussed hereinafter).
The energizing pulses on line 29 are coupled by way of a capacitor 241 to a tank circuit consisting of a capacitor 242 and the primary inductance of transformer 243 in the clock circuit 24. Each pulse on line 29 causes this tank circuit to ring and the Q of the tank circuit is large enough to sustain oscillations during the gaps that are present on line 29 when no pulses are present. The oscillations produced by this tank circuit are coupled from the secondary of transformer 243 through a resistor 244 to the positive input of a high gain differential amplifier 245. The negative input of differential amplifier 245 is connected to reference potential. A capacitor 246 connected between the positive input of differential amplifier 245 and reference potential causes an almost 90° phase shift to occur in the oscillations provided by the secondary of the transformer 233 to the input of the differential amplifier. This almost 90° phase shift is added to the 90° phase shift already present in the oscillations provided at the output of transformer 243 to result in a total phase shift of almost 180° for the entire clock circuit. Although some attenuation is introduced by the filter consisting of resistor 244 and capacitor 246, the gain of differential amplifier 245 is so high such that all sinusoidal voltage variations from the tank circuit cause the amplifier to saturate. In the embodiment constructed, a Texas Instruments SN 75107A was utilized as amplifier 245 and voltages in excess of 0.25 volt caused the amplifier to saturate. As a result, differential amplifier 245 provides a square wave voltage waveform on line 31 of the type shown as waveform H in FIG. 3. As indicated in waveform H the period of this clocking waveform on line 31 is equal to 2 times the interval for each bit present in the incoming binary bit stream.
As will be appreciated by those skilled in the art the type of clock generating circuit under consideration has considerable inertia and therefore a single error in the pulse stream provided by way of line 29 is unlikely to have a significant effect on the clocking signal generated by the clock circuit. Therefore even when an error in transmission causes an erroneous forbidden word to occur during the two bit interval used in the decoding, the clock circuit is essentially unaffected by this occurrence.
The clock pulses generated on line 31 by clock circuit 24 are coupled to one input of each of two NAND gates 221 and 222. NAND gate 221 has a second and third input coupled to the Q outputs of flip-flops 201 and 202, respectively. Similarly, NAND gate 222 has second and third outputs connected to the Q outputs of flip-flops 201 and 202, respectively. Each of the NAND gates 221 and 222 develops a digital 0 at its output only when all of its respective inputs are presented with a digital 1. NAND gate 221 operates to develop a digital 0 at its output only when digital 1s are present in each of flip-flops 201 and 202 and when the clock pulse is present from clocking circuit 24. Similarly, NAND gate 222 develops a digital 0 at its output when digital 0s are present in both flip-flops 201 and 202 and when the clock pulse is present from clocking circuit 24. As a result of the approximately 180° phase shift from pulses on line 29 to pulses on line 31, the between-the-word detection of the forbidden word results in an on-the-word framing of the information read by NAND gates 221 and 222. As will be appreciated by those skilled in the art, the coincidences of the pulses generated on line 31 by clock circuit 24 with the digital bits present in flip-flops 201 and 202 need not be perfect inasmuch as the outputs of NAND gates 221 and 222 are properly clocked in a manner to be described hereinafter by D-type flip-flops 223 and 224, respectively.
D-type flip-flop 223 operates in response to each positive-going transition in the inverted clock waveform available on line 263 at the output of NOR gate 260 to sample the digital state present at the output of NAND gate 221. Similarly, D-type flip-flop 224 responds to the positive-going transition in the clocking waveform on line 263 to sample the digital state present at the output of NAND gate 222. In this way the digital states at the outputs of NAND gates 221 and 222 are properly clocked and available at the outputs of D-type flip-flops 223 and 224, respectively. The type of waveform available on line 261 at the output of NAND gate 221 is illustrated as waveform I in FIG. 3 and the output of NAND gate 222 is illustrated as waveform J in FIG. 3. The resulting digital states available at the Q outputs of flip-flops 223 and 224 are illustrated as waveforms L and M, respectively, in FIG. 3. As indicated in waveform L in FIG. 3, the Q output of flip-flop 223 develops a digital 1 each time that the digital word 11 is stored in the input 2-cell shift register 21 during the clocking pulse from clock circuit 24. As indicated in waveform M of FIG. 3, the Q output of flip-flop 224 develops a digital 1 each time that the digital word 00 is stored in 2-cell shift register 21 during the clocking pulse from clock circuit 24.
The Q output of flip-flop 223 is coupled through a resistor 225 to the base electrode of a transistor 227. Similarly, the Q output of flip-flop 224 is coupled through a resistor 226 to the base electrode of a transistor 228. The emitter electrodes of both transistors 227 and 228 are coupled to a reference potential. Resistors 225 and 226 are present solely for the purpose of limiting the amount of current flow in the base-emitter junction of their respective transistors. The collectors of transistors 227 and 228 are connected to opposite ends of primary winding of a transformer 229, the center tap of this primary winding is connected to a positive potential source 230. Accordingly, the digital 1s present in the Q outputs of flip-flops 223 and 224 are amplified in their respective transistors 227 and 228 and transformer 229 provides at its secondary on line 30 a bipolar waveform of the type illustrated as waveform N in FIG. 3. Each digital 1 amplified by transistor 227 appears as a positive pulse on line 30, and each digital 1 amplified by transistor 228 appears as a negative pulse on line 30.
The implementation described hereinabove for the practice of the present invention is merely illustrative of one mode of practicing the invention. Numerous modifications may be made by those skilled in the art without departing from the spirit and scope of the present invention. For example, NAND gate 231 can be replaced by an AND gate having its inputs connected to lines 26 and 28. The other forbidden word, 01 can be detected by connecting a NAND gate to lines 26 and 28 or an AND gate to lines 25 and 27. In addition, the data modification process may be made completely independent of the decoding process by providing separate shift registers for the data input provided to the gate in the data modifier, or other type circuits may be utilized to detect the presence of the forbidden word in the binary pulse stream.
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An optical communication system is disclosed in which a bipolar signal of the type transmitted in digital transmission systems is converted into a unipolar binary signal for transmission over an optical transmission medium. The three levels of the bipolar signal are converted into three pairs of bits in the binary signal. One pair of bits is not utilized in the conversion and is therefore labeled as a forbidden word. Synchronization is achieved at the receiving location for the purpose of decoding by detecting the presence of the forbidden word in the binary signal and in response to this detection an energizing pulse is produced. This energizing pulse drives a clock circuit which in turn drives a decoding apparatus utilized to translate the binary signal back into the bipolar signal. As a result of this type of word synchronization, individual errors introduced into the binary signal do not result in a framing error.
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BACKGROUND OF THE INVENTION
The present invention relates to a process for the production of hydrogen by catalytic reforming of methanol with water vapor.
The process produces hydrogen with carbon dioxide as the principal impurity.
At the present time it is known that the major part of the hydrogen used in the world comes from the catalytic reforming of natural gas.
The latter is not always available at the desired location. Also, for the limited needs of some places, it is preferred to start from liquid charges more easily storable than methanol.
The production of hydrogen from methanol is based on the well-known reaction (FR-1549 206 and 1599 852) of reforming methanol with steam:
CH.sub.3 OH+H.sub.2 O⃡CO.sub.2 +3H.sub.2 (1)
which can theoretically be employed in the presence of any one of the catalysts already proposed for the reverse reactions of methanol synthesis:
CO+2H.sub.2 ⃡CH.sub.3 OH (2)
CO.sub.2 +3H.sub.2 ⃡CH.sub.3 OH+H.sub.2 O (3)
In practice however when it is sought to reform methanol, an accelerated deactivation of the catalytic system is experienced. The same observation has been made by the applicants of Belgian Pat. No. 884720 who propose to remedy this either by the use of modified catalysts, less active at low temperature, or by the use of a particular starting method, or lastly by the use of two successive catalyst beds, one for performing the cracking of the methanol according to the reverse reaction (4) from reaction (2):
CH.sub.3 OH⃡CO+2H.sub.2 ( 4)
the other for converting the carbon monoxide obtained:
CO+H.sub.2 O⃡CO.sub.2 +H.sub.2 ( 5)
It has now been found that the employment of these measures is not necessary and that it suffices to avoid the deactivation of a catalyst containing copper, to add a critical proportion of carbon dioxide to the reagents, water and methanol, before putting them into contact witht he catalyst.
It is known that the massive injection of CO 2 into the reforming system of methanol with steam is an effective though expensive means for increasing the ratio CO/H 2 of the synthesis gas manufactured.
Thus, the Belgian patent alreay cited teaches that, by varying the molar ratio CO 2 to methanol between 0.8 and 2.4, it is possible to change the content of CO of the manufactured gas from 31 to 41% by volume approximately, with a simultaneous lowering of the yield of hydrogen.
GENERAL DESCRIPTION OF THE INVENTION
It is an object of the invention to provide a method for the production of hydrogen, while avoiding as far as possible the formation of carbon monoxide which is a very heavy consumer of hydrogen, as shown by equation (6), the reverse of (5):
CO.sub.2 +H.sub.2 ⃡CO+H.sub.2 O (6)
According to the invention, this problem is solved in the following manner:
A mixture of methanol, of water and of carbon dioxide are passed into contact with a catalyst containing copper, in a fixed bed, in a catalytic zone at a temperature comprised between 150° to 400° C., preferably between 180° to 290° C., the molar ratio of the carbon dioxide to the methanol, at the entrance of the catalytic zone, being comprised between 0.001 and 0.2, preferably between 0.01 and 0.15.
When hydrogen is present, at the same time as CO 2 , the molar ratio of the hydrogen to the methanol, at the entrance of the catalytic zone, is advantageously from 0 to 3, preferably from 0 to 1.
Too low a content of CO 2 and/or an excessive proportion of hydrogen do not permit good stability of the copper containing catalyst to be ensured.
Too high a content of CO 2 is, on the other hand, prejudicial to the productivity of the process.
In a preferred embodiment, processing is carried out between 180° and 290° C., a range wherein the yield of hydrogen is a maximum and where the presence of CO 2 shows itself to be very useful to reduce or eliminate the loss of activity of the catalyst.
The carbon dioxide, used in the process of the invention may be either a pure gas, or a CO 2 -rich gas, and preferably a gas whose principal impurity is hydrogen, for example, a gas formed of 25-100% CO 2 and 75-0% H 2 in moles, preferably 60-100% CO 2 and 40-0% H 2 and more particularly 65-96% CO 2 and 35-5% H 2 .
It is possible to operate under a pressure of for example, 0.1 to 20 MPa, preferably 0.2 to 10 MPa.
According to equation (1), the ratio between the water and the methanol must be equal to at least one mole per mole, for example, 1.1 to 10 moles per mole, preferably 1.2 to 4 moles per mole.
The hourly space velocity (H.S.V.)--ratio between the hourly liquid flow rate by volume of methanol and the volume of catalyst--is comprised between 0.1 and 30 and preferably between 0.2 and 10.
The catalyst contains copper, preferably associated with one or several elements such as zinc, aluminum of chromium, in the form of mixed oxides or again of a mixture in various proportions of the simple constituent oxides. A preferred composition comprises 50-75% CuO, 20-40% ZnO and 5-15% Al 2 O 3 , by weight.
The catalyst contains preferably other elements such as iron, manganese or cobalt.
In particular, the presence of iron oxide in a mixture of copper oxide and chromium oxide improves the productivity of the catalytic system.
A preferred catalyst contains 40-75% CuO, 20-45% Fe 2 O 3 and 5-25% Cr 2 O 3 , by weight.
The catalysts may be either solid, that is to say, constituted by oxides of the active elements, or supported.
Their binders or their supports may be, for example, silica, alumina, a mixture of these two materials, a more complex support such as aluminates with a spinel structure (an aluminate of magnesium, of zinc, of iron or of cobalt) or a perowskite structure, (aluminates of rare earths of atomic numbers 57 to 71 inclusive) or again, constituted of mixed oxides based on zirconia (ZrO 2 -MgO, ZrO 2 -rare earths, etc. . . ).
Certain of these catalysts have been described, for example, in patents FR No. 1549301, Fr, No. 1599852, U.S. Pat. No. 4,552,861 and U.S. Pat. No. 4,596,782).
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a first embodiment of the process according to the invention.
FIG. 2 illustrates a modification of the embodiment of FIG. 1.
DESCRIPTION OF PREFERRED EMBODIMENTS
Liquid methanol is introduced through pipe 1 into the reforming unit and at the same time, the liquid water necessary for the reforming is introduced through the pipe 3 into the flask 4 where it is if necessary mixed with water and with methanol which have not reacted. This mixture arrives through the pipe 5, the pump 6 and the pipe 7 into the duct 1 where it encounters the added methanol. This pipe 1 ends at the exchanger 2 whose purpose is to vaporize the liquid charges of the unit.
All of the agents, vaporized by 2, pass to the superheater 9 through the pipe 8.
At the exit from 9, the charges are brought through the pipe 10 to the reactor 11.
In the pipe 10, arrives carbon dioxide coming from the pipe 12.
Reactor 11 is, for example, an exchanger reactor whose tubes are filled on the inside by the catalyst and regulated thermally on the outside, by a flow of heat conveying fluid.
It is known in fact, that the reaction 1 is a globally endothermic reaction and that to be able to reform 1 kmole of alcohol, it must provide to it about 50,000 kjoules.
It is preferred to operate at a temperature difference between the inlet and the outlet of the one or more catlaytic beds of less than 100° C., and preferably less 50° C.
From the reactor 11, the effluent products formed pricipally of hydrogen, of carbon dioxide and a small amount of carbon monoxide, water and methanol which have not been converted, emerge through the pipe 13a to be brought to the exchanger 9.
From 9 through the pipe 13b, these products are led to the exchanger 14 where the unconverted reagents are recondensed.
The gas-liquid mixture arrives through the pipe 15 at the separator flask 4.
In 4, the condensate rejoins the fresh water of addition to be sent to the reactor.
The uncondensable gases emerge through the pipe 16, and enter the washing column 17.
From the top of the column 17, there is sent through the pipe 18, a flow of solvent intended to absorb the CO 2 contained in the gas.
The solvent is any one of the solvents known for this use, for example, a solution of alkali metal carbonate or an amine solution.
Column 17 is usefully provided with a conventional contacting device such as plates with perforations or with valves, a packing such as Raschig rings or Pall rings, etc. . .
At the top of the column 17, the gas, formed essentially of hydrogen freed from CO 2 , emerges through the pipe 19. If it is desired to further purify this hydrogen, it can be reheated in the exchanger 20 and directed through the pipe 21 to the methanization reactor 22.
In this reactor, the CO, which can constitute a poison for subsequent uses of the hydrogen, is converted into methane and water.
This water is condensed by the exchanger 24 where the gases arrive through the pipe 23.
The gas mixture, plus condensate, emerges from 24 through the pipe 25 which opens into the separator 26. The condensate is removed through the pipeline 26a.
At the top of 26, the purified hydrogen is sent to the users through the pipe 27.
The solvent charged with CO 2 is sent through the pipe 28 into the column 29 where it is regenerated by heating by means of the reboiler 30.
The CO 2 revaporized by 30 reascends the column 29 and traverses the exchangers 31 which frees it from solvent entrained by condensation.
It is finally evacuated from the unit through the pipe 32.
A part of this CO 2 is however taken up by means of the branch pipe 33.
This CO 2 is taken up again by the compressor 34 to be sent through the pipe 12 into the reactor 15, in a mixture with the fresh charge.
The regenerated solvent collected at the bottom of the column 29, passes through the pipe 35, is taken up by the pump 36 which sends it through the pipe 37 to the cooler 38.
From 38, it rejoins the washing or absorption column 17, through the pipe 18.
The heat necessary for the endothermic reforming reaction may be supplied by a heat transmitting fluid the flow of which is ensured by the pump 39.
From 39, through the pipe 40, the fluid arrives to vaporize the liquid charges through the exchanger of 2.
From 2, through the pipe 41, it arrives at the furnace 42 whence it emerges reheated through the pipe 43.
In 43, the fluid is divided into two. One part through 44 comes to heat the reactor 11 directly.
A second part comes to the methanization preheater 20 and then rejoins the reactor 11 by means of the pipe 45.
In the unit thus described, the CO 2 necessary for the stability of the catalyst is injected into the reactor 11 by means of a compressor 34.
This is an apparatus, expensive to acquire, and which demands constant supervision, difficult to ensure when it relates to capacities of small size.
A modification of the process is shown in FIG. 2.
In this modification, a portion of the methanol from the pipe 1 is sent first into the column 47 equipped with two gas-liquid contacting zones 48 and 49.
The fresh methanol introduced through 1 sprays the contacting zone 48 traversed from bottom to top by the crude gas mixture, freed previously from liquid condensates by means of the separating balloon flask 4.
The second gas-liquid contacting zone 49 located above 48 is sprayed by at least a portion of the fresh make-up water coming from the pipe 3.
The contacting zone 48 is for the purpose of saturating the fresh liquid methanol and water charges with CO 2 .
The contacting zone 48 has a double purpose: to partly saturate with CO 2 , the fresh make-up water and to trap the methanol vapor drawn off by this gas during the liquid-gas contacting in the zone 48.
The contacting zones 48, 49 may contain, for example, perforated or valved trays, or a packing of Raschig or Pall rings etc. . .
In FIG. 2, the column 47 is mounted directly on the top of the balloon flask 4, but it is however possible to construct 4 and 47 as separate elements joined by suitable pipes.
The liquids collected are, at least in part, sent to the reactor 11.
In a modification, the column 47 comprises a wahsing zone in which the effluent gas is washed by a water plus methanol mixture, which may be constituted by the fresh reagent charge.
This charge dissolves carbon dioxide and is then sent to the reforming reactor for the methanol.
It is also possible to bubble the effluent gases into a liquid phase formed by methanol, by water or by a methanol plus water mixture.
EXAMPLE 1 (Comparative example without CO 2 )
A conventional catalyst for synthesis of methanol is selected with the following composition by weight:
______________________________________OXIDES % weight______________________________________CuO 61.0Al.sub.2 O.sub.3 7.85% wtZnO 31.15______________________________________
70 cm 3 of this catalyst is charged into a tubular reactor of diameter 20 mm and over a height of bed or 250 mm.
The catalyst is reduced at atmospheric pressure with a mixture of 3% hydrogen in nitrogen between 100° and 270° C. for 72 hours.
After the reduction step, the unit is pressurized at 3 MPa. There is then injected, at 270° C., the water-methanol reaction mixture (molar ratio H 2 O/CH 3 OH=1.5) at a flow rate of 105 cm 3 /hour; the liquid space velocity being 1.5 h -1 . The catalytic bed is kept at 270° C. (input) and 260° C. (output).
The composition by volume of the effluent gas is as follows:
______________________________________Constituents % volume______________________________________CO 1.7CO.sub.2 23.7CH.sub.4 0.1CH.sub.3 OH 0.1H.sub.2 74.4______________________________________
The conversion proportion of methanol after 24 hours of operation is 88% but, after 10 days of operation it is no more than 78%.
In Example 1, as in the following examples 2 to 6, the yield of hydrogen is 97%, calculated with respect to the methanol converted.
EXAMPLE 2
The catalyst and the operating conditions remaining the same as those of Example 1, there is injected in cocurrent with the water-methanol charge, carbon dioxide, at an hourly flow rate of liter/hour. The partial pressure of the carbon dioxide at the input of the catalytic bed was 0.063 MPa and the reagent molar ratios CO 2 /CH 3 OH and CO 2 /reactants were respectively equal to 0.0536 and to 0.0210. Under these conditions the conversion of the methanol (86% on the first day) was established at 87% at the third day and then barely varied until the end of the test (tenth day).
EXAMPLE 3
The same operating conditions were used as in Example 2, but with a flow rate of CO 2 of 7 liter/hour, namely at the input of the reactor:
a partial pressure of CO 2 of: 0.209 MPa
a molar ratio CO 2 /CH 3 OH of: 0.1876
a molar ratio CO 2 /reagents of: 0.0698 The conversion level of the methanol was practically stabilized at 92%, on the tenth day of the test.
EXAMPLE 4
The same experiment as that of Example 1 was repeated, but by introducing at the same time as the water-methanol charge a H 2 --CO 2 mixture with 39.1% volume of hydrogen and 60.9% volume of CO 2 and at a flow rate of 11.5 l/h.
The values of the partial pressures and of the molar ratios are as follows:
______________________________________pCO.sub.2 = 0.2 MPa PH.sub.2 = 0.129 MPaCO.sub.2 /H.sub.2 = 1.556 CO.sub.2 /CH.sub.3 OH = 0.1876 CO.sub.2 /H.sub.2 O = 0.125______________________________________
It is observed, by comparison with Example 1, that there is an improvement in the stability (drop in conversion of 0.25 unit daily approximately instead of one unit) and of catalytic activity (94% of conversion of the methanol instead of 88% on the first day). However, this stabilizing effect of the catalytic activity by the H 2 --CO 2 mixture is appreciably less than that of CO 2 alone (Example 3).
EXAMPLE 5
Operations were under the same conditions as those of Example 1 however by introducing with the reagents a H 2 --CO 2 mixture with 75.0 molar % of hydrogen and 25.0% of CO 2 and a flow rate of 8 l/h.
The values of the different molar ratios were as follows:
CO.sub.2 /H.sub.2 =0.333, CO.sub.2 /CH.sub.3 OH=0.0536
The conversion of the methanol was 89% after 24 hours. It then dropped on the average by 0.75 point daily. This shows that the stabilizing effect of the injection of an H 2 --CO 2 mixture with the molar ratio H 2 /CO 2 of 3 is much weaker than that obtained with mixtures richer in CO 2 (Examples 2 and 3).
EXAMPLE 6
Witha catalyst of composition by weight:
______________________________________CuO = 50.32Fe.sub.2 O.sub.3 = 33.82 % weightCr.sub.2 O.sub.3 = 15.86______________________________________
the same type of test as in Example 2 was carried out with the difference that the reaction temperature was 265° C. and the flow rate of CO 2 was 5 l/h. The conversion levels of the methanol are given in the Table below and compared with those obtained in the absence of CO 2 .
______________________________________ Conversion level of the methanol (%) 1st day 10th day______________________________________without CO.sub.2 88.6 79.2with CO.sub.2 88.1 87.3______________________________________
As in the case of the Cu-Al-Zn catalyst, there is observed, for the Cu-Fe-Cr catalyst, a beneficial effect of the injection of CO 2 at the head of the reactor, on the stability and on the catalytic activity.
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The invention relates to a process for the production of hydrogen by catalytic reforming of methanol with water vapor. A mixture of methanol, water and carbon dioxide is passed in contact with a catalyst, containing copper, in a fixed bed, in a catalytic zone, at a temperature comprised between 150° and 400° C., the molar ratio of the carbon dioxide to the methanol, at the entrance of the catalytic zone, being comprised between 0.001 and 0.2.
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TECHNICAL FIELD
This invention relates to vehicles, and particularly to a mechanism for storing and deploying a spare tire mounted on the vehicle.
BACKGROUND OF THE INVENTION
Virtually every vehicle in use today carries a spare tire for emergency purposes. A great many techniques have been used to store the spare tire within the vehicle, often without any concern to the convenience or ease of removing the tire for use. This lack of concern exists even though the very need for use of the spare implies an emergency situation has arisen where one of the tires on the vehicle has failed. Unfortunately, tires often fail in inconvenient locations and in inclement weather, situations which compound the difficulty of tire retrieval.
A number of attempts have been made in the past to simplify access to the stored spare tire. However, many of these designs are so complex as to be simply impracticable. Vehicle manufacturers are resistant to complicated mechanisms which are expensive to manufacture. Further the complexity of a device often decreases its reliability.
The problem of retrieving the spare tire is amplified when considering a vehicle such as a pickup, or other truck. The spare wheel can be very heavy and awkward for anyone. Even a spare tire used on a common passenger car can be quite difficult for an elderly or weaker person to work with.
Therefore, a need exists for a more effective way of storing and retrieving a spare tire within a vehicle which does not require the exertion of an extraordinary effort to retrieve the tire when needed.
SUMMARY OF THE INVENTION
In accordance with one aspect of the present invention, a spare tire rack is provided for holding a spare tire on a vehicle having parallel frame members. The rack includes first and second brackets, each mounted on one of the parallel frame members. A rod is pivotally supported between the first and second brackets for pivotal motion about a horizontal axis. A first arm, having an inner end and an outer end, is secured at its inner end to the rod proximate the first bracket. A second arm, also having an inner end and an outer end, is fastened at its inner end to the rod proximate the second bracket. A cross piece is pivotally connected between the first and second arms at their outer ends for limited pivotal motion relative to the arms, limited by a stop on one of the arms.
The arms, rod and cross piece form a movable section. Structure is provided for pivoting the movable section relative to the brackets between a storage position and a release position. The cross piece pivots against the stop proximate the storage position to store the tire horizontally while pivoting relative to the arms a the movable section moves to the release position to provide easy access to the tire. In accordance with another aspect of the present invention, the spare tire is held in the storage position between the cross piece and the rod. In accordance with another aspect of the present invention, the brackets are mounted underneath the vehicle proximate a bumper. As the movable section pivots to the release position, the spare tire is moved from under the vehicle, below the bumper to a position beyond the bumper for easy access to the tire.
In accordance with another aspect of the present invention, the pivoting structure includes a sector gear mounted on the rod proximate the first bracket. The second arm is shorter than the first arm to compensate for the elastic twisting of the rod to ensure that the tire is essentially level in the storage position. The tire also tilts downwardly as it moves away from the storage position which permits the tire to be removed from the rack without moving the rack completely to the release position. In the release position, the tire is directed upwardly for ease of access.
BRIEF DESCRIPTION OF THE DRAWINGS
For a more complete understanding of the present invention, and the advantages thereof, reference is now made to the following description, taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a perspective view of a tire rack forming a first embodiment of the present invention mounted on a pickup truck;
FIG. 2 is a perspective view of the tire rack;
FIGS. 3A-D illustrate the operation of the tire rack as it is moved between the storage and release positions; and
FIG. 4 is an exploded perspective view of the sector gear used in the tire rack.
DETAILED DESCRIPTION
With reference now to FIG. 1, a tire rack 10 forming a first embodiment of the present invention is illustrated mounted on a pickup truck 12. The truck is of conventional construction, having a pair of parallel frame members 14 and 16 extending along the length of the vehicle on opposite sides of the center line of the vehicle. A truck bed 18 is supported on the frame members. In the storage position, the tire rack 10 holds the spare tire 20 against the bottom of the truck bed 18 between the frame members 14 and 16, providing excellent ground clearance (see FIG. 3D). When moved to the release position, the tire 20 has been lowered to ground level, moved behind the bumper 22 of the truck and tilted somewhat upwardly for ease of removal of the spare tire (see FIG. 3A).
With reference now to FIG. 2 and 3, details of the tire rack 10 will be described. The rack includes first and second brackets 24 and 26. Each bracket is mounted on one of the frame members of the truck. A rod 28 extends between the brackets and is mounted to the brackets for pivotal motion about a horizontal axis 30 which is generally perpendicular the center line of the truck. A first L-shaped arm 32 is secured to the rod at the inner end 34 of the arm proximate the first bracket. A second arm 36 is secured to the rod near the inner end 38 of the second arm. Again, second arm 36 is L-shaped as well. The outer end 40 of first arm 32 and outer end 42 of second arm 36 both form the shorter section of the L-shape for each arm. As will be clear from FIG. 3, one corner 44 of each outer end is rounded while the other corner 46 is formed by a sharp angle.
A cross piece 48 extends between the outer ends of the arms and is pivoted to the arms for pivotal motion about a horizontal axis 50. The cross piece 48 is formed of an angle member 52 having upturned ends 54, an overlying U-shaped channel 56 having upturned ends 58, and a tongue 60 having a upturned end 62. As can be seen from the drawings, ends 54 and 58 are paired and separated just far enough to permit the outer end of an arm to pass between and be pivoted thereto with pins 64 lying on axis 50. The cross piece 48 can pivot about axis 50 relative to the arms until a portion of the angle member 52 contacts the sharp corners 46 of the arms as shown in FIG. 3C.
At the end of rod 28 proximate the first bracket, a sector gear 66 is mounted. As best seen in FIG. 4, the sector gear is constructed of three individual gear pieces 68 bolted-together by bolts 70 to form the complete gear 66. This assembly permits the gear pieces to be stamped out of a sheet of metal without expensive gear cutting machines, but permits a strong gear to be formed by a placing multiple sections together to form a single, larger gear.
A worm gear 72 is mounted for rotation on the first bracket and engages the teeth of the sector gear 66. A locking plate 74 is mounted at one end of the gear 72 and has a plurality of holes 76 about its circumference. An L-shaped bracket 78 is mounted on the first bracket 24 so that a hole 76 can be aligned with a hole 80 formed in the bracket 78. A combination or key padlock can be passed through the aligned holes to lock the tire rack in the storage position.
A handle 82 with a shaped end 84 can be attached to the worm gear 72 to rotate the worm gear. The handle can be removably attached to the worm gear, or permanently mounted thereto as desired.
With reference now specifically to FIGS. 3A-D, the operation of the tire rack will be described. FIG. 3A illustrates the tire rack moved to the release position where the spare tire 20 can be easily pulled from the rack. When the tire is to be replaced, it is slid over the top of cross piece 48 so that the front portion of the tire contacts the end 62. The end 62 is positioned so that the center of mass of the tire and bracket lies forward of the axis 50, or to the right of axis 50 as shown in FIGS. 3A-D. The center of mass of the cross piece 48 without a tire resting on it also falls forward of the axis 50 so that the bottom of tongue 60 near the end 62 lies on the ground 86 when the rack is in the release position whether carrying a tire or not.
To move the spare tire to the storage position, the operator simply engages the handle 82 with the worm gear 72 and begins to rotate the worm gear. The worm gear, in turn, rotates sector gear 66 and rod 28 in the counter clockwise direction as shown in the FIGURE, with the arms pivoting about axis 50 relative to the cross piece with a portion of the cross piece still resting on the ground.
As shown in FIG. 3C, the arms will eventually pivot about axis 50 to the point where the sharp corners 46 of each arm contact the angle member 52. Pivotal motion of the arms relative to the cross piece is then no longer possible as the rack continues to be cranked to the storage position. In the position shown in FIG. 3C, the tire is tilted slighted down toward the front end, or right in the FIGURE.
However, if the vehicle is positioned so that there is insufficient clearance to fully move the rack to the release position, the cross piece 48 and tire 20 can be manually pivoted to tilt the tire the opposite way to slide the tire out of the rack.
As the worm gear continues to rotate, the back end, or left side of the tire in FIG. 3D, hits the bottom of the truck bed 18 and causes the tire and cross piece 48 to pivot slightly so that the tire ends up in the storage position essentially flat and pressed against the underside of the truck bed. The shorter portion of the second arm 36 is preferably somewhat shorter than the shorter portion of the first arm 32 to compensate for elastic twisting of the rod 28 resulting from the proximity of the sector gear near the first arm to provide a uniform holding force across the width of the tire and truck bed.
Deployment of the spare tire essentially operates in the reverse manner. It should be noted that the back end, or left side, of the tire as shown in FIGS. 3A-D passes beneath and behind the bumper 22 of the truck. This eliminates the need for the operator to reach beneath the truck to get the spare tire, making the task far easier. The pitch of the worm gear 72 and sector gear 66 is preferably such that the rack will be selfheld within a particular position with no need for any locking structure.
One rack constructed in accordance with the teachings of the present invention employed a rod 28 having a one inch diameter. The length of the shorter leg of the L-shaped arm 36 was one-half inch less than the length of the shorter leg of the first arm to compensate for the elastic twisting of the rod. The sector gear 66 was formed of three pieces, each having a one-eighth inch thickness bolted together to form a sector gear having a thickness of three-eighths inch.
While one embodiment 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 of parts and elements without departing from the spirit of the invention.
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An improved tire rack (10) is disclosed for use on any vehicle, but which is particularly suitable for use on a pickup truck (12). Brackets (24, 26) are mounted on the frame members of the truck and support a rod (28) and arms (32, 36) for pivotal motion between a storage position and a release position. In the storage position, the spare tire is held horizontally against the bottom of the bed of the truck. When moved to the release position by rotating a worm gear (72) to pivot the sector gear (66) on the rod (28), the tire rack moves the spare tire below and behind the bumper of the vehicle for ready access.
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TECHNICAL FIELD
The present invention relates to a spectrophotometer for the analysis and characterisation of samples by measurement of their absorption or fluorescence spectra, particularly when the analytical samples are liquid samples presented to the spectrophotometer in a well plate.
BACKGROUND OF THE INVENTION
The following discussion of the background to the invention is included to explain the context of the invention. This is not to be taken as an admission that any of the material referred to was published, known or part of the common general knowledge in Australia as at the priority date of any of the claims.
Analytical samples can be characterised and analysed by spectrophotometric measurements of the absorption of light by a sample. Analytical samples can also be characterised and analysed by spectrophotometric measurements of the fluorescence of a sample.
To perform a spectrophotometric measurement of the absorption of light by a sample a source of substantially monochromatic light of a selected wavelength is provided for the purpose of illuminating an analytical sample. Such substantially monochromatic light is conveniently obtained by providing a continuum light source such as a xenon arc lamp or flash lamp and also providing a wavelength selective means such as a grating monochromator between the continuum light source and the analytical sample. A means of detecting and measuring the intensity of the substantially monochromatic light after its passage through an analytical sample in an appropriate sample container is also provided so that the absorption of light by the analytical sample can be measured.
To perform a measurement of the fluorescence of a sample a source of substantially monochromatic light of a first wavelength is similarly provided for illuminating an analytical sample and causing the sample to emit light. The substantially monochromatic light of a first wavelength that illuminates the analytical sample is called the excitation light, and the light emitted by the illuminated analytical sample is called the emission light. A means of selecting from the emission light substantially monochromatic light of a second wavelength is provided and this light is transmitted to a light detecting device for detection and measurement. Such selecting means can be for example a second grating monochromator between the analytical sample and the light detecting device.
Light detecting devices useful in spectrophotometers include photomultiplier tubes, photodiodes and charge-coupled devices. All such devices produce an electrical signal that is proportional to the quantity of light (i.e. to the number of photons per second) reaching the device. It is a characteristic of such light detecting devices that the signal-to-noise ratio is less when the quantity of light failing on the device is less, provided that the quantity of detected light is always sufficiently low that the detecting device is able to operate correctly. In practice, the design of the spectrophotometer ensures that the quantity of detected light is always kept sufficiently low that the detecting device is able to operate correctly. Consequently, the best signal-to-noise ratio is achieved when as much detectable light as possible reaches the detecting device.
To achieve the best signal-to-noise ratio the analytical sample should be uniformly illuminated with the required substantially monochromatic light, and such uniform illumination ideally should be achieved while allowing all the available substantially monochromatic light to enter the sample container and interact with the sample. Any of said light that does not enter the sample container is wasted, and the signal-to-noise ratio of the measurement is less than it might otherwise be. Similarly, it is also desirable that light of interest transmitted through or emitted by the illuminated sample be efficiently collected and transmitted to the light detecting device. Any light of interest that is not collected and transmitted to the light detecting device is wasted, and the signal-to-noise ratio of the measurement is less than it might otherwise be.
Liquid analytical samples are advantageously presented to a spectrophotometer with the aid of a device called a “microplate” or “well plate”. These terms are synonymous; for convenience, the term “well plate” will be used herein. A well plate consists of a multiplicity of sample containers rigidly mounted in an array. Movement of the array with respect to the optical path in the spectrophotometer allows each sample in turn to be illuminated with appropriate substantially monochromatic light so that light of interest can be detected and measured. In the case of absorption measurements the light of interest will be light that has passed through the sample. In the case of fluorescence measurements the light of interest will be light that has been emitted by the illuminated sample. This arrangement allows rapid and convenient analysis of a large number of individual analytical samples. A spectrophotometer arranged to operate in this fashion is known as a well plate reader or microplate reader. In order to provide as many sample containers as possible in a well plate of constant area, it is common to make such sample containers much deeper than they are wide. This long, narrow configuration of the sample container introduces difficulties in the illumination of the sample contained therein. It also introduces difficulties in the collection of light of interest from the sample for detection and measurement.
For example, in prior art well plate readers it is common to illuminate the sample with a cone of substantially monochromatic light formed between the focusing component and the focus. The focus is positioned in the well below the surface of the sample. The subtended angle of the cone of light is made as large as possible to maximise the quantity of light provided. The limitation of this arrangement becomes evident when only a limited volume of sample is available and consequently the surface of the sample is considerably below the top of the well. When the focus is positioned below the surface of the sample the top edges of the well obscure some of the light that is intended for illumination of the sample.
When absorbance measurements are being made any obstruction of light by the top edges of the well inevitably reduces the amount of light reaching the absorbance detector and thereby reduces the signal-to-noise ratio of the absorbance measurements.
When fluorescence measurements are being made the quantity of fluorescently emitted light is proportional to the quantity of light illuminating the sample, so any reduction in the quantity of illuminating light is inevitably associated with a reduction in the quantity of light fluorescently emitted by the sample. This in turn reduces the signal-to-noise ratio of the fluorescence measurements.
The prior-art arrangement for collecting fluorescently emitted light is the same as that just described for illumination. This results in a further shortcoming for fluorescence measurements of a sample having a surface considerably below the top of the well. The optical path defined by the collection angle of the fluorescently-emitted light is obscured by the top of the well. The effective collection angle is thereby reduced. This reduces the quantity of light reaching the fluorescence detector by a factor similar to that by which the illumination of the sample is reduced. This results in a further reduction of the signal-to-noise ratio of the fluorescence measurements.
DISCLOSURE OF THE INVENTION
An object of the present invention is to provide a spectrophotometer having improved sensitivity and flexibility for detecting fluorescence, phosphorescence and absorption in liquid samples contained in a well.
Accordingly, in a first aspect the present invention provides a spectrophotometer having an optical system for directing a beam of substantially monochromatic light into a liquid sample in a well,
the optical system including a first aperture and a second aperture and focussing means for forming conjugate images of the first and the second apertures outside of the well to establish therebetween a beam region of monochromatic light, wherein the first and second apertures are sized and shaped for said beam region to have a shape that is similar to the internal shape of the well, and imaging means for imaging said region of the beam to a size corresponding to the internal size of the well at the well for the imaged said region of the beam of monochromatic light to illuminate substantially all of the liquid sample in the well without the well obstructing any portion of the imaged said region of the beam.
The arrangement to provide the conjugate images to establish the region of the beam of light of similar shape is an example of “Kohler illumination” conjugation. It provides the most uniform and limited-glare illumination with minimal energy loss in the system. The region of similar shape between the conjugate images also advantageously provides for convenient insertion of filters, apertures and polarisers and permits the use of small filters and polarisers, which are normally more cost effective than larger ones.
A Kohler illumination conjugation region that is of substantially constant cross-section is preferably established because this suits the normal internal shape of the wells in a well plate, i.e. it suits a well that is parallel walled and has a greater depth than width. However, given that the three dimensional shape of the Kohler illumination conjugation region depends on the shape and size of the images of the two apertures that establish the region, which in turn depends upon the shape and size of the first and second apertures, it is to be understood that those apertures may be shaped and sized to establish a Kohler illumination conjugation region that is appropriately shaped to suit a differently shaped well. For example, for a well having inwardly tapered walls a Kohler illumination conjugation region of frustoconical shape could be established by appropriately shaping and sizing the first and second apertures.
A particular advantage of the invention (as will be described in more detail hereinbelow) is that it allows for accurate measurement of an analytical sample in a well notwithstanding that the sample does not fill the well.
Preferably the focussing means for providing the Kohler illumination conjugation region is a telecentric mirror (i.e. one in which the chief rays are parallel to one another).
Preferably the imaging means for demagnifying and imaging, that is coupling, the Kohler illumination conjugation into the well space is an off-axis ellipsoidal mirror. This mirror performs demagnification volumetric imaging in the optical system. It reduces the three-dimensional region of the beam of substantially monochromatic light into the well of, for example, a 384 multi-well plate without clipping on the wall of the well. This volumetric conjugation imaging provides two main advantages. Firstly, substantially all the liquid sample in the well is uniformly illuminated with limited glare because the volumetric imaging couples the Kohler illumination conjugation into the well space. Secondly, the focussing is insensitive to the height of sample in the well because the beam in the well is of a substantially cylindrical or rectangular parallelepiped shape (depending upon the shape of the apertures), which illuminates the sample in the entire depth of the well with minimal intensity change.
The means for providing the substantially monochromatic light is preferably a monochromator, in which case the first aperture is an entrance slit of the monochromator and the second aperture is the aperture of the diffraction grating of the monochromator. Alternatively the means for providing the substantially monochromatic light may be an optical band pass filter, and the first and second apertures are appropriate apertures on either side thereof, or a prism, also with appropriate apertures to provide the first and second apertures.
The spectrophotometer will include a detection system which may be a system for absorbance measurements, that is, for detecting residual light of the substantially monochromatic beam of light that emerges from the liquid sample, for example through a transparent base of the well.
Alternatively the detection system may be for fluorescence and/or phosphorescence measurements. A spectrophotometer according to the invention may include a detection system for absorption and a detection system for fluorescence/phosphorescence measurements.
A fluorescence/phosphorescence detection system preferably includes an optical system (hereinafter emission optical system) in which the imaging means performs magnification volumetric imaging of the well volume to establish a substantially constant cross-section region of the emission light, this region being established between, in the direction of light travel, an image of the bottom of the liquid sample in the well and an image of the top surface of the liquid sample in the well, with for example an approximate 1:3 transverse magnification. This region allows the insertion into the emission optical system of emission filters, polarisers and apertures of minimal physical size.
Preferably the emission optical system includes focussing means, such as for example a telecentric mirror, for transferring said three-dimensional emission light region into an emission monochromator. Such focussing means re-images the image of the bottom surface of the well in conjugation with the exit slit of the emission monochromator and the image of the top surface of the well in conjugation with the grating aperture of the emission monochromator. This arrangement follows the Kohler illumination conjugation example (previously described) and ensures that the emission from the liquid sample in the well can be collected with maximised collecting power with minimal energy loss in the emission optical path. It also minimises the variation of the collecting power for light emitted at different positions in the well.
An advantage of a spectrophotometer according to the invention is that an optical system thereof that is optimised for a specific type of well plate (such as for example a plate having 384 wells) can be easily modified to measure a different type of well plate (such as for example a plate having 1536 wells) in which the wells have a different aspect ratio. Simply inserting an appropriate pair of apertures into the constant cross-section region of the excitation optics can provide a beam size to suit a smaller diameter well such as that of the 1536 well plate. This configuration is also suitable for absorption measurements.
The invention encompasses a spectrophotometer that provides for a Kohler illumination conjugation region in the emission optical system (as just described) either with or without a similar Kohler illumination conjugation region in the excitation optical system. Thus according to a second aspect, the invention provides a spectrophotometer including
a light source, a sample position, an excitation optical system for directing a beam of substantially monochromatic light derived from the light source to a liquid sample when contained in a well when located at the sample position, and an emission optical system and a detector, the emission optical system for directing light emitted from the liquid sample after interaction of the beam of substantially monochromatic light therewith to the detector, the emission optical system including (i) imaging means for providing an image of the bottom surface of the well and an image of the top surface of the liquid sample in the well whereby there is established outside of the well and between the images a region of the emitted light having a shape that is similar to the internal shape of the well, (ii) focussing means and means for providing substantially monochromatic light from the emission light, the focussing means for focussing the region of emitted light of similar shape onto the means for providing substantially monochromatic light,
the detector arranged to detect the substantially monochromatic emission light from the means for providing such light.
For a normally shaped well, that is one that is parallel walled and has a greater depth than width, the region of the emitted light of similar shape will have a substantially constant cross section. If the shape of the internal space of the well is cylindrical, then the similar shape of said region of the emitted light will be cylindrical.
Preferably the imaging means for magnifying and imaging the well volume to establish said region of the emission light of similar shape is an off-axis ellipsoidal mirror. Preferably the focussing means is a telecentric mirror and the means for providing the substantially monochromatic emission light is a monochromator, although it could instead be a prism or an optical bandpass filter.
For a better understanding of the invention and to show how it may be performed, a preferred embodiment thereof will now be described, by way of non-limiting example only, with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B schematically show prior art slit or grating imaging for illuminating a sample in a well.
FIGS. 2A and 2B schematically show slit or grating imaging as occurs in a sample well in an embodiment according to the invention.
FIG. 3 schematically illustrates a spectrophotometer according to a preferred embodiment of both aspects of the invention.
DESCRIPTION OF PREFERRED EMBODIMENT
According to a preferred embodiment, a spectrophotometer includes a spectrophotometer including
a light source, a sample position, and an optical system for directing a beam of substantially monochromatic light derived from the light source to a liquid sample when contained in a well when located at the sample position, the well having an internal shape, the optical system including,
(i) for deriving the beam of substantially monochromatic light, an entrance aperture followed by a second aperture associated with means for providing the substantially monochromatic light, (ii) focussing means for providing conjugate images of the entrance and second apertures whereby there is established between the conjugate images a region of the beam of substantially monochromatic light that has a particular shape as determined by the shape and size of the conjugate images, and (iii) imaging means for demagnifying and imaging the region of the beam of light of particular shape into the well for interaction with the liquid sample therein, wherein the particular shape of the region of the beam of light corresponds with the internal shape of the well for substantially all of the liquid sample to be uniformly illuminated without the well obstructing any portion of the beam of light,
the spectrophotometer further including a detection system for detecting light from the liquid sample after interaction of the substantially monochromatic beam of light therewith.
The following Legend applies to FIGS. 1A and 1B , 2 A and 2 B and 3 :
1 is a second image of an excitation diffraction grating 28 2 is a second image of the entrance slit 46 of an excitation monochromator 29 3 is a target well 4 (not used) 5 are wells adjacent to target well 3 6 (not used) 7 is the optics for an absorption detector 8 8 is an absorption detector 9 is an off-axis ellipsoidal mirror 10 is a large flat (plane) mirror 11 is a main beam splitter 12 is a beam splitter for a fluorescence reference detector 16 13 is a first attenuator 14 is a curved mirror for a fluorescence reference detector 16 15 is a second attenuator 16 is a fluorescence reference detector 17 is a beam splitter for an absorbance reference detector 23 18 indicates the position of a first image of an entrance slit 16 of an excitation monochromator 29 19 is an excitation polariser 20 is an excitation filter 21 indicates the position of a first image of the ruled surface of an excitation diffraction grating 28 of excitation monochromator 29 22 is a curved mirror for an absorbance reference detector 23 23 is an absorbance reference detector 24 is a focusing mirror (excitation) 25 is a flat (plane) mirror (source optics) 26 is a lens (source optics) 27 is a xenon arc flash lamp 28 is the ruled surface of an excitation diffraction grating of excitation monochromator 29 29 is an excitation monochromator 30 is a collimating mirror of excitation monochromator 29 31 is a focusing mirror of excitation monochromator 29 32 is a collimating mirror of an emission monochromator 34 33 is a focusing mirror of the emission monochromator 34 34 is an emission monochromator 35 is the ruled surface of an emission diffraction grating of emission monochromator 34 36 is a curved mirror for an emission detector 37 37 is an emission detector 38 is a focusing mirror (emission) 39 indicates the position of an image of the top of target well 3 40 is an emission filter 41 is an emission polariser 42 indicates the position of an image of the bottom of target well 3 43 (not used) 44 (not used) 45 is an attenuator for the absorbance reference detector 23 46 is an entrance slit of the excitation monochromator 29 47 is an exit slit of the excitation monochromator 29 48 is an entrance slit of the emission monochromator 34 49 is an exit slit of the emission monochromator 34 .
The optical throughput of a spectrophotometer according to an embodiment of the invention is dependent on two apertures of a monochromator: the aperture of the entrance slit and the aperture of the grating, or conjugation images of this pair. The system throughput can be calculated by:
T sys =A s ×A g /F 2
or
T sys =A si ×A gi /L 2
where
A s —the aperture area of the entrance slit A g —the aperture area of the grating F—the focal length of the monochromator A si —the image area of the aperture of the entrance slit A gi —the image area of the aperture of the grating L—the distance between of two images
The top aperture and bottom apertures of the well in a well plate reader limit the maximum throughput of light supplied into or collected from a well. The maximum throughput of the well can be calculated by:
T well =A t ×A b /D 2
where
A t —the top aperture area of the well A b —the bottom aperture area of the well D—the depth of the well
When the throughput of the system is properly matched with the maximum throughput of the well, i.e. T sys =T well , optimal system efficiency is achieved. However, if the T sys >T well , then a part of the throughput from the system is wasted. If the T sys <T well , the volume of the well is not fully illuminated.
In the presented invention, the system has reached optimal efficiency, i.e. T sys =T well .
In FIG. 1A , a prior art optical system produces a second image 2 of the entrance slit of an excitation monochromator which is positioned at the top of the well 3 with its size substantially the same as that of the bottom of the well 3 . The second image 1 of the grating of the excitation monochromator is positioned at a distance that is twice the depth of the well 3 from the second image 2 of the entrance slit. According to the optimal condition of T sys =T well , the entire throughput of the excitation optical system can be transferred into the well 3 and the emission from the entire well 3 can be collected by an emission optical system. In FIG. 1B , however, when the bottom of the well 3 moves closer to the second image 2 of the entrance slit, the top aperture of the well 3 blocks a section of the throughput of the excitation optical system out of the well 3 . The geometrical optics of FIG. 1 is therefore not efficient even when the condition of T sys =T well is met.
In FIG. 2A , the optical system of a spectrophotometer according to an embodiment of the invention as shown in FIG. 3 produces a second image 2 of the entrance slit 46 of excitation monochromator 29 which is positioned at the top of the well 3 with its size substantially the same as that of the bottom of the well 3 . The second image 1 of the grating 28 of excitation monochromator 29 is positioned at a distance that is substantially the same as the depth of the well 3 from the second image 2 of the entrance slit 46 . According to the optimal condition of T sys =T well , the entire throughput of the excitation optical system can be transferred into the well 3 and the emission from the entire well 3 can be collected by the emission optical system. In FIG. 2B , when the bottom of the well 3 moves closer to the second image 2 of the entrance slit 46 , the top aperture of the well 3 does not block any part of the throughput of the system. The geometrical optics in FIGS. 2A and 2B is therefore more efficient than the prior art system shown in FIGS. 1A and 1B . Furthermore a well plate reader according to an embodiment of the invention is able to function efficiently even when only a small fraction of target well 3 is filled with sample.
Referring now to FIG. 3 , light from source 27 (preferably a xenon flash lamp) is focussed by source optics comprising lens 26 and flat mirror 25 onto entrance slit 46 of excitation monochromator 29 . Light emerging from slit 46 falls on collimating mirror 30 and is thereby made into a substantially parallel beam that falls on ruled surface 28 of a diffraction grating. Dispersed light from the ruled surface 28 strikes focussing mirror 31 and is brought to a focus forming a substantially monochromatic image of entrance slit 46 at exit slit 47 of excitation monochromator 29 . Substantially monochromatic light emerging from exit slit 47 falls on focussing means 24 , for example a telecentric mirror 24 . Mirror 24 forms an image 21 of ruled surface 28 and an image 18 of entrance slit 46 in a Kohler illumination arrangement. The entrance slit 46 and aperture of grating 28 constitute an first aperture and second aperture according to the invention. If required a filter 20 and/or polariser 19 are advantageously placed in the substantially constant narrow light beam region between images 21 and 18 . (Note that although references 18 and 21 illustrate stops, such stops are not necessary in that the embodiment merely involves the respective images being established at the positions of 18 and 21 ). The small size of the narrow light beam region between 21 and 18 allows physically small filters or polarisers to be used, with corresponding savings in cost.
Light from image 18 falls on a first beam splitter 17 . A first portion of this light is reflected from the first beam splitter 17 through attenuator 45 and onto curved mirror 22 that brings the first portion of light to a focus forming an image of ruled surface 28 on absorbance reference detector 23 . The electrical signal from reference detector 23 is used as a reference for absorbance measurements and thus compensates for variations in the intensity of source 27 . A second portion of the light from image 18 passes through first beam splitter 17 and falls on a second beam splitter 12 . A first portion of the second portion of the light is reflected from the second beam splitter 12 through a first attenuator 13 and onto a curved mirror 14 that reflects the first portion of the second portion of light through a second attenuator 15 and brings it to a focus on a fluorescence reference detector 16 . A second portion of the second portion of light passes through the second beam splitter 12 and falls on a third beam splitter 11 (the main beam splitter).
Light reflected from the third or main beam splitter 11 falls on a large flat mirror 10 and is reflected therefrom onto an off-axis ellipsoidal mirror 9 that focuses it in target well 3 as previously explained with reference to FIG. 2B . The off-axis ellipsoidal mirror 9 constitutes an imaging means according to the invention.
Absorbance Measurements
Light emerging from the transparent base of target well 3 is brought to a focus by absorption detector optics 7 onto absorbance detector 8 . The electrical signal from absorbance detector 8 is used in conjunction with the electrical signal from absorbance reference detector 23 to generate a measurement of the absorbance of a test solution (not shown) in target well 3 .
Fluorescence/Phosphorescence Measurements
If a test solution in target well 3 emits light fluorescently when illuminated as just described, fluorescently emitted light collected from the sample emitted follows the same path, but in the opposite direction, as described above for light travelling from main beam splitter 11 to target well 3 . A portion of the fluorescently emitted light passes through the main beam splitter 11 and forms an image 42 of the bottom of target well 3 and an image 39 of the top of target well 3 . The narrow emission light beam region between images 42 and 39 forms a Kohler illumination arrangement as previously described for the excitation light beam between images 21 and 18 . Again, if required a filter 40 and/or polariser 41 are advantageously placed in the narrow emission light beam region between images 42 and 39 . (Note that although references 42 and 39 illustrate stops, such stops are not necessary in that this embodiment of the invention merely involves the respective images being established at the positions of 42 and 39 ). The small size of the narrow emission light beam region allows physically small filters or polarisers to be used, with corresponding savings in cost.
Light from image 39 falls on focusing mirror 38 , for example a telecentric mirror, which brings it to a focus on entrance slit 48 of emission monochromator 34 . Light emerging from slit 48 falls on collimating mirror 32 and is thereby made into a substantially parallel beam that falls on ruled surface 35 of a diffraction grating of emission monochromator 34 . Dispersed light from the ruled surface 35 strikes focussing mirror 33 and is brought to a focus forming a substantially monochromatic image of entrance slit 48 at exit slit 49 of emission monochromator 34 . Substantially monochromatic light emerging from exit slit 49 falls on focussing mirror 36 and is brought to a focus on fluorescence detector 37 . The electrical signal from fluorescence detector 37 is used in conjunction with the electrical signal from fluorescence reference detector 16 to generate a measurement of the fluorescence of the test solution (not shown) in target well 3 .
When an embodiment of a spectrophotometer according to the invention is used to carry out measurements of fluorescently emitted light as just described, the samples are preferably presented in wells having opaque bottoms to prevent reflection of light from the absorbance optics 7 and detector 8 onto mirror 9 and thus ultimately into emission monochromator 34 where it would be a potential source of stray light. It is, however, feasible to use wells having transparent bottoms and to make absorbance and fluorescence measurements on the same sample. The usefulness of such measurements is limited by the fact that a fluorescent sample of sufficient concentration to give a useful absorbance signal would normally generate an excessive fluorescence signal.
Results of a Test of a Spectrophotometer According to the Invention
The detection limit is an important figure of merit for an analytical instrument. The detection limit is defined as the concentration of a specified substance that can be detected with a specified level of confidence under specified conditions. The detection limit is commonly specified as the concentration that gives a signal equal to three times the standard deviation of the signal from a series of measurements of a sample that does not contain the specified substance. The lower the detection limit, the better.
An advantage of the invention is that detection limits measured on samples that do not completely fill a well in a well plate are superior to those found with the prior art. The reason for this is the superior signal-to-noise ratio arising from more efficient illumination of such samples and from more efficient collection of fluorescently emitted light from such samples, as already explained.
As an illustration of the improvements in detection limits achieved by use of a spectrophotometer according to the invention, Table 1 shows the limits of detection for fluorescein calculated from results of fluorescence measurements of a test solution containing 10 picomoles of fluorescein per litre using first, a prior art well plate reader (corresponding to FIG. 1 ) and second, a well plate reader corresponding to FIG. 2 . In each case the test solution placed in a well 3 in a well plate having 384 wells, a 50/50 beam splitter 11 was used and measurements were made using 10 cycles of 30 flashes. When a 100 microlitre sample of test solution was used, the well was nearly full and the detection limits were the same for each instrument. When the sample volume was reduced to 50 microlitres, the well 3 was only about half full. The detection limit with the spectrophotometer instrument according to an embodiment of the invention deteriorated by a factor of two, but that with the prior art instrument deteriorated by a factor of six. This illustrates the advantage of the invention over the prior art in making measurements of low concentrations of substances of interest in limited volumes of sample solution.
Theoretical considerations indicate that reducing the volume of illuminated sample by a factor of two should ideally cause the signal-to-noise ratio (and thus the detection limit) to deteriorate by a factor of two, if the sample is completely illuminated and the collection efficiency of the fluorescently emitted light remains unchanged. Such a deterioration in the detection limit by a factor of two was observed with the spectrophotometer instrument according to an embodiment of the invention. With the prior-art instrument, however, the deterioration was much worse (a factor of six, instead of a factor of two).
TABLE 1
Detection limits for fluorescein in a well plate having 384 wells.
Detection limit with a
Detection limit with a 50
Instrument
100 microlitre sample
microlitre sample
Prior art
5 × 10 −13 M
3 × 10 −12 M(ie. 30 × 10 −13 )
According to the
5 × 10 −13 M
1 × 10 −12 M(ie. 10 × 10 −13 )
invention
It is to be understood that where reference if made to a monochromator in the above description, the monochromator may be replaced by an optical filter, or an optical filter may be used in conjunction with the monochromator. Furthermore, it is to be understood that any monochromator may be double or single. It is also to be understood that the invention is not limited to optical systems using the specific type of monochromator that is shown in FIG. 3 to illustrate the invention. It is to be understood that the invention is also applicable to optical systems using other types of monochromators.
The invention described herein is susceptible to variations, modifications and/or additions other than those specifically described and it is to be understood that the invention includes all such variations, modifications and/or additions which fall within the scope of the following claims.
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A spectrophotometer having an optical system for directing a beam of substantially monochromatic excitation light to a liquid sample contained in a well ( 3 ) of a well plate for interaction with the sample for absorption or emission measurements to analyse the sample. The optical system includes two apertures ( 46, 28 ) for establishing a Kohler illumination region outside the well, that is an excitation beam region between conjugate images ( 18, 21 ) of the two apertures. This excitation beam region is then demagnified and imaged ( 10, 9 ) into the well ( 3 ). The invention provides for the shape of the Kohler illumination region to correspond to the shape of the well space so that all of the liquid sample is uniformly illuminated without the well obstructing any portion of the illuminating excitation beam of light. Advantages of the invention are that the Kohler illumination region of the excitation beam is convenient for insertion of filters ( 20 ), apertures and polarisers ( 19 ) into the excitation optical system and permits use of small and thus cheaper filters and polarisers. Also the invention provides for accurate absorption or emission measurements from a liquid sample in a well notwithstanding that the sample may only partially fill the well.
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RELATED APPLICATION
This application is related to U.S. Provisional Application Ser. No. 60/838,656, filed Aug. 18, 2006, in the name of the same inventor listed above, and entitled, “A NETWORK OF SINGLE-WORD PROCESSORS FOR SEARCHING PREDEFINED DATE IN TRANSMISSION PACKETS AND DATABASES”. The present patent application claims the benefit under 35 U.S.C. §119(e).
FIELD OF INVENTION
The present invention relates to ultra-fast database inquiries and real-time monitoring of network data. In particular, the present invention relates to equipment for ultra high date rate analysis and processing of internet protocol (IP) packets to enable real-time network security applications. In addition, the equipment will allow tracking of illegal activities over networks and provide personal and intellectual property protection. The present invention facilitates ultra-fast searches of databases for specific strings of data and can be used by Internet search engine providers to respond to Internet Recipient (IR) queries with fast and precise responses.
BACKGROUND OF THE INVENTION
Internet and databases are becoming key strategic corporate and government resources that need to be protected against all kinds of cyber-crime. It is thus desirable to monitor Internet transmissions for their content and take appropriate actions when they violate corporate or government security. The present invention facilitates low cost, ultra fast packet payload analysis and database searches and provides dynamic protection on the use of specific elements of that database.
The most popular software-based internet packet analysis software is called SNORT. It includes over 2400 rules in its version 2.2, and is so slow that it cannot work effectively with the current high speed internet links. SNORT could provide some protection at the end user sites, but since end users are often careless about updating their antivirus (AV) software on a daily basis, the antivirus protection should be put into the servers and routers that operate under continuous maintenance. However, this requires that Internet packets must be processed at ultra high speeds of servers and routers. The present invention facilitates placing such ultra-fast packet payload analysis means in internet routers and servers.
The existing firewalls that check the source of messages by analyzing packet headers do not provide proper protection against many types of malware because transmissions coming from trusted websites can also be corrupted. To assure better protection, the internet packet payloads have to be also analyzed. Intrusion Detection Systems (IDS) scan packets payload for malware. In addition, there are also Intrusion Detection and Preventions Systems (IDPS) that perform both detection of malware and their removal. However, since these operations are typically performed in software, they are not suitable for acceptance at Network Aggregation Points (NAPS) and other servers, where they would be most effective. The present invention can be put into a single ASIC device to facilitate low cost, ultra fast packet payload analysis and elimination of malware at the servers and routers.
The complexity of today's technologies makes it almost impossible to monitor the flow of proprietary data out of corporations and government institutions. Now, the companies and government agencies can install inexpensive Internet payload monitoring devices, as per the present invention, which will warn and even stop the flow of confidential information out of corporations and government institutions. The present invention allows augmenting the existing firewalls with a device for controlling the flow of confidential data.
There is an explosion of abuses of intellectual property due to the ease of transmitting movies, songs, games, design software, and other copyrighted material between individuals. Ultra high speed and efficient monitoring of internet transmission for copyrighted material will slow the theft of intellectual property and stimulate creativity in many artistic, scientific and business fields. The present invention allows fast packet payload searches for strings of intellectual property.
We are becoming a society oriented towards databases that store a lot of personal data, such as health conditions, financial data, personal purchasing preferences, etc. Some of this information is crucial to individual's freedom and there have to be put strict rules on dissemination of information stored in national databases. One of the best ways to implement such restrictions on database access is using devices as per the present invention to monitor and control all downloads of such restricted information.
National security, tax evasion, and drug trafficking have become a major concern. Scamming for these criminal messages has to be conducted at multiple servers in the Internet network. The present invention allows linear, remotely controlled growth of the searched strings of data in many languages, including Kanjii, Farsi, and others.
It is therefore the object of the present invention to provide a method and apparatus for fast scanning of Internet data packets and databases for the desires strings of characters and graphic symbols.
BRIEF DESCRIPTION OF THE INVENTION
The purpose of this invention is to provide low cost, ultra-fast Internet packet payload analysis apparatus for monitoring illegal intellectual property transfers over the Internet network. The same devices can also be programmed to search for viruses, criminal messages, and to protect corporate and government databases from criminal or incidental information accessing and dissemination.
The device architecture as per the present invention is based on a network of parallel single bit processors. U.S. Pat. Nos. 6,578,133 and 6,915,410 describe a network of single bit processors that operate synchronously under control of a single clock. The current invention also uses network processors but they are single-word instead of single-bit processors, and they detect asynchronously the desired word strings in Internet traffic and database searches.
Each single-word processor is programmed to detect a single 8-bit ASCII or 16-bit Unicode character. Once that word is detected, the processor enables the output of the interconnected processor that is looking for the following word in a string of words. This way, a chain of words can be encoded in a network of processors. Each processor that finds its key word is immediately sending a so called “output enable” signal to the next processor in the chain. Should the next processor find its key word as well, it will send its own “output cable” signal to the next processor in the chain.
The processors' outputs in a processor network will be activated one by one as new words are detected. This process will continue till the desired sequence of words is detected by the network of the interconnected single-word processors.
Each processor can activate several other single-word processors' outputs, if they are processing words that form a logical OR operation on words in a string, as explained in the Example 1, below.
EXAMPLE 1
If we are searching for a key words sequence (KWS) consisting of key words:
brown (dog or Lassie) jumped over (fence or stream or bicycle), then:
Word Processor 1 (WP1) will be assigned detection of the word “brown”.
Word Processor 2 (WP2) will be assigned detection of the word “dog”.
Word Processor 3 (WP3) will be assigned detection of the word “Lassie”.
Word Processor 4 (WP4) will be assigned detection of the word “jumped”.
Word Processor 5 (WP5) will be assigned detection of the word “over”.
Word Processor 6 (WP6) will be assigned detection of the word “fence”.
Word Processor 7 (WP7) will be assigned detection of the word “stream”.
Word Processor 8 (WP8) will be assigned detection of the word “bicycle”.
The moment the WP1 processor detects the word “brown”, it activates the WP2 and WP3 processors to start searching for “dog” and “Lassie”, respectively. If either WP2 or WP3 detect the assigned word (“dog” or “Lassie”), they activate the WP4 processor that will start searching for “jumped”. Once the word jumped has been detected, the WP4 processor will activate the WP5 processor that will start searching for the word “over”. After “over” is detected, the WP5 processor will activate in parallel the WP6, WP7 and WP8 processors searching for words “fence”, “stream” and “bicycle”, respectively. If WP6, WP7 or WP8 detect their assigned word, they will generate message, “Detected string: brown (dog or Lassie) jumped over (fence or stream or bicycle).”
Since the key words, such as “brown”, “dog”, “Lassie”, etc. can be interlaced with some irrelevant words, the WP2, WP3 and other processors in the network, when activated, are looking only for the specific word that they have been programmed to detect. These processors will ignore all other words, except those for which they have been programmed to locate. The processors in the network are programmed for the specific words, and the interconnections between these processors correspond to the positions of key words in the string for which the apparatus is searching.
EXAMPLE 2
If a word-processor network has been programmed for searching the text patterns in Example 1 and the string of words is as follows: “brown with white dog jumped carefully over a big fence”, then the WP2 processor will ignore words “with” and “white”, and will detect only the word “dog”. The processor WP5 will filter out the words: “brown”, “with”, “white”, “dog”, “jumped”, and “carefully”, because it was programmed to detect “over”. Similarly, processor WP6 will filter out the words “brown”, “with”, “white”, “dog”, “jumped”, “carefully”, and “over” and will detect the word “fence”.
DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts connections between compiler, programmer and processor networks.
FIG. 2 shows connections between network processors and Internet bus.
FIG. 3 illustrates a single-word processor embodiment.
FIG. 4 show processor's output enable logic.
FIG. 5 depicts detection of a key words string by processor matrix.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The basic arrangement of processing blocks within the apparatus as per the present invention is shown in FIG. 1 . The searched database 82 is typically derived from Internet packets by an Internet router or Internet server hardware. The database 82 can be stored in FIFO hardware, dual ported RAM, or other types of memory. The database 82 , also called the data input means 82 , feeds its contents over the signal lines 83 into the EOL & EOW detector 84 . If the EOL & EOW detector 84 detects end-of-line (EOL) or end of word (EOW) characters within the data provided on its input signal lines 83 , it will produce EOL signal on signal line 51 or EOW signal on signal line 52 , respectively.
The key word strings (KWS) are entered into the KWS editor 4 . The KWS editor 4 can be any text editor, such as provided within Active-HDL 7.1 software or the like. The text from editor 4 is fed via signal line 5 into the KWS compiler 6 that distributes the key words among the processors 22 - 11 through 22 - im ( FIG. 2 ), residing within the Processor Matrix 1 - 1 . The algorithm for distribution of key words within a processor network can be based on various algorithms known in the field, such as simulated annealing, genetic, heuristic, “tabu search”, greedy or the like.
Each single-word processor 22 - 11 through 22 - im as shown in FIG. 2 , is typically connected to eight or more of its neighboring processors and can be made as honeycomb, hexagonal, etc. connectivity structures. The connections between processors are preferably two-way, so the processors can be interconnected in various configurations. The processor connectivity is specific to the device architecture. To save on silicon area, the interconnections between processors could be bidirectional instead of two-way connections that have separate wires for each direction of signal flow. The compiler 6 , after analyzing the entered keyword strings will select, which of the processors will be used, and which of the connections between processors will be enabled.
The KWS compiler 6 computes optimal distribution of key words in the single-word processors 2 - 11 through 22 - im , residing within Processor Matrix 1 - 1 . As shown in FIG. 1 , a system for detecting word sequences can have multiple matrices 1 - 1 through 1 - n to provide for large numbers of searched patterns. The KWS compiler 6 generates a series of ASCII character codes for key words that are then loaded into processors 22 - 11 through 22 - im . The KWS compiler 6 also establishes connectivity between these processors by loading an appropriate control word into the connectivity control register CCR 44 , shown in FIGS. 3 and 4 . If the WP1 processor from Example 1 has been loaded into the processor 22 - 11 and WP2 and WP3 into processors 22 - 12 and 22 - 22 , respectively, then compiler 6 will activate links between processors WP1, WP2 and WP3 by placing appropriate enable bits in the connectivity control register 44 of 22 - 12 and 22 - 22 that will enable signals provided on signal lines 73 and 74 , respectively. The signals on signal lines 75 and 76 will be disabled by compiler 6 , which will place appropriate disable bits in the connectivity and control register 44 of processors 22 - i 1 and 22 - 21 , respectively.
Referring again to FIG. 1 , the compilation results are fed via signal line 7 into PMP matrix programmer 8 . The PMP matrix programmer 8 provides the compilation results via signal line 9 to local programmers 18 ( FIG. 3 ), located within single-word processors 22 - 11 through 22 - im , shown in FIG. 2 . The local programmers 18 also control loading of ASCII characters into local data memory memories 12 ( FIG. 3 ) of processors 22 - 11 through 22 - im . The local programmers 18 could be combined into the processor matrix programmer 8 .
The architecture of a single-word processor, such as 22 - 11 is shown in FIG. 3 . The key elements of a single-word processor are: bus 30 that carries input data sent over the Internet or from a corporate database and which need to be scanned for key words, 4-bit address counter 11 that addresses data memory 12 storing characters of the word to be detected in the stream of data on bus 30 , which is representing searched database or data input means, and comparator 13 that compares data on its signal lines 29 with data on bus 30 and issues a compare signal on signal lines 23 if a match of character has been detected.
The address counter 11 is reset by a mismatch signal produced by word comparator 13 on signal line 23 , and fed via controller 10 and signal on signal line 31 . If word comparator 13 is fed an active CS signal on signal line 38 , then it will ignore the differences between the upper and lower cases and will produce the character detected signal between corresponding upper and lower case characters. The bit 5 in the ASCII character code differentiates between the upper and lower case. By ignoring bit 5 in the ASCII character comparison, all differences between the upper and lower case are eliminated. The detector 84 can perform Unicode mapping and provide appropriate characters on bus signal line 30 .
The key word to be detected by processor 22 - 11 is stored in its data memory 12 . Each letter or character of a key word, such as “brown” will be stored in the sequential order of their 8-bit ASCII character code representation. The 9th bit in the data memory 12 denotes the last character of the key word stored in data memory 12 . Detection of the 9 th bit sends a signal on signal line 71 that causes resetting of address counter 11 by counter controller 10 .
In the initial state, data memory 12 produces on its output signal line 29 the first letter or character of the key word that the processor 22 - 11 has been programmed to detect. This character will be compared continuously within the word comparator 13 with the string of characters provided on bus line 30 , representing the searched database. Should a match occur, word comparator 13 will produce character detected signal on signal line 23 . The counter controller 10 is responsive to character detected signal on signal line 23 and produces a signal on its output signal line 27 that enables address counter 11 to increment its count by one on the next clock edge, provided on signal line 21 . As a result, counter 11 will be addressing the next character of the key word stored in data memory 12 . If the comparator 13 detects different characters on its 28 and 30 inputs it will generate character miss-detected signal on signal line 23 . Responding to character miss-detect signal, counter controller 10 will reset address counter 11 via signal line 31 , unless bits WDB 36 ″ and EMB 37 ″ in register 20 are set active, as will be explained below in reference to FIG. 3 .
There are many ways to implement programmer 18 . One of the programmer 18 implementations is shown in FIG. 3 . The programmer 18 is responsive to signals 41 , 42 , and 43 , all being part of the bus signal line 9 , generated by the processor matrix programmer 8 . The signal line 41 provides addresses of characters in data memory 12 , selects operational mode register 20 and connectivity control register 44 . The signal line 42 provides data to be written into data memory 12 , operational mode register 20 and connectivity control register 44 . The write enable signal on signal line 43 is converted by programmer 18 into memory write enable signal on signal line 46 , register 20 enable signal on signal line 47 and register 44 enable signal on signal line 48 . The enable signals on signal lines 46 , 47 , and 48 are preferably clocked with clock signal on signal line 21 .
Responding to data on signal lines 41 and 43 , the programmer 18 issues load signals 46 , 47 , and 48 that load data from signal lines 42 into data memory 12 , operational mode register 20 and connectivity control register 44 , respectively.
Responding to the user setups, compiler 6 writes appropriate control bits into operational mode register 20 that stores WDB or word discontinuity bit 36 ″, CCS or character case sensitivity bit 38 ″, PWB or partial word bit 39 ″ and EMB or embedded word bit 37 ″.
Very often, senders of malicious or criminal messages try to avoid detection of key words by intermixing lower and upper case letter in the same word. The user of the device built as per present invention can request compiler 6 to ignore the difference between the upper and lower case characters. In such a case compiler 6 will enable bit CCS 38 ″ in the OMR operational mode register 20 , via signal line 7 , processor matrix programmer 8 , bus signal line 9 and programmer 18 , located within the processor 22 - 11 in FIG. 3 .
The WDB data on signal line 36 allows detection of key words despite some incorrect characters inserted anywhere in the key word. For example, the word s?t % c#@a!1*i&ng can still be detected as the word stealing. To accomplish this, the controller 14 , which is being responsive to the WDB signal on signal line 36 and character mismatch signal on signal line 23 , issues a HOLD signal on signal line 24 that stops counter controller 10 from resetting the address counter 11 for one character mismatch signal sent over signal line 23 . Only when there are two consecutive character mismatches sent over signal line 23 , the hold controller 14 will send a signal over signal line 24 that will cause the counter controller 10 to reset the address counter 11 .
For example, if the second letter on the signal line 30 is not the same as the second letter of the key word in data memory 12 fed on signal line 29 , then the signal on signal line 23 will activate the hold controller 14 , which will put on hold any action by controller 14 till the arrival of the third character on signal line 30 . If the third character on signal line 30 is identical to the second character in data memory 12 , then hold controller 14 will advance the counter 11 via output signal line 24 , counter reset controller 10 and its output signal line 27 . However, if the third character on signal line 30 is not identical to the second character in data memory 12 , the counter 11 will be reset by the hold controller 14 via signal line 24 , counter controller 10 and reset line 31 . After the counter 11 is reset via signal line 31 , it addresses the first character of the key word in data memory 12 , and the search for the key word will start anew. The hold controller 14 may be programmed to skip two or more incorrect characters on signal line 30 instead of one incorrect character as described above.
Some criminals may attempt to hide key words of a message by embedding it within other words. The EMB bit 37 ″ within operation mode register 20 will instruct controller 14 to search for embedded words. For example, it will detect the word cat in tomcat, concatenation, etc. In such a situation, controller 14 allows detection of key word starting from a character other than space, and allowing a key word to end on other character than space. The embedded character mode will also detect a word, which character may reside in several consecutive words. For example, apparatus built as present invention will detect key words “steal money” in the sentence steam locomotives are newer than yachts. This mode terminates search of the specific key word only after an end-of-line or ‘period’ character has been detected.
The search for the embedded characters is facilitated by the present invention because all single-word processors are running all the time. The controller 14 controls the operation of the single word processor via signal line 24 . The EMB bit 37 ″ in register 20 allows detection of key words that are embedded in other words. Responding to the EMB signal on signal line 37 , controller 14 can start detection of a key word without the presence of a space character before or after the key word. The controller 14 also will prevent counter controller 10 from resetting address counter 11 on character mismatches provided on signal line 23 . Only EOL signal on signal line 51 or master reset mRST on signal line 53 will terminate the search for the key word by controller 14 . In its standard mode of operation, with the EMB bit 37 ″ inactive in OMR register 20 , the controller 14 will look for key words having a space character before and after the searched key word.
Some languages such as German are known for long strings of letters in a word. Also some viruses have very long strings of characters. However, the optimal solution was found to use 16-character word detection processors in typical implementations. To accommodate a word with more than 16 characters, the KWS compiler 6 is splitting each long word into a set of characters that fit within the single-word processors. For example compiler 6 may divide a long word into a set of 16-character entities and feeds them into separate single-word processors 22 - 11 through 22 - im like they were separate words. For compiler's simplicity, it is desirable that all these 16-character words be located within the same processor matrix 1 - 1 or similar.
The compiler 6 sets the partial word PWB bit 39 ″ in OMR register 20 via signal line 7 , processor matrix controller 8 , signal line 9 and programmer 18 , in a manner described above in reference to bits CCS 38 ″, WDB 36 ″, and EMB 37 ″ in register 20 . All partial words generated by compiler 6 from a very long word, with the exception of the last word, have the PWB bit 39 ″ in register 20 set active.
For words with 16 characters of less, EOW signal on signal line 52 is inactive, and it does not reset the PF flip-flop 56 via output control register 15 and signal line 54 . However, if the PWB bit 39 ″ is active, denoting that a partial word is being processed by single-word processor, then EOW signal on signal line 52 will reset PF flip-flop 56 via control register 15 and signal line 54 .
The last section of a long word split into shorter words will have PWB bit 39 ″ set inactive by compiler 6 . This will inhibit resetting of PF flip-flop 56 by the EOW signal provided on signal line 52 . For example, the TV-videocassette recorder long word will be split by compiler 6 into 2 words: TV-videocassette and recorder. If data means 82 provide on signal bus 30 sequences of words: TV-videocassette recorder, then EOW space character after the first word TV-videocassette will reset PF flip-flop 56 of processor handling this word. The processor handling the recorder word will not be activated because PF flip-flop 56 of the preceding processor handling TV-videocassette will be already reset by the ‘space’ or EOW signal appearing before the word recorder.
The processors 22 - 11 through 22 - im in FIG. 2 are having two-way connections with other processors in the processor matrix 1 - 1 . For example, processor 22 - 11 is connected with processor 22 - 12 with signal lines 73 and 73 ′. The signal line 73 conducts signals from processor 22 - 11 to 22 - 12 and 73 ′ conducts signals in the opposite direction. Similarly, 22 - 11 is connected with 22 - 21 by means of signal lines 76 and 76 ′. The connections between processors 22 - 11 through 22 - im are generally limited to eight neighboring processors to save on silicon area. However, the larger the number of connections, the greater the flexibility of the processor matrix 1 - 1 , and two-way connectivity with 64 neighboring processors in large processor matrices would be desirable. The neighboring processors are connected to processor 22 - 11 via signal lines 73 ′ 74 ′, 75 ′ and 76 ′. If PW1 is the first processor handling a string of words, and it if has been loaded into processor 22 - 11 , compiler 6 will set the FW bit in register CCR 44 of processor 22 - 11 to its active state. The bits EP 12 , EP 21 , EP 22 , etc. in register 44 will all be disabled as the associated with them processors 22 - 12 through 22 - im do not have any influence over the operation of the first processor 22 - 11 in a word string.
To set up the connectivity between processors 22 - 11 through 22 - im , compiler 6 analyzes the entered key-word patterns into KWS editor 4 and creates a set of enable bits EP 12 through EPin for each processor in the processor matrix 1 - 1 that will activate certain links between processors as described above in reference to FIG. 4 . Next, compiler 6 will send the E 12 through EPin data through signal line 7 , matrix programmer 8 , signal line 9 and processor programmer 18 , which will download these bits into the CCR connectivity control register 44 , in the corresponding processors 22 - 1 through 22 - im.
If the processor 22 - 11 is the first processor in the chain, then the FW bit in the connectivity control register 44 will be set high by compiler 6 during the system setup. If the FW bit is set high, a logic ‘one’ will be fed via signal line 65 to the OR logic gate 70 , and will produce on its output logic ‘one’ that will be fed as signal PEN-11 via signal line 50 to the pattern found controller 15 . If a single-word processor is the first in a chain of words, its output will have no dependencies on other single-word processor outputs.
FIG. 4 depicts how the enable bits EP 12 through EPi 1 generate the processor's 22 - 11 PEN-11 enable signal and provide it on signal line 50 , which in turn enables output control register 15 of processor 22 - 11 . If register 15 receives in addition active signal on signal line 71 that carries the last character signal, signal on signal line 23 that carries the character detected signal and signal on signal line 52 that carries the EOW signal, then output control register 15 will activate via signal line 54 the pattern found PF flip-flop 56 . An active PF-11 output signal, provided by PF flip-flop 56 on signal line 55 indicates that the single-word processor 22 - 11 has detected the key word it was searching for. In our example, signal PF-11 is sent over signal line 73 to processor 22 - 12 that is looking for “dog” and to processor 22 - 22 , which is looking for “Lassie”. The signal PF-11 will be used within block 60 of processor 22 - 12 to enable its output control register 15 over the internal signal line 50 .
If signal on signal line 71 indicates the last character present, and signal on signal line 23 indicates character match but PEN-11 signal on signal line 50 is inactive then the pattern found controller 15 does not set the PF flip-flop 56 . If signal on signal line 71 indicates the last character present, and signal on signal line 23 indicates character match then controller 10 , in response to signals on those two signal lines, will reset the address counter 11 via signal line 31 .
The 9 th bit in data memory 12 indicates the last character of the searched of word. If there is a character match detected by word comparator 13 and the 9 th bit in data memory 12 , sent over signal line 71 is inactive, then it is not end of the word, and controller 10 will advance the address counter 11 by count of one via signal line 27 , to address the next character stored in memory 12 . However, if EOL signal on signal line 51 is active, controller 10 will reset address counter 11 via signal line 31 .
If the character comparator 13 detects a match between character provided on signal lines 29 and 30 , it issues a character match signal on signal line 23 . If the 9 th bit in data memory 12 indicates the last character of the word, and the PEN-11 signal on signal line 50 is active, then the pattern found controller 15 will set the PF flip-flop 56 on via signal line 54 . If the 9 th bit in the data memory 12 is active, it will also force, via signal line 23 , the counter controller 10 to reset the address counter 11 via signal line 31 , and counter 11 will address the first character in data memory 12 .
Once enabled, the PF signals remain active till EOL end-of-line signal is detected. In typical applications, the PF signals from all processors in processor matrix 1 - 1 are connected to the PF status register 101 - 1 through 101 - n . The EOL signal on signal line 51 loads the PF signals on signal lines 86 - 1 through 86 - n into the PF status registers 101 - 1 through 101 - n.
The EOL signal on signal line 51 also activates string processor 117 , which reads the outputs of registers 101 - 1 through 101 - n , provided via signal lines 102 - 1 through 102 - n . The signals on signal lines 101 - 1 through 102 - n can be read as independent signal lines, via a multiplexer built into the input of processor 117 . The signal lines 102 - 1 through 102 - n can be combined into a tristate bus 87 and then fed into processor 117 .
Responding to EOL signal on signal line 51 , the strings processor 117 also reads the status of EOL counter 110 , provided on signal line 111 and status of strings matrix register 106 provided on signal line 108 . The string matrix 106 responds to signals on signal lines 55 and records, which word strings have been detected. The EOL counter provides information how many end of line characters have been detected, and which sentence is being currently processed. The string matrix register 106 provides information where PF signals from each processor 22 - 11 through 22 - im reside. This data allows the processor 117 to determine, which key word strings and in which sentences have been detected, and feed this information on signal line 89 to TCP Egress processing blocks that will determine what to do with the detected strings.
The processor matrix controller 8 enables via signal on signal line 122 the master reset controller 123 . The enable signal on signal line 122 is generated by processor matrix programmer 8 upon completion of programming the processor matrices 1 - 1 through 1 - n . The user console 120 generates user-activated signal on signal line 121 , which forces controller 123 to generate mRST signal on signal line 53 . A server 124 or router 126 that acquired new strings of data for analysis can generate reset signals on signal lines 125 and 127 , respectively, which force master reset controller 123 to generate the master reset signal mRST on signal line 53 .
There are many ways to save on the number of signal lines 102 - 1 through 102 - n . For example, only selected processors 22 - 11 through 22 - im could be allowed to be the top processor in a string of processors and generate the PF signal on their signal lines 55 . In such a case, compiler 6 would distribute words for single-word processors starting from the top of the string.
Still another way to save on wiring is to have all PF signals grouped into registers 102 - 1 through 102 - n and activate their tri-state outputs 102 - 1 through 102 - n onto bus 87 fed into processor 117 . Upon detection of the EOL signal, the processor 117 could activate register 101 - 1 through 101 - n outputs via signal lines 112 - 1 through 112 - n.
To speed processing of PF signals provided on signal lines 86 - 1 through 86 - n , the apparatus can have interrupt detection circuits 103 - 1 through 103 - n that are associated with signal lines fed into the registers 101 - 1 through 101 - n . The interrupt circuits 103 - 1 through 103 - n can sense the status of signal lines 86 - 1 through 86 - n and instruct processor 117 , via signal lines 104 - 1 through 104 - n , which registers 101 - 1 through 101 - n should be read. To simplify the drawing, signal lines 104 - 1 through 104 - n are shown combined into a bus signal line 80 that is entering the Interrupt port of string processor 117 .
Prompted by interrupt signals on signal lines 104 - 1 through 104 - n , the processor 117 can feed the tri-state outputs of registers 101 - 1 through 101 - n into bus 87 by issuing proper select signals on signal lines 112 - 1 through 112 - n . The outputs of register 101 - 1 through 101 - n contain the detected word string information to be further processed by string processor 117 and then provided on signal line 89 to TCP Egress Equipment controlling flow of Internet data.
To simplify explanation of the subject matter, searched database 82 represents such data means as Internet traffic or corporate database. Similarly, the EOL detector 84 represents a circuit that detects specific characters in the Internet packets or in corporate database. It can be end-of-line, end-of-word or any other character that users of apparatus built as present invention may wish to incorporate into the character string detection process. Specifically, the users may add schemes to detect excessive number of EOL signals, or they may use other characters than end of line for marking sentences and groups of words subject to analysis. The present invention allows all these changes to be added by manufacturers of the apparatus built as per the present invention.
An apparatus built as the present invention allows adding even more complex word string search capabilities than described above. There can be also made some simplifications for reduced functionality equipments. However, if any such apparatus is based on the single-word processor networks and it applies the general spirit of the present invention, it will fall within the scope of the present invention.
This disclosure provides exemplary embodiments of the present invention. The scope of the present invention is not limited by these exemplary embodiments. Numerous variations, whether explicitly provided for by the specification or implied by the specification, such as variations in structure, dimension, type of material and manufacturing process may be implemented by one of skill in the art in view of this disclosure.
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The present invention related to monitoring internet traffic for illegal Intellectual Property transfers, viruses, criminal and other illegal activities. It also assists the Internet search engine providers in generating fast and accurate responses to Internet Recipient (IR) database queries. A massively parallel network of processing units residing within a single programmable ASIC device assures speeds in excess of 100 Gigabits/second.
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BACKGROUND OF THE INVENTION
Field of Invention
The invention relates to a metal-ion-free developer which contains water and at least a water-soluble organic basic compound, and also to a corresponding concentrate. The developer is suitable for imagewise irradiated, positive-working recording layers--in particular photoresist layers.
Radiation-sensitive mixtures which are used in the production of printing plates, dry resists or photoresists usually contain naphthoquinone diazide derivatives as radiation-sensitive component. It is also possible to combine a compound which produces acid on exposure to actinic radiation with a compound which is cleaved by said acid and consequently becomes more soluble in the developer subsequently used. In addition, these mixtures usually contain polymeric binders which carry phenolic hydroxyl groups. Generally these are novolaks or polyhydroxystyrenes. They give the radiation-sensitive layer mechanical strength and resistance. Substrates from which capacitors, semiconductors, multi-layer printed circuits or integrated circuits can be produced are coated with such mixtures. Special mention should be made of silicon substrates which are also thermally oxidized and/or coated with aluminum and may also be doped. Metal plates and metal sheets, for example composed of aluminum, copper and zinc and bimetal and trimetal sheets, and also electrically nonconducting sheets which are vapor-coated with metals, and paper are also suitable. These substrates may be thermally pretreated, superficially grained, incipiently etched or pretreated with chemicals to improve desired properties, for example to increase the hydrophilic nature. In order to impart a better cohesion and/or a better adhesion to the substrate surface to the radiation-sensitive layer, it may contain an adhesion promoter. In the case of silicon substrates and silicon dioxide substrates, adhesion promoters of the aminosilane type, such as 3-aminopropyltriethoxysilane or hexamethyldisilazane are suitable for this purpose.
These recording materials are usually developed after imagewise irradiation with aqueous alkaline solutions which frequently contain tetraalkylammonium hydroxide as alkaline component. As a rule, aqueous solutions of tetramethylammonium hydroxide, (2-hydroxyethyl)trimethyl-ammonium hydroxide (=choline) or corresponding mixtures are used (U.S. Pat. No. 4,239,661). Such metal-ion-free developers have gained acceptance in the semiconductor industry, in particular in the production of integrated circuits with high resolution. The contamination of the semiconductor material with metal ions would result in malfunctions in the operation of the semiconductor component.
The semiconductor industry is producing with increasing frequency integrated circuits having structures which are markedly less than 1 μm. The increased integration density increases the requirements imposed on the photolithographic process for patterning the photoresist. If very small structures, for example vias, are to be imaged, an incomplete development is often observed in the exposed areas after the development with metal-ion-free developers--even in the case of those containing surface-active additives. Either too little or too much of the resist structures is dissolved away. Of the development faults which occur, scumming, microgrooving and T-topping are the most frequent.
"Scumming" refers to resist residues in the nonimage areas. "Microgrooving" manifests itself in the formation of small recessed or eroded regions at the base of the resist structures and occurs, in particular, in the case of high-resolution resists. The cause of "T-topping" is a sparingly soluble skin which results in a T-profile of the resist edges after the development.
These defects cannot be completely overcome by varying the lithographic process in order to generate clean, defect-free structures in the resist. For that purpose, a subsequent processing of the patterned resist layer in an oxidizing plasma reactor or by sputtering is necessary.
In the case of the subsequent etching processes for altering the substrate surface, which, for structures having a size of less than 1 μm, usually involves plasma etching, scumming or other development defects result in variable etching results or, as a result of necessary overetching, in alterations in the dimensions of the structures.
In particular, T-topping interferes with the inspection of the line width or line spacings and, in the subsequent dry etching process, affects the dimensionally faithful transfer of the dimensions of the resist structures into the substrate.
The formation of microgrooves manifests itself adversely in the etching process by increasing the extent of etching.
The effective suppression of development defects was virtually impossible with the surfactants hitherto used. At high surfactant concentrations, a high dark erosion of the resist in the unexposed areas could be observed. This resulted in the development of shallow resist profiles and in the loss of resolution.
SUMMARY OF THE INVENTION
An object of the present invention is therefore to provide an aqueous developer for positive-working photo-resist compositions with which the problems described above can be overcome. In particular, scumming, microgrooving and/or T-topping should no longer occur if this developer is used.
The object is achieved by a metal-ion-free developer which also contains certain anionic and, optionally, nonionic surfactants in addition to at least one of the standard basic compounds.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
A feature of the invention consequently relates to a metal-ion-free developer containing (a) water and (b) at least one water-soluble organic basic compound, which developer additionally contains
c) at least one anionic surfactant of the formula
R.sup.1 -- O--CH.sub.2 --CH.sub.2 --!.sub.z --O--CH.sub.2 --COOH(I)
or
R.sup.1 -- O--CH.sub.2 --CH.sub.2 --!.sub.z --O--CH.sub.2 --SO.sub.3 H(II),
where
R 1 is a (C 1 -C 20 ) alkyl radical or a (C 6 -C 20 ) aryl radical optionally substituted with up to 3 branched or straight-chain alkyl groups and
z is an integer from 1 to 60,
optionally
d) at least one nonionic surfactant of the formula
C.sub.m H.sub.2m+1 -- O--CH.sub.2 --CH.sub.2 --!.sub.x O--CH(CH.sub.3)--CH.sub.2 --!.sub.9 OH (III)
or
C.sub.m H.sub.2+1 -- O--CH.sub.2 --CH.sub.2 --!.sub.x O--CH(CH.sub.3)--CH.sub.2 --!.sub.y O--C.sub.n H.sub.2n+1(IV),
where
m is a number from 10 to 22,
n is a number from 1 to 6, and
x and y are, independently of one another, a number from 3 to 30,
and also optionally,
e) at least one surfactant of the formula
HC--═C--CR.sup.2 R.sup.3 -- O--CH.sub.2 --CH.sub.2 !.sub.x OH(V)
or
HO-- CH.sub.2 --CH.sub.2 --O--!.sub.x --CR.sup.4 R.sup.5 --C--═C--CR.sup.2 R.sup.3 -- O--CH.sub.2 --CH.sub.2 --!.sub.x OH(VI),
where
R 2 -R 5 are, independently of one another, hydrogen atoms or (C 1 -C 5 )alkyl groups and
r is a number from 1 to 60;
or of the formula
HO-- CH.sub.2 --CH.sub.2 --O--!.sub.s CH(CH.sub.3)--CH.sub.2 --O--!.sub.t H(VII),
where the ratio s:t is from 10:90 to 80:20, or of the formula
R.sup.6 -- O--CH.sub.2 --CH.sub.2 --!.sub.o --OH (VIII)
where
R 6 is a (C 6 -C 20 ) aryl radical optionally substituted with up to 3 branched or straight-chain alkyl groups, and
o is a number from 1 to 60,
the proportion of the anionic and nonionic surfactants being 10 ppm to 6,000 ppm, based on the total weight of the developer, with the proviso that the weight ratio (c): (d)+(e)! is 3:7 to 8:2 and the proportion of the surfactants (c) is always greater than the proportion of the surfactants (d) .
The C m H 2m+1 radical in the compounds of the formulae III and IV is generally an unbranched, fairly long-chain alkyl radical.
The developer according to the invention generally has a pH in the range from 11 to 13.5.
Preferred water-soluble organic basic compounds (b) are aliphatic or aromatic amines, such as propane-1,3-diamine or 4,4'-diaminodiphenylamine, and basic heterocyclic compounds which contain, in addition to 3 to 5 carbon atoms, at least one nitrogen atom and, optionally, also oxygen atoms or sulfur atoms in the ring, such as pyrazoles, pyrrolidines, pyrrolidinones, pyridines, morpholines, pyrazines, piperidines, oxazoles and thiazoles. Also preferred are quaternary ammonium compounds, in particular optionally substituted tetraalkylammonium compounds in which the alkyl groups have no more than 4 carbon atoms in each case. Particularly preferred compounds of this type are tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (=choline). Mixtures of different bases may also occur in the developer according to the invention. The proportion of the compounds (b) is generally 0.5 to 20 percent by weight, based on the total weight of the developer.
Preferred anionic surfactants (c) are O-carboxymethyl O'-isononylphenyl polyethylene glycols, in particular those containing 6 to 30 ethylene oxide units in the polyethylene glycol chain (formula I, z=6 to 30, R 1 =(H 3 C) 2 CH-- CH 2 ! 6 --C 6 H 4 --).
Of the nonionic surfactants (d) of the formulae III and IV, those are preferred in which m=12 to 18 and n=2 to 4, x=2-8 and y=3-8.
The optionally present surfactants (e) serve to adjust the rate of development. In this connection, r is preferably 3 to 40.
"Metal-ion-free" means that the developer according to the invention contains no more than 100 ppb of metal ions.
The developer according to the invention is usually produced as a concentrate containing the constituents (b) to (e) specified above in 2 to 8 times the amount. Said concentrate according to the invention is stable, i.e. no phase separation, precipitation or turbidity occurs. It can readily be diluted again using deionized water to produce a ready-to-use, equally stable developer having optimum properties. Scumming, microgrooving and T-topping are effectively prevented by the developer according to the invention, and resolution and processing latitude are decisively improved.
EXAMPLES 1 TO 8 AND COMPARISION EXAMPLES C1 TO C2
Aqueous solutions were first prepared which contained 2.38 percent by weight of tetramethylammonium hydroxide or 4.20 percent by weight of choline. The solutions had a pH of 13. The surfactants (c), (d) and, optionally, (e) were then added in the amounts shown in the table in order to obtain the developer solutions according to the invention.
As a comparison, a developer was chosen which contained 2.38 percent by weight of TMAH and 2000 ppm of dinonyl-phenol ethoxylate, 18 EO groups (proportion of dinonyl 50 percent).
The following lithographic process was carried out:
A silicon wafer having a diameter of 3 inches was coated with a resist in accordance with EP-A 0 508 267 on a spin coater. After the subsequent baking process (prebake) at 100° C. for 120 s on a hotplate, the thickness of the resist was 1.1 μm. The coated wafer was imagewise UV-irradiated through a mask using an apparatus for reduced-scale projection (stepper FPA 1550, g-line, 0.35 NA, 400 mW/cm 2 , Canon Ltd.). The exposure was followed by a second baking process (post-exposure bake) at 120° C. for 80 s on a hotplate.
The wafers were developed for 50 s on a track system in the puddle mode using the developer solutions described in the table. After completion of the development, the wafers were rinsed with deionized water and spin-dried.
In the table below:
A) is the resist erosion in the unexposed areas;
B) is the irradiation time (in milliseconds) for the 1:1 imaging of the mask structures in the photo-resists (the radiation energy per unit area =irradiation! is equal to the irradiation time multiplied by the irradiance in the present case 400 mW/cm 2 !);
C) is the irradiation time for the field point;
D) is the ratio of (B) to (C) as a measure of the process latitude of the resist/developer system.
The developed structures were evaluated as follows with the aid of a scanning electron microscope:
++ very clean structures with very steep resist edges,
+ clean structures with steep resist edges,
- slight resist residues (scum),
-- marked scumming and T-topping.
TABLE__________________________________________________________________________Surfactant Assessment criteriaExampleanionic nonionic additive Concentration A B C StructuralNo. * **/**** *** ppm nm\50 s ms ms D quality__________________________________________________________________________1 100% -- -- 1000 12 340 215 1.58 +2 100% -- -- 2000 15 340 225 1.51 +3 100% -- -- 4000 15 270 180 1.50 +C1 40% 60% -- 3000 10 300 180 1.67 -4 66.7% 33.3% -- 3000 10 340 220 1.55 ++5 75% 12.5% 4000 16 280 200 1.40 ++6 60% 12.5% 20% 5000 19 280 200 1.40 ++7 40% 20% 20% 5000 18 270 180 1.50 ++8 33.3% 40% 33.3% 2000 14 250 160 1.56 ++C2 -- 33.3% -- 2000 42 320 180 1.80 -- 100%****__________________________________________________________________________ Surfactant* Polyoxyethylene isononylphenyl ether carboxylic acid, 6 ethylene oxide units (EO) Surfactant** Fatty alkohol alkoxylate R(EO).sub.3.5(PyO).sub.5.3 --OH, R H.sub.3 C--(CH.sub.2).sub.16 -- PyO = propylene oxide units Additive*** Polyoxyethylene isononylphenyl ether, 30 EO Surfactant**** Dinonylphenol ethoxylate, 18 EO
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The invention relates to a metal-ion-free developer which contains, in addition to at least one of the standard basic compounds, certain anionic and, optionally, non-ionic surfactants, and to a corresponding concentrate.
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CROSS-REFERENCE TO RELATED APPLICATIONS
Not Applicable
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH
None Applicable
REFERENCES TO SEQUENCE LISTINGS, TABLES OR COMPUTERS
None
PROGRAM LISTINGS, COMPACT DISK APPENDIX
None
BACKGROUND OF THE INVENTION
In recent years people with antisocial aberrations have undertaken lethal hijackings of aircraft resulting in severe losses of life and property. Among the solutions to this problem which have been advanced are strengthened physical security at airports, various baggage security techniques, the introduction of armed air marshals on flights, arming of pilots, and strengthening of cockpit doors. The latter procedure has proven effective in incidents which have occurred since the recent emphasis on the process of “hardening” aircraft doors, but it is apparent that the brute force solution of requiring a plurality of iron bars to be built into the doors for hardening, while effective against a frontal assault, does not protect against missiles tossed into the cockpit, and adds an undesirable amount of unproductive weight to the aircraft, inhibiting performance and reducing the potential payload.
DISCUSSION OF THE PRIOR ART
Security doors and cells (robber traps) are well known in the patent literature with respect to static structures such as financial and retail institutions, with variations on the theme of two remotely controlled lockable doors, or revolving doors which lock in position to prevent a robber's escape. Given terrestrial installation, the design of such cells is usually dominated by commercial considerations to disguise the cell to appear as open and inviting as possible so as not to discourage the entry of the general public who wish to do business with the establishment. Precluding claustrophobia is a major terrestrial design consideration since the very idea of a security cell tends to inhibit people from coming through the cell on their way into a store or bank. Illustrative of the terrestrial security cylindrical cell art, see U.S. Pat. No. 6,073,394, to Uhl, and U.S. Pat. No. 5,181,018, to Cowie.
SUMMARY OF THE INVENTION
This invention relates to a cylindrical module which may be retrofit into the passageway of an aircraft which communicates between the cockpit and the passenger cabin. The cylindrical module, installed as fixed to the aircraft structure, is provided with two apertures, one facing into the cockpit and the other facing into the passenger cabin. A pair of arcuate doors (i.e. arcuate conformably to the cylindrical arc of the module) are slidably mounted into the apertures on tracks and are connected to remotely-controlled driving means which enable the doors to slide back along the cylinder walls. The doors are normally closed. In operation the captain of the aircraft in the cockpit opens the aft door from the passenger cabin in response to a request from a candidate for entrance, whereupon the candidate enters the interior of the cylindrical module and the aft door closes behind the candidate. The module would be equipped with a variety of readers, sensors and detectors to examine the candidate for identity and absence of weapons. When the captain is content that the candidate has cockpit business and is authorized for entry, the forward door is opened and the candidate is permitted to enter the secure cockpit.
Transplanting the security cell into an aircraft presents a number of special considerations. Unlike the terrestrial application, the weight of the airborne security cell must be carried for the entire duration of flight as a continuing drain on the power supplied by the aircraft engines, so it must be lightweight. Space is at a premium since the aircraft has already been designed and configured to use virtually all the space between the cockpit and the passenger cabin, so a retrofit module must be capable of fitting into a narrow, predetermined space and shape. Crew are themselves chosen in part for their compact size and shape and are typically subject to weight limits. It is desirable that the chamber defined by the cylinder be small enough to admit only one person at a time, thereby discouraging hostage taking and contributing to the compactness of the design. Even for aircraft designs with ample space in the passageway to the cockpit, it is preferred that the cylindrical security module of our invention be kept small enough to permit passage through the cell of only one person at a time. The aircraft may be operated in abnormal attitudes so the direction of verticality may be, or seem to be, displaced. Even in normal operations, the mechanisms of the cell may be subjected to abnormal gravitational, centrifugal and centripetal forces, but they must nevertheless continue to work effectively and without delays. Finally, given the rigors of aircraft operation, failure of the security system cannot be tolerated and hence immediately-operable manual overrides must be provided to permit prompt ingress and egress.
Thus it is an object of this invention to provide an easily retrofittable module for effective secure access control for aircraft cockpits.
It is a further object of this invention to provide a security module for aircraft which has simple and uncomplicated design and construction.
It is a further object of this invention to provide a lightweight security module for use in aircraft.
It is a further object of this invention to provide a security module for aircraft with minimal to moderate power consumption requirements.
It is a further object of this invention to provide a security cell for aircraft which fits into space which is available within the existing configuration of the aircraft.
It is a further object of this invention to provide a security cell for aircraft which blocks line-of-sight openings between the cockpit and the passenger cabin during operation of the aircraft.
It is a further object of this invention to provide a security cell for aircraft which, although small enough to be retrofit, nevertheless offers ample space for readers, sensors and detectors to test the acceptability of a candidate who presents for admission.
It is a further object of this invention to provide a security cell for aircraft, which adapts proven security techniques and design considerations for airborne use.
It is a further object of this invention to provide a security cell for use in aircraft which can be relied upon to be operable despite being subjected to abnormal gravitational, centripetal or centrifugal forces.
It is a further object of this invention to provide a power operated airborne security cell which has manual override features to permit quick and convenient egress in case of power failure.
It is a further object of this invention to provide a retrofittable aircraft security module which, when designed for retrofit into a specific aircraft model, can be quickly installed during routine maintenance so as to minimize the time delay in getting the aircraft back into service.
It is a further object of this invention to provide a security module for aircraft made from bullet-resistant materials and which is resistant to other forms of mechanical attack.
It is a further object of this invention to provide a cylindrical airborne security module with rack and pinion drive means for selectively and smoothly driving arcuate doors for opening and closing access apertures in the cylindrical module.
It is a further object of this invention to provide a cylindrical security module for aircraft which may serve as an entrapment mechanism for hijackers seeking entry to the cockpit, and which is tamper resistant to preclude escape of a hijacker so entrapped.
It is a further object of this invention to provide a security module for airborne application which is readily and easily serviceable by maintenance and security personnel.
It is a further object of this invention to provide an airborne security module with identification and testing means, of sufficiently small size as to preclude easy admission to the interior of the module by more than one person at a time.
Those skilled in the art will readily appreciate that many of the substantial and distinguishable structural functional abilities and advantages disclosed herein represent significant advances over the prior art and that individual features disclosed herein may be applicable in the field of secure access control for ground applications as well as for airborne applications.
The foregoing and other objects of the invention can be achieved with the present invention, device and system which is a cell door system principally for aircraft security.
The invention, in a broad sense, is provided as a security cell system having mechanical drive means, two door panels and a selectively operable geared disconnect assembly, for engaging and disengaging the door panels in relation to the drive means; therefore providing respective opening and closing movements along a displacement path and selective access to the cockpit secured area. The invention may be installed and utilized in an aircraft, or similar, structure, such as an adjacent or proximately located support structure for an aircraft of other structure close to or for use while servicing an airplane.
The security cell system is provided with a cylindrical containment cell area having two substantially parallel partitioned inner compartment walls that form a short internal hallway between the two arcuate sliding door panels. The door panels are secured in place between two semicircular grooved tracks, one such grooved track that supports the bottom of both door panels while the other grooved track secures the tops of the door panels. The tracks may be thought of as circular for convenience only, since they might as easily be two semicircular tracks, each of which permits excursion of a door panel through a 180° arc, and there is no need for the two semicircular track sections to be coextensive as a 360° circle, nor that the two semicircular track members share a common central axis. The bottom ends and the top ends of the two arcuate doors are v-shaped along the curved surface to match the grooves in the (semi-) circular tracks, the upper track and the lower tracks having substantially the same arcuate radii as the corresponding door panels.
The doors 14 are fabricated preferably from bullet-resistant material such as Kevlar™ or other lightweight, composite, bullet-resistant material, to preclude attempts to deliver bullets or other missiles from the passenger cabin into the cockpit.
Each of the two door panels is provided with one lower arcuate rack and one upper arcuate rack attached to the inside of each door. Each door is provided with a long, vertical shaft having upper and lower pinions mounted thereon to mesh with the lower and upper arcuate racks for driving the doors respectively to their open and closed positions. The vertical shaft, with pinions, is provided to assure that the doors are driven at both the top and bottom for even driving pressure to prevent the doors from binding in the course of their opening/closing excursions. Reference here to vertical, top, or bottom, assumes the cell, and the aircraft, are at rest on the ground. Since, in flight, the cell will be in whatever attitude the aircraft is in, the G forces acting on the cell and its components, may be varied and strong.
The interior of the security cell has substantially parallel sides, substantially flat panels which extend generally from the top of the interior chamber to the bottom. A top down cutaway view would show that the inside of the flat panels define a chamber, or an equipment bay, with the inside wall of the module, and within the equipment bay, an assortment of readers, sensors and detectors may be installed, as well as an array of gas dispensers, electronic stun apparatus, or other means for subduing a hijacker. The vertical shafts which carry the pinions which drive the doors to their open and closed positions, are also concealed behind these flat panels.
The opening and closing power derives from small electric motors powered by the aircraft's electric power system, and mounted advantageously in a ceiling chamber of the module. The power is transmitted to the drive shaft through a power train which includes a worm gear, an arrangement which is very difficult to reverse, and thereby making the system virtually impervious to attempts by the person inside the cell to open or reopen the door once inside by pushing on the door. The door is smoothly formed, precluding handholds which might give purchase in an attempt to move the door sideways. The module has therefore additional utility in being useful as a detainment cell pending landing of the aircraft so that the inhabitant of the cell can be turned over to ground security personnel.
The module may be further arranged to keep at least one of the doors closed at all times while the aircraft is in operating mode, i.e., loading, taxiing, flying, landing, and unloading. This feature prevents an attacker from having an opportunity to present missiles, e.g., bombs, explosives, gas canisters, gunfire or other hazardous items from being thrown or delivered from the passenger compartment into the cockpit during critical moments in the operation of the aircraft.
The pilot has total control of the security module, as all control mechanisms are operable solely from the cockpit, including emergency releases.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 : A plan view of the front section of an aircraft giving an overall view of how a security module after our invention would be retrofit into the passageway between the cockpit and the passenger cabin of an aircraft.
FIG. 2 . Enlarged view of the center portion of FIG. 1 , showing a cross section of our module with both doors closed and a candidate for admission approaching the rear door of the module.
FIG. 3 . Same as FIG. 2 , but the rear door has opened and the candidate has taken station inside the module.
FIG. 4 . Same as FIG. 3 , but the rear door has closed around the candidate.
FIG. 5 . Cutaway cross section side view showing the motor, drive shaft, disengagement lift, upper track, door with upper arcuate rack engaged with the upper pinion, and in the lower portion of the drawing, the lower part of the door with the lower arcuate rack engaged with the lower pinion, and the lower track.
FIG. 6 . An enlarged portion of the upper part of FIG. 5 showing the driver clutch lifted out of engagement with drive shaft.
FIG. 7( a ) Vertical section through the emergency door release showing the spline sleeve coupling fully engaged with the lower shaft gear for normal operation.
FIG. 7( b ) Similar to (a) but with the spline sleeve coupling raised to disengage from the lower shaft gear, leaving the doors free to rotate for manual operation in emergency door release mode.
FIG. 7( c ) Horizontal section of FIGS. 5 and 6 showing the lifting fork which disengages the spline sleeve coupling from the lower shaft gear.
FIG. 7( d ) Detail of spline sleeve coupling shown in vertical and horizontal cross section.
FIG. 7( e ) Detail of the drive line components from the upper drive shaft to the lower drive shaft showing the respective parts which achieve smooth engagement/disengagement of the drive mechanism.
FIG. 8 . Illustration of a candidate inside the module with both doors closed, waiting for the cockpit (forward) access door to be opened for admission into the secure cockpit space.
FIG. 9 Horizontal section showing the configuration of the left and right door frames when the door is closed.
FIG. 10 . Horizontal section showing the floor plate. Both doors are shown partly open for clarity, but in practice at least one door would be fully closed while the aircraft is operational.
FIG. 11 . Horizontal section with the top cover plate removed, showing the location of the two drive motors and the emergency manual door release cables, which are controllable solely from the secure portion of the aircraft.
FIG. 12 . Like FIG. 10 , but with cutouts showing the lower drive pinions engaged with the arcuate racks on the lower edge of the doors. One door is shown partly open for clarity.
FIG. 13 . Horizontal section of the sub floor plate, beneath the floor plate shown in FIG. 10 . Shows the bearing assemblies which support the long vertical drive shafts. Also shows the central support members provided for stability of the unit in its connection to the floor of the aircraft.
FIG. 14 . Vertical schematic sectional view (not to scale) through the security module showing the general juxtaposition of the respective major portions of the module.
FIG. 15 . Schematic diagram of the electrical control system of the security module.
FIG. 16 . Horizontal section illustrating a single door version of the security module in open and closed positions.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The retrofittable security door module of our invention is preferably installed in the passageway between the cockpit and the passenger cabin of an airliner as shown in FIG. 1 .
The module is attached to the aircraft by custom brackets, or even wall sections 53 which are fabricated as necessary to interface with a particular aircraft configuration. These brackets will typically be consistent over a plurality of individual aircraft of the same model, thereby affording a measure of repetitivity in manufacturing of the brackets. Other components of the module are designed to be interchangeable over substantially all aircraft into which they might be installed.
In operation, a candidate 56 for admission to the cockpit, is shown in FIG. 2 approaching the security module rear door 14 . The candidate 56 is admitted to the module when a pilot activates the control which opens the arcuate door 14 , causing the door 14 to be driven into a recess between in inner and outer walls of the module, permitting the candidate 56 to enter the module, as seen in FIG. 3 . Once inside the module, the door 14 closes, as shown in FIG. 4 . While enclosed in the module, the candidate may be examined by a plurality of instruments which are installed in the equipment bays 51 . These may include video, card readers, retina scanners, magnetic weapons detectors, fingerprint readers, and such other scanning and reading devices as may be appropriate for identification and authentication of the candidate 56 , or as might be required to fulfill the security protocols of the organization which operates the aircraft. In addition to identification apparatus, the equipment bays may contain apparatus for gaseous discharges or electronic stun equipment for disabling the candidate 56 if that person should prove to be an attacker.
With reference now to FIG. 5 , it may be seen that the doors 14 are held in place between upper 15 door frame guides and lower 44 door frames. Both the frame members 15 and 44 are provided with V-shaped edges which are cooperatively positioned into the inverted V-shapes formed in the upper 16 and lower 45 track members and are rollably separated from them by the bearings 36 .
The lower frame member 44 is provided with a groove into which the closure plate 43 fits to provide a loose seal sufficient to prevent substantial particles from falling through into the track and drive mechanisms below.
Both the door frames 15 and 45 are provided with arcuate rack sections 1 conforming to the arcuate shape of the doors 14 . The rack sections 1 are meshed cooperatively with pinion gears 2 which are mounted respectively at the upper and lower portions of drive shaft 3 , at locations which are respectively above the ceiling and below the floor of the candidate reception chamber. Drive shafts 3 are held in position at the upper end by stabilizing bearings 33 which are attached to the upper door tracks 16 , and are held at the lower end by the bearing assemblies 38 which are attached to the base of the module.
Colinear with each lower drive shaft 3 and above it, are upper drive shafts 4 , driven by a worm 26 and worm gear arrangement powered by motors 5 . The upper drive shaft 4 is held in decoupleable engagement with the lower drive shafts 3 by springs 7 and splines 10 . The decoupling mechanisms will be explained in greater detail below with respect to FIG. 7( a ) to ( e ). The decoupling mechanism is activated in the absence of power by the manually operated release cable 19 , or if power is available by the door release cable 20 which operates the solenoid 21 .
FIG. 6 shows the upper part of the same sectional view as FIG. 5 , but the mechanism is in reaction to a power-on door release signal. Upon receipt of an electrical charge delivered through the electric cable 20 , solenoid 21 is activated, drawing the shift fork sleeve 25 upward along the shift fork sleeve shaft 22 and carrying the shift fork 9 upward to lift the spline sleeve coupling 10 up and clear of the lower shaft gear 13 , thereby leaving the lower drive shaft 3 free to turn and permitting the door to slide freely to any desired position. The shaft 22 and solenoid 21 are securely affixed to the support bracket 23 which is secured to the exterior wall 17 . Also held by the bracket 23 is the sleeve 27 which guides the travel of the shift fork sleeve shaft 22 . The solenoid 21 is held in its normal position, when not activated, by the spring 24 .
Alternatively, manual activation of the release cable 19 can draw the lifting fork 9 upward to achieve disengagement of the spline sleeve coupling 10 from the lower shaft gear 13 , with the same result.
It may be seen in FIG. 7( a ) that when operationally coupled together, collinear drive shafts 3 and 4 are connected by means of the upper shaft gear 11 which is attached to shaft 4 to rotate as shaft 4 rotates. When coupled, shaft 4 is received in the lower shaft gear 13 by the pilot bearing 32 . The upper shaft gear 11 is attached to the spline sleeve coupling 10 and the splines of the coupling 10 fit down over the teeth of the lower shaft gear 13 . As seen in FIG. 7( b ), when the lifting fork 9 raises the spline sleeve coupling 10 to disengage from the lower shaft gear 13 , the coupling connection between the upper drive shaft 4 and the lower drive shaft 3 is broken and the associated door 14 is free to move.
Operation of the lifting fork 9 is best understood with reference to FIG. 7( c ) where the fork 9 is engaged with the coupling sleeve 10 . The fork 9 is carried by the hollow square cross sectioned shift fork sleeve 25 which rides on the shift fork sleeve shaft 22 , separated from it on all four sides by the sleeve bushing 28 .
The spline sleeve coupling 10 is illustrated in FIG. 7( d ), where the coupling 10 holds the spring retainer 6 and the bumper rings 8 are provided to form a groove to securely receive the lifting fork 9 .
In FIG. 7( e ) the arrangement for driveable connection between drive shafts 4 and 3 is illustrated. Note from comparison of FIGS. 7( a ) (engaged) and 7 ( b ) (disengaged), the shafts 3 and 4 are in collinear, tandem juxtaposition, and the engagement is achieved through the spline sleeve 10 which is moved up to disengage and down to engage. Even when disengaged, the shaft 4 spins fruitlessly in the pilot bearing 32 which is secured within the lower shaft gear 13 to maintain the colinearity between the shafts 3 and 4 .
FIG. 8 shows a candidate for admission to the cockpit secure area standing in the interior of the security cell with orientation arrows identifying the location of the cross sectional view of FIG. 9 . The arcuate doors are shown for convenience in FIG. 9 as thought they were planar rather than arcuate. The doors 14 fit into a door frame 47 . When fully driven to the end of its excursion, the door frame, comprising an after section 47 and leading section 54 , which is shaped to complement the shape of the door stop 50 , comes to rest against the door stop 50 . The door frame 47 is lightly in contact with door spacer 49 which is adhered to the exterior cylinder wall 17 on one side, and is similarly lightly in contact with the angle door spacer 48 on the other side. The angle door spacer 48 is adhered on one side to the intermediate wall 46 and on the other to the interior wall panel 41 . It may be seen that the interior wall panel 41 defines a cavity in which the lower drive shaft 3 is enclosed.
With reference now to FIG. 14 , it may be seen that the next series of drawings, FIGS. 10 , 11 , 12 , and 13 , are cross sections of the module of our invention at the respective levels and from the respective directions therein indicated.
FIG. 10 is a cross section through the lower central portion of the security module looking down. The doors 14 are shown in their true arcuate configuration, and are depicted partially open for clarity. It will be appreciated that while the aircraft is in operation at least one of the doors 14 will be in the closed position at all times. The doors 14 are driven into and out of the recessed pockets which are defined between the exterior walls 17 and the intermediate walls 46 , by the rack and pinion arrangement previously discussed, under the positive drive forces transmitted through the lower drive shaft 3 . The interior walls 41 define the equipment bays 51 in which may be mounted such readers, sensors, detectors, dispensers and other security apparatus as may be chosen for the security design of the aircraft owner.
FIG. 11 is the view down upon the ceiling plate 52 , showing the motors 5 which, through a worm mechanism, drive the pinions 2 to activate the racks 1 which are attached to the doors 14 so as to propel them along their respective tracks in their excursion from fully closed (as is the door at the top of FIG. 11 ) through a partially open position (as is the door at the bottom of FIG. 11 ) to the fully open position when the door 14 is drawn to its maximum extent into the recess defined between the outer wall 17 and the intermediate wall 46 . Also shown in FIG. 11 are the door stops 50 and the manual emergency release cables 19 .
FIG. 12 is the view down on the floor plate 39 with part of the plate 39 cut away to show the lower drive shaft 3 carrying the lower pinion 2 which is engaged with the lower rack section 1 for driving the doors. The cut away view also shows the sub floor plate 37 and the floor support channel 40 , which supports part of the floor plate 39 .
FIG. 13 provides a view down upon the sub floor plate 37 showing the bearings 38 which support the lower drive shafts 3 . The sub floor plate 37 is also supported by the floor support channel 40 and the floor support plates 55 .
FIG. 14 provides a diagrammatic cross section, not to scale, of the cell fully assembled. From top to bottom, we see the top cover plate 18 , the interior ceiling 52 , the floor plate 39 and the sub floor plate 37 . The door 14 is held in a frame 47 ( FIG. 9 ) which has arcuate upper 15 and lower 44 members, and to which are attached the rack sections 1 . The upper portion of the arcuate upper frame member 15 is V-shaped to fit cooperatively with the inverted V of the arcuate upper track 16 , while the lower portion of the arcuate lower frame member 44 , is similarly V-shaped to fit cooperatively with the inverted V of the arcuate lower track 45 . The frame members and track members are separated by small bearings 36 ( FIG. 5 ) for smooth, positive movement throughout the excursions of the doors 14 .
FIG. 15 is an illustration of the Door Control Panel and Related Circuitry. The two push button switch for O 1 , 102 , (Open first door), C 1 , 104 , (Close first door), is a unit with two single contacts designed to operate alternately from close door to open door and vice-versa, contacts are normally open. The two push button switch for O 2 , 106 , (open second door) and C 2 , 108 , (close second door) is similar. The “E” Emergency control, 110 , is DPDT with normally closed contacts that are in series with the two closed door solenoids C 1 , 112 , and C 2 , 114 . It has a large push button and when pressed in, will lock in, in the on position, for both doors to fully open until the Door Limit Switches, 116 , 118 , are contacted. The emergency switch is released by a slight turn of the button and it returns to normal position. This also reconnects the circuit so the doors can be closed. Arrows, 120 , 122 , indicate the direction for the doors to close. The emergency button is protected with a hinged cap lid designed to prevent accidental emergency button engagement.
The On-Off switch, 124 , is a DPST which activates solenoid “P”, 126 , that connects current to the door motor controls. Each door has 3 limit switches. Two are SPST and one is DPST. The DPST D 1 LO, 128 , and D 2 LO, 130 , are for limiting door opening travel and individual door circuitry. The SPST D 1 LC, 132 , and D 2 LC, 134 , are for limiting the door closing travel. The other SPST switches, 136 , 138 , are close tolerance to the door opening preventing the other door from opening when one door is already open.
Except for the emergency switch, all push buttons are below the panel surface to inhibit accidental activation. Fuses or circuit breakers, 140 , 142 , are provided for Line 1 and similar mechanisms, 144 , 146 , are provided for Line 2 and also for the solenoid circuitry. Door motors M 1 , 148 , and M 2 , 150 , are reversible by the O 1 , 152 , and C 1 , 112 , and 02 , 154 , and C 2 , 114 , solenoids. These motor controls are interlocking so that only one set of contacts at a time can close. No part of the circuitry is dependent upon any particular gravitational angle so that the door controls remain operable irrespective of G forces acting upon the aircraft.
FIGS. 16( a ) and ( b ) respectively show a single door version of our invention in the closed FIG. 16( a ) and in one of the open FIG. 16 ( b ) positions. As shown, the door 14 extends through 270° of arc, whereas each of the two doors 14 as illustrated at FIGS. 2 , 3 , 10 , 11 , and 12 , extend only through substantially 90° of arc. The exterior cylinder wall 17 is provided with two apertures in the same way as the two-door version above described, but the controls are arranged to drive the door 14 to three different positions: open to the cockpit, FIG. 16( a ), closed, FIG. 16( b ), and open to the cabin which is like FIG. 16( a ) but with the door 14 rotated 180° from the position shown in FIG. 16( a ). To admit a candidate, the door would be rotated so as to be open to the cabin, the candidate would enter the interior of the module and the door would be rotated to the closed position as shown in FIG. 16( b ). After satisfactory examination of the candidate, the door would be rotated to the cockpit-open position and the candidate would be admitted to the cockpit.
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A generally cylindrical security door module is designed for retrofit into the passageway of an aircraft leading to the cockpit. Two doors, forward and aft, are provided which are mounted for opening and closing upon commands emanating from the cockpit. Both doors are normally closed and only one normally opens at a time. A candidate for entrance to the cockpit is permitted to enter the module when the cockpit personnel open the aft door, which is then closed. Sensing apparatus may be employed to establish the identity and clearance of the candidate. Upon approval, the cockpit personnel open the forward door to admit the candidate. Emergency release apparatus is also described.
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CROSS-REFERENCE TO RELATED APPLICATIONS
Pursuant to 35 USC §119, this application claims the benefit of and priority to German patent application no. 102014216593.8, filed on Aug. 21, 2014, which is herein incorporated by reference in its entirety.
FIELD OF THE DISCLOSURE
The invention relates to an operator assistance system for an agricultural machine which has at least one variable operating parameter which influences a plurality of different result parameters of the working result of the machine.
BACKGROUND
Agricultural machines such as tractors, combine harvesters and field choppers comprise a relatively large number of actuators for setting operating parameters, which actuators have to be placed in a suitable position in order to achieve a satisfactory harvesting result with appropriate application of resources. These operating parameters include in harvesting machines, for example, the rotational speed of the internal combustion engine, the propulsion speed (which defines the harvested crop throughput rate) as well as operating parameters of harvested crop-processing devices such as, in the case of a field chopper, the cutting height of the harvesting attachment, the feed speed in the intake duct, the number of chopper blades of a chopper drum and the distance between two rollers of a harvested crop post-processing device. In the case of a combine harvester, the threshing parameters and cleaning parameters have to be set. In tractors it is also necessary to make various settings and predefinitions, such as the predefinition of a propulsion speed and penetration depth of a soil working tool when working in soil.
Since, in particular, inexperienced operators such as often used as seasonal workers for harvesting generally experience great difficulty in setting the operating parameters to suitable values, especially since they mainly have to carry out other tasks during harvesting, such as steering, monitoring a transfer process, etc., in the past various systems have been proposed which propose suitable operating parameters to the operator so that the operator can set them or which automatically set the operating parameter. In this respect, reference is made, for example, to the prior art according to EP 0 928 554 A1 which describes a combine harvester with a driver assistance system which, after information about external harvesting conditions has been input, permits a selection of different target predefinitions on the basis of which ultimately proposals for operating parameters are provided. The target predefinitions are, in particular, the area output (throughput rate) and the losses which occur, wherein a weighting of both target predefinitions can also be performed on the basis of a two-dimensional curve in which the losses are plotted as a function of the throughput rate.
EP 2 042 019 A2 describes a driver assistance system which permits the operator to propose a change in an operating parameter of a combine harvesters and then displays an expected tendency for the working result.
EP 0 586 999 A2 presents another driver assistance system in which the operator can input operating parameters of a combine harvester and the weighting of target predefinitions, and the system then outputs expected working results.
In another system “Harvester assistant MDA 120” from Aclantec GmbH from 1995, the operator can select, for the purpose of calculating harvesting processes in advance, whether he predefines a loss or urgency of the harvesting. The system then outputs the respective throughput capacity or the speed for the harvesting process.
EP 2 132 974 A1 describes a field chopper in which the operator can input a target predefinition with respect to the compressibility of the harvested crop which is to be achieved. The operator assistance system checks, on the basis of the cutting length and the moisture of the harvested crop, whether the target predefinition can be achieved, and said operator assistance system displays other suitable operating parameters of the field chopper if the target predefinition does not appear to be achievable.
In the prior art according to EP 0 928 554 A1 there is therefore the possibility of selecting a result parameter (throughput rate and/or losses) which is to be optimized of the working result for an operation which is to be carried out. The operator assistance system then outputs the operating parameter (threshing unit and cleaning setting) to be set, but does not display to the operator which result parameter is actually being achieved. The inexperienced operator is presented here with the difficulty of selecting the result parameter which is to be optimized.
The operator assistance systems according to EP 2 042 019 A2 and EP 0 586 999 A2 leave it to the operator to input different settings of the operating parameter and display an expected tendency or an expected result. The optimization of the operating parameter is therefore not carried out automatically in these operator assistance systems by the operator assistance system but rather by the operator who has to try out a plurality of settings in order to find the optimum setting, which will not always lead to optimum settings.
The operator assistance system according to MDA 120 merely permits the value of the result parameter to be achieved (loss or working speed) to be input and outputs the operating parameters to be set for the combine harvester. Here, the operator must therefore input the value of the optimum result parameter himself, which exceeds the abilities of inexperienced operators.
Finally, EP 2 132 974 A1 knows only a single result parameter, that is specifically the compressibility of the harvested crop. However, many harvesting tasks in which it would be advantageous to optimize other result parameters are conceivable.
The present invention has the object of developing an operator assistance system for a field chopper which is further developed compared to the prior art and in which the abovementioned disadvantages do not occur, or occur to a reduced degree.
SUMMARY
The present invention is defined by the patent claims.
An operator assistance system for an agricultural machine which has at least one variable operating parameter which influences a plurality of different result parameters of the working result of the machine is equipped with an input device, a processor connected to the input device and a display device connected to the processor. The processor is programmed to receive, via the input device an input of a selectable result parameter, to be optimized, of the working result for an operation to be carried out, to calculate an optimized operating parameter on the basis of the input, and to output, on the display device, an expected value, associated with the optimized operating parameter, for the working result of the machine for the operation.
In other words, the operator can use the input device to select which result parameter is to be optimized from a plurality of different result parameters of the working result of the agricultural machine for an operation which is to be carried out. The processor of the operator assistance system then calculates, as a function of the selected result parameter, an optimized operating parameter and an expected value, associated with the optimized operating parameter, for the working result of the machine for the operation, and displays this value on the display device.
In this way, the operator is provided with the possibility of having different result parameters optimized in a virtual way before the start of the work or during the work, and to have the associated, expected values for the working result of the machine for the operation displayed on the display device. The operator can then discern which type of optimization has which effects on the value for the working result. As a result, an inexperienced operator can also easily select the most suitable type of optimization for the operation and arrive at an optimum operating parameter of the machine. This operating parameter can finally be set actually on the machine by the operator or directly by the operator assistance system.
In particular, the input device can permit an input of one or more or of all the following result parameters: (a) maximum efficiency of the operation, (b) maximum productivity of the operation and (c) maximum quality of the working result. In the case of the quality of the working result a possibility of inputting by the operator can be provided in order to define in a more detailed way what an optimum quality should look like. In the case of a field chopper with a harvested crop post-processing device (grain processor), it is possible to input, for example, whether the grains are only to be beaten or to be ground.
It is possible to display one or more or all of the following values for the working result of the machine for the operation on the display device: throughput rate of harvested crop, fuel consumption, working time and a measure of the quality of the harvested crop.
The input device preferably permits a selection of a relative weighting of the possible result parameters. In this context, the processor can be programmed to calculate, for a selected result parameter which comprises a plurality of the possible result parameters in a weighted measure, the operating parameter as a function of the relative weighting of the respective result parameters in that it permits greater deviations from an operating parameter which results in the case of a pure selection of a single result parameter, the smaller the weighting of the respective result parameter.
The processor is, in particular, programmed to display a graphic representation on the display device, in which representation different result parameters are assigned to defined points of a geometric body (in the case of three selectable result parameters, for example corners of a triangle), and a cursor serving to select the result parameter can be moved over the geometric body with the input device. The cursor can be moved by means of separate elements of the input device, for example pushbutton keys or a mouse or a ball, or the display device is embodied in a touch-sensitive fashion and then serves simultaneously as an input device.
The machine is, in particular, a field chopper which has an internal combustion engine, a harvesting attachment which has a drive connection to the internal combustion engine, a harvested crop feed device which is arranged downstream of the harvested crop collecting device, has a drive connection to the internal combustion engine and has pre-pressing rollers, a chopper device which is arranged downstream of the harvested crop feed device and has a drive connection to the internal combustion engine, a harvested crop post-processing device which is arranged downstream of the chopper device and has a drive connection to the internal combustion engine, and a transfer device, arranged downstream of the harvested crop post-processing device, for chopped harvested crop. The processor is programmed in this case to optimize one or more or all of the following operating parameters: the rotational speed of the internal combustion engine, the propulsion speed of the field chopper, the cutting length of the harvested crop and a degree of action (which influences the opening—“cracking”—of the grains in the harvested crop) of the harvested crop post-processing device.
The processor can be supplied with information relating to one or more or all of the following variables and can be programmed to take into account the variables during the optimization of the operating parameter and of the expected value for the working result: moisture content of harvested material to be collected, crop density of a field which is to be harvested and has a crop, type of plants of the field to be harvested, intended use of the crop, type of harvesting attachment, number of blades of a chopper drum, cutting height of the harvesting attachment, a predefinable lower and/or upper limit of the cutting length, weather history and any types of linear or non-linear relationships, which are theoretical or based on empirical values between the aforementioned variables and the resulting operating parameter and/or the expected value for the working result.
The operator assistance system can be implemented physically on a portable hand-held device which can be disconnected from the machine and connected to a bus system of the machine. However, it is also conceivable to implement the operator assistance system as an on-board computer of the machine.
BRIEF DESCRIPTION OF THE DRAWINGS
An exemplary embodiment of the invention which is described in more detail below is illustrated in the drawings, wherein the reference symbols must not be used to make a limiting interpretation of the patent claims. In the drawings:
FIG. 1 shows a schematic side view of a machine in the form of a self-propelling field chopper,
FIG. 2 shows a schematic illustration of an operator assistance system and of its connection to a communication system of the machine,
FIG. 3 shows a flowchart, according to which the operator assistance system proceeds during the processing of a work order,
FIG. 4 shows a flowchart according to which the operator assistance system proceeds during field mode, and
FIG. 5 shows an example of an image which is displayed by the display device of the operator assistance system during the optimization of the operating parameters of the machine.
DETAILED DESCRIPTION
FIG. 1 illustrates a self-propelling agricultural machine 10 of the type of a self-propelling field chopper in a schematic side view. The machine 10 is built on a frame 12 which is supported by front driven wheels 14 and steerable rear wheels 16 . The operator control of the machine 10 is carried out from a drivers cab 18 , from which a harvesting attachment 20 in the form of a rotary crop header for maize plants can be seen. Harvested crop, for example maize or the like, which is collected from the ground by means of the harvesting attachment 20 is fed via an input feeder with pre-pressing rollers 30 , 32 , arranged within an input housing on the front side of the machine 10 , to a chopper device 22 , in the form of a chopper drum, which is arranged underneath the drivers cab 18 and chops said harvested crop into small pieces, and, after it has passed through a harvested crop post-processing device 28 with cooperating processor rollers, passes it to a feed device 24 . The material leaves the harvesting machine 10 and passes to a transportation vehicle travelling alongside, by means of a transfer device 26 which can be rotated about an approximately vertical axis and has an adjustable inclination. A sensor 38 for sensing harvested crop properties 38 , in particular the moisture of the harvested crop, is mounted on the transfer device 26 .
An internal combustion engine 50 drives the chopper device 22 , the harvested crop post-processing device 28 and the feed device 24 via a mechanical drive train. Furthermore, said internal combustion engine 50 drives hydraulic pumps (not shown) which in turn supply hydraulic motors 52 , 54 for driving the harvesting attachment 20 and the pre-pressing rollers 30 , 32 . Reference is made in this respect to the disclosure in DE 10 2009 003 242 A1.
Directional information such as at the front, at the rear, on the side, at the bottom and at the top relate below to the forward direction V of the machine 10 which runs to the left in FIG. 1 .
Reference will now be made to FIG. 2 . The machine 10 comprises a first (machine) bus 40 which serves to transmit parameters which are relevant for controlling the machine 10 and can be embodied, for example, as a CAN bus. A control unit 42 , which serves to control control units 44 , 46 , 48 , is connected to this bus system. The control unit 44 controls, for example, operating data of the internal combustion engine 50 , such as the fuel supply and therefore the rotational speed of the internal combustion engine 50 , which serves to drive the machine 10 . The control unit 46 controls operating data of a hydraulic motor 52 , which serves to drive the harvesting attachment 20 , while the control unit 48 controls operating data of a hydraulic motor 54 which serves to drive the pre-pressing rollers 30 , 32 . The control unit 42 accordingly controls, inter alia, the rotational speeds of the internal combustion engine 50 and of the hydraulic motors 52 and 54 .
The machine 10 also comprises a second (communication) bus 56 which operates, in particular, according to the Standard ISO 11783. It serves, inter alia, to transmit position data and harvested crop data because the sensor 38 , a position-determining system 80 for acquiring signals from satellites of a navigation system (GPS, Galileo or Glonass) and a virtual terminal 60 are connected to it. A first communication interface 58 connects the second bus 56 to the first bus 40 . A second communication interface 62 connects the second bus 56 to an operator assistance system 64 which is embodied as a separate, portable device and which can be embodied as what is referred to as a tablet computer or smartphone and comprises a processor 68 , a memory device 70 , in which programs and data for the processor 68 are stored, a display device 66 , an input device 72 and a wireless, third communication interface 74 which serves for wireless communication with a computer 78 which is arranged at a remote point 76 . The third communication interface 74 can operate according to any desired protocol, in particular for mobile telephony (for example GSM) or data transmission (for example UMTS or LTE or WLAN) and can use intermediately connected relay stations to carry out, in particular Internet-protocol-based communication with the computer 78 . The second communication interface 62 can interact with the operator assistance system 64 via a wire-bound protocol (for example Ethernet) via a line or in a wireless fashion (for example WLAN or Bluetooth). The operator assistance system 64 can be arranged in a holder in the cab 18 which serves as a docking station and supplies the operator assistance system 64 with current and connects it to the second communication interface 62 .
FIG. 3 shows a flowchart according to which the processor 68 of the operator assistance system 64 proceeds when the latter is used for processing harvesting orders. After the start in step 100 , an operator can log onto the operator assistance system 64 in step 102 , in particular after inputting an identity reference and a password. In the following step 104 the operator can have the orders lined up for the respective day (and if appropriate following days) displayed to him on the display device 66 , which orders the operator assistance system 64 receives from the computer 78 via the third communication interface 74 . The computer 78 can be located, for example, in the office of a contractor and can be supplied with the orders by said contractor, or the orders are input by clients (for example farmers) into an Internet-based system which runs on the computer 78 .
If the operator then wishes to carry out an order, he causes the operator assistance system 64 to go to the step 105 by means of a suitable input into the input device 72 . In this context, preparations for the harvesting are made, for example, the machine is refueled, if appropriate cleaned, and a harvesting attachment 20 which is suitable for the order is hitched. Grinding processes for sharpening the chopper blades of the chopper device 22 and/or setting the counter blade distance can also be carried out. For this purpose, corresponding instructions can be issued to the operator on the display device 66 , which operator then carries out the necessary steps himself even though those steps which do not require any manual action by the operator, such as the grinding process or the counter blade setting, can also be brought about by the operator assistance system 64 , which then correspondingly activates the control unit 42 .
In the following step 106 , the operator is navigated to the field to be harvested in that, for example, a map is displayed on the display device 66 according to which the operator drives the machine 10 to the field. The position data can be made available here by the position-determining system 80 via the second communication interface 62 , or by an internal position-determining system of the operator assistance system 64 .
After the arrival at the field, the operator can cause the operator assistance system 64 to go to the step 108 , i.e. to commence the field operation, by means of a suitable input into the operator input device 72 . This step 108 is explained further below on the basis of FIG. 4 . The end of the field operation (step 108 ) is followed by the step 110 in which the operator can input that his orders for the day are ended, after which the logging off takes place in step 112 . Otherwise, the step 104 follows again.
In steps 102 , 104 , 105 , 106 , 108 , 110 and 112 , different contents, corresponding to the respective step, are respectively displayed to the operator on the display device 66 .
The step 108 is now described in detail on the basis of FIG. 4 . Firstly, the step 114 is carried out in which preparations for the harvesting work are carried out. In this context, the operator assistance system 64 can display on the display device 66 necessary measures which the operator is to carry out. Furthermore, transport protection devices are to be removed from the harvesting attachment 20 and the (multi-part) harvesting attachment 20 is to be pivoted into a harvesting position.
In step 116 , a working mode of the machine is then selected. In response to corresponding instructions on the display device 66 of the operator assistance system 64 , the operator can for this purpose switch over to field mode a safety switch which serves to switch over between road mode and field mode, and the operator can then close a clutch in the drive train between the internal combustion engine 50 on the one hand, and the chopper device 22 , the feed device 24 and the harvested crop post-processing device 28 , on the other, in order to set the chopper device 22 in motion. The machine 10 is then ready for harvesting, and this is the case because the hydraulic motors 52 , 54 are also rotating.
In the following step 118 , a number of settings of the machine 10 are defined in order to permit optimum operation. The step 118 could also be carried out before the step 114 or 116 and can also be repeated during the harvesting which follows in step 120 . During the execution of the step 118 , the image which is displayed in FIG. 5 is displayed on the display device 66 .
The display device 66 displays that currently a setting of the machine 10 is to be optimized (field 200 ). Furthermore, in a field 202 respectively currently set operating parameters of the machine 10 are displayed, specifically the cutting length l, which is 5 mm, the distance d between the process rollers of the harvested crop post-processing device 28 , which is 1.5 mm, the rotational speed of the internal combustion engine 50 , which is 1850/min, and the preselected propulsion speed v, which is 3 km/h. A text 204 which is arranged above the latter clarifies that the settings are the currently selected ones.
In a further field 206 , values for the working result of the machine 10 for the operation, which are expected given the currently selected settings, are displayed. Here, the throughput rate, which is 200 t/h, the fuel consumption of 1.7 l/t harvested crop, the expected harvesting time of 12 hours and a gradation of the quality of the harvested crop, which is displayed here as a mark of 2, are displayed.
In a further field 208 , a geometric body 210 in the form of a triangle is displayed in which defined points, which are here the corners, are assigned different optimizable result parameters of the working process. The productivity is assigned to a (left-hand lower) corner 214 of the body 210 , the quality is assigned to a (right-hand lower) corner 216 of the body 210 , and the efficiency is assigned to a (middle upper) corner 218 . A cursor 212 can be moved over the body 210 by means of the input device 72 , which can also be embodied as a touch-sensitive display device 66 . If the cursor 212 is in the displayed position, the processor 68 will optimize the efficiency of the operation, i.e. find operating parameters at which the harvesting process is carried out with minimum fuel consumption. If the operator moves the cursor 212 into the corner 214 which is assigned to the productivity, the processor 68 will optimize the productivity of the operation, i.e. find operating parameters at which the harvesting process is carried out with minimum time and the highest possible throughput rate. If the operator moves the cursor 212 into the corner 216 which is assigned to the quality, the processor 68 will optimize the quality of the working result, i.e. find operating parameters at which the harvesting process is carried out with the best possible result in terms of harvesting quality. The cursor 212 can also be moved into any desired intermediate position, for example in the centre of the triangle, at which a compromise is sought between the three abovementioned result parameters. The cursor 212 can also be placed at a position at the edge of the triangle with the result that a compromise is then determined between two result parameters. The nearer the cursor is positioned to one of the corners 214 , 216 , 218 , the higher the weighting with which the associated result parameter is included in the selection of the operating parameters.
In a further field 220 , the display device 66 displays which values are to be expected for the working result of the machine 10 for the operation if operating parameters calculated according to the current position of the cursor were to be set. FIG. 5 illustrates the throughput rate, which is 250 t/h, a fuel consumption of 1.5 l/t harvested crop, an expected harvesting time of 9 hours, and a gradation of the quality of the harvested crop, which is displayed here as a mark between 3 and 4. It would be conceivable to highlight changes compared to the current values (field 206 ) by means of the colour (green for better, red for worse) and/or arrows. Furthermore, the operating parameters calculated on the basis of the position of the cursor 212 could also be displayed on the right next to the field 202 , but this has not been shown in FIG. 5 for the sake of clarity. A field 222 shows that in field 220 the values are shown which are expected if the type of optimization which is selected with the cursor 212 is selected and serves to determine the operating parameters.
The operator can therefore try out different settings of the cursor 212 within the body 210 and determine in what way the selected optimization acts on the values for the working result. The operator can therefore very easily determine which position of the cursor 212 , and therefore which optimization, appears most appropriate to him. The operator also learns the relationships between the type of optimization and the expected values for the working result, with the result that a learning effect for inexperienced, and even for experienced, operators occurs, in particular at the start of a harvesting season. The operator can, if appropriate, also compare a setting which has been predefined by a client with an optimized setting and propose to the client that the predefinition or setting be changed. For this purpose, the operator can show the operator assistance system 64 to the client in situ, or can transmit the contents of the display device 66 to the client via the third communication interface 74 . Furthermore, it would also be conceivable that the optimization which is to be used is already predefined with the order (cf. step 104 ) and cannot be changed by the operator. In this case, if appropriate only an operator with corresponding authorization would be able to overwrite the predefined optimization.
The processor 68 then outputs the calculated operating parameters (field 202 ), in particular in response to a confirmation input by the operator, so that the operator can set said operating parameters at the machine 10 , or the processor uses the second communication interface 62 and the first communication interface 58 to make the control unit 42 set the calculated operating parameters automatically.
The step 118 can be repeated during the harvesting, either in response to an operator input or if the processor 68 determines that one or more of the values of the working result (cf. field 206 ) is currently worse, by more than a predefinable or predefined threshold value, than a value which can be achieved given suitable optimization (i.e. the position of the cursor 212 ) should be. The operator is provided in this case with a corresponding warning message and the window according to FIG. 5 opens.
The processor 68 is supported by a large amount of data in making the calculations for the step 118 , i.e. the determination of optimized operating parameters and associated values for the working result on the basis of the position of the cursor 212 . On the basis of the order (step 104 ), the processor is provided with information relating to the position of the field and of the crop (type of plant, type of soil, weather data of the growth period this year, best-in-class information, yield data and associated machine settings during previous harvests, in particular including associated historic weather information, empirical reports, expert knowledge) which the processor can obtain from the computer 78 or from some other suitable source, for example via the Internet. The expected throughput rates and harvested crop moisture levels are thus already known even though they can still be updated or corrected during the harvesting by means of the sensor 38 (which can be embodied as a close-range infrared sensor in order to determine the harvested crop moisture level) and a sensor (not shown) for detecting the gap between the upper and lower pre-pressing rollers or some other sensor which detects the throughput rate. The cutting height of the harvesting attachment 20 is also taken into account since it influences the throughput rate through the machine 10 . The cutting height can be predefined by the order (step 104 ) or can be controlled by the operator or is only defined during the harvesting on the basis of a proportion of soiling in the harvested crop (for example particles of soil adhering to the plants) detected with the sensor 38 .
During the evaluation of the quality, the purpose of use of the harvested crop is taken into account, which use can already be contained in the order (step 104 ) or can be input by the operator. It is therefore possible in the case of the use as feed for animals, that the opening of grains by the harvested crop post-processing device 28 , in order to utilize their energy content, is particularly important for the quality. Given use in a biogas system, the avoidance of excessively long cutting lengths may tend to influence the quality. The importance of various parameters for the quality could also be displayed by sliding controllers 224 on the display device 66 and set by means of the input device 72 , which may be embodied, in particular, as a touch-sensitive display device 66 . The upper sliding controller could therefore represent the importance of the opening of the grains and the lower sliding controller could represent the avoidance of excessively large cutting lengths.
If it is also to be possible to optimize a further result parameter of the working process, such as for example the generation of noise during the harvesting process, the body 210 could also be embodied as a rectangle. The fourth corner is then assigned to the fourth result parameter of the working process.
Finally, the processor 68 is also provided with data relating to the type of machine 10 , in particular relating to the number of blades distributed around the circumference of the chopper device 22 , the type and the width of the harvesting attachment 20 and, preferably, also details of the characteristic curves of the internal combustion engine 50 , said number of blades being required for the control of the cutting length and for the calculation of the energy requirement of the chopper device 22 . In addition, an upper and/or a lower limit of the cutting length can be predefined.
During the optimization of the operating parameters as a function of the selected working result which is to be optimized, the processor 68 uses a database which is based on empirical values, previous or simultaneously occurring trials and harvesting processes (which have been carried out with the same machine 10 and/or other machines and with the current operator and/or other operators) and expert knowledge. In each case the energy requirement of the chopper device 22 , of the pre-pressing rollers 30 , 32 , of the harvesting attachment 20 (if appropriate driven at a speed which is dependent on the propulsion speed V and/or the cutting length and/or the throughput rate) and of the harvested crop post-processing device 28 is respectively taken into account, and nevertheless efforts are made to achieve usable values for the quality even if optimization of the efficiency and/or productivity is selected. The influence of the cutting length on the grains is also taken into account because in the case of relatively short cutting lengths more grains will already be cut into (and therefore do not need to be opened by the harvested crop post-processing device 28 ) than in the case of relatively large cutting lengths.
If pure optimization of the efficiency is selected, the processor 68 will actuate on the characteristic curve of the internal combustion engine 50 a working point of said internal combustion engine 50 which is as favourable as possible in terms of consumption, and will derive the remaining operating parameters therefrom, while maintaining acceptable quality. Analogously, the processor 68 will, if pure optimization of the productivity is selected, set the working point of the internal combustion engine 50 to maximum performance and derive the remaining operating parameters therefrom while maintaining acceptable quality. Given optimization of the quality, the processor 68 will predominantly optimize the cutting length and the harvested crop processing device 28 and derive the other operating parameters therefrom. If now a result parameter is selected which comprises one or more of the possible result parameters to a weighted degree, i.e. the cursor 212 is placed at a point on the body 210 which does not correspond to one of the corners, the processor 68 will calculate the operating parameters as a function of the relative weighting of the respective result parameters by permitting greater deviations from an operating parameter which occurs in the case of a pure selection of a single result parameter the smaller the weighting of the respective result parameter.
It is also to be noted that in the illustration according to FIG. 5 some text or all of the text could be replaced by symbols.
In the step 120 which follows step 118 the actual harvesting process is then carried out.
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An operator assistance system for an agricultural machine which has at least one variable operating parameter which influences a plurality of different result parameters of the working result of the machine is equipped with an input device, a processor and a display device. The processor is programmed to receive, via the input device an input of a selectable result parameter, to be optimized, of the working result for an operation to be carried out, to calculate an optimized operating parameter on the basis of the input, and to output, on the display device, an expected value, associated with the optimized operating parameter, for the working result of the machine for the operation.
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FIELD OF INVENTION
This invention relates generally to imaging of envelopes and, more specifically, to an envelope transport structure that minimizes wrinkling of envelopes during an imaging process.
BACKGROUND OF THE INVENTION
In electrostatic or electrophotographic image forming apparatus, such as monochrome and color laser printers and photocopiers, it is common to fuse a loose toner image by passing the imaged media through a fusing nip. The fusing nip is typically formed from a first fusing roller urged against a second fusing roller to create a pressurized nip through which the media passes. One or both of the fusing rollers are typically heated to increase the temperature within the nip.
In those imaging systems utilizing a fusing nip as described above, wrinkling of envelopes within the fusing nip has been a continuing problem. Previous attempts to reduce envelope wrinkling have involved relieving the pressure on the envelopes at various points in the fusing operation. An example of this approach is found in U.S. Pat. No. 5,268,726 to Oleksa et al.
It is also known to utilize individual support ribs or fingers within a paper path to reduce friction between the moving media and the surfaces of the paper path. The support fingers also serve to lessen pre-heating of the media due to heat transfer from the support surfaces of the paper path. Additionally, to prevent any one point on the image from being in extended continuous contact with a single support finger, the fingers may be angled with respect to the direction of travel of the media. This helps to avoid uneven heating of the media and image that can cause print defects and variations in the gloss of the printed image.
It is also known to angle the support fingers away from the center line of the paper path to prevent the leading corners of a media sheet from catching the sides of the fingers and pushing the media laterally to either side of the paper path. Should the media be pushed laterally prior to the fusing nip, wrinkling can occur and, in a worst case scenario, a paper jam may be created. An example of utilizing support fingers that are canted away from the center line of the paper path is found in U.S. Pat. No. 5,870,661 entitled APPARATUS AND METHOD FOR CONTROLLING MEDIA TEMPERATURE IN AN IMAGING APPARATUS and assigned to the assignee of the present application.
It has been found that support fingers that are canted away from the center line of the paper path have a disadvantage when printing envelopes. When the addressee side of an envelope is printed and the envelope travels along the paper path, the flap of the envelope on the opposite side hangs down at an angle that is canted away from the center line of the paper path, similar to the angle of the canted support fingers. As the envelope travels over the support fingers, the flap may catch the side of a finger and cause the envelope to be pushed laterally to the side or opened while moving through the fuser. This can cause severe wrinkling, print defects, and/or a media jam.
The present invention seeks to overcome the disadvantages of previous implementations of canted support fingers by changing the angle of the support fingers directly under the envelope to prevent the envelope flap from catching the side of a support finger. More specifically, the support fingers directly under the envelope in a central area are canted toward the center line of the paper path to allow the envelope flap to pass over the support fingers at an angle oblique to the angle of the support fingers. The support fingers on either side of the area over which the envelope passes are canted away from the center line of the paper path to prevent the corners of full width media from catching the surface of a rib. Accordingly, a reduction in wrinkling of both envelopes and full width media is achieved with a simple, low-cost structure.
SUMMARY OF THE INVENTION
It is an aspect of the present invention to provide a media transport unit including an envelope transport structure for supporting an envelope traveling along a media path in an imaging apparatus.
It is another aspect of the present invention that the media transport unit utilizes a plurality of media supports grouped in a first lateral portion, a second lateral portion, and a center portion between the first and second lateral portions.
It is a feature of the present invention that the center portion of media supports are canted toward the center line of the media path to allow an envelope flap to travel over the media supports without being urged laterally by a support.
It is another feature of the present invention that the media supports in the first and second lateral portions are canted away from the center line of the media path to prevent the leading corners of a full width media sheet from catching a media support and pushing the media laterally.
It is an advantage of the present invention that the envelope transport structure allows the use of individual media supports in the paper path while also preventing media and envelope wrinkling.
It is another advantage of the present invention that the envelope transport structure comprises a simple and compact design that utilizes low-cost components.
Still other aspects, features, and advantages of the present invention will become apparent to those skilled in this art from the following description, wherein there is shown and described a preferred embodiment of this invention, simply by way of illustration of one of the modes best suited to carry out the invention. As it will be realized, the invention is capable of other different embodiments and its several details are capable of modifications in various, obvious aspects, all without departing from the invention. Accordingly, the drawings and descriptions will be regarded as illustrative in nature and not as restrictive. And now for a brief description of the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of an electrophotographic printing apparatus showing the media path through the printer.
FIG. 2 is a schematic perspective view of a pair of fusing rollers forming a fusing nip and an envelope traveling along the media path and approaching an envelope transport structure upstream from the fusing nip.
FIG. 3 is a schematic top view of the envelope transport structure showing the positioning and orientation of the individual media supports and an envelope approaching the supports.
FIG. 4 is an enlarged schematic top view of the envelope traveling over the media supports.
Reference will now be made in detail to the present preferred embodiment of the invention, an example of which is illustrated in the accompanying drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 is a schematic illustration of the media path 12 in an electrostatic or electrophotographic image forming apparatus 10 that utilizes the envelope transport structure of the present invention. The following description of a preferred embodiment of the invention refers to its use in an electrostatic printing apparatus. It will be appreciated, however, that the apparatus of the present invention may be used with other types of electrostatic imaging apparatus, such as photocopiers, and with other types of imaging apparatus, such as aqueous ink jet printers. Accordingly, the following description will be regarded as merely illustrative of one embodiment of the present invention.
With continued reference to FIG. 1 a receiving substrate 11 , such as a sheet of paper or an envelope, is picked from a media tray 14 by a conventional pick roller mechanism (not shown). The receiving substrate 11 travels along the media path 12 and through an imaging station 16 which deposits a toner image on the receiving substrate. An example of an electrostatic imaging station is found in U.S. Pat. No. 5,576,824 (the '824 patent) entitled FIVE CYCLE IMAGE ON IMAGE PRINTING ARCHITECTURE. The '824 patent is hereby incorporated by reference in pertinent part.
After passing through the imaging station 16 , the receiving substrate 11 travels over a media transport unit 18 that includes an envelope transport structure, described in more detail below. The media transport unit 18 is positioned in a pre-nip portion of the media path 12 upstream from the fusing nip 20 . The fusing nip 20 is created by urging together fusing rollers 22 and 24 . In the fusing nip 20 , the toner image is permanently affixed to the receiving substrate 11 . After passing through the fusing nip 20 , the receiving substrate is transported out of the printer 10 for retrieval by a user.
With reference now to FIGS. 2 and 3, the arrangement and operation of the media transport unit 18 and envelope transport structure 19 of the present invention will now be described in more detail. The media transport unit 18 includes a plurality of media supports for supporting a sheet of media or an envelope as the sheet or envelope approaches the fusing nip 20 . In the preferred embodiment, the media supports comprise elongated, spaced apart support fingers indicated by the even numbered reference numerals 30 - 52 , with each finger including a first end and a second end indicated by a prime and double prime, respectively, of the corresponding reference numeral. For example, finger 30 includes a first end 30 ′ and a second end 30 ″.
The support fingers are arranged in a first lateral portion 60 comprising support fingers 30 , 32 , 34 , and 36 , and a second lateral portion 62 comprising support fingers 46 , 48 , 50 , and 52 . Between the first lateral portion 60 and the second lateral portion 62 is a center portion 64 comprising support fingers 38 , 40 , 42 , and 44 . As explained below, the center portion 64 of support fingers corresponds to the envelope transport structure 19 . It will be appreciated that any suitable number of support fingers may be utilized in any of the first lateral, second lateral and center portions.
With continued reference to FIG. 3, the media path 12 includes a center line indicated by the dotted line 15 . Sheets of media and envelopes travel in the direction of action arrow A along the media path 12 and are generally centered over the center line 15 . As shown in FIG. 3, the support fingers in the first and second lateral portions 60 , 62 are canted away from the media path center line 15 . Preferably, each of the support fingers in the first and second lateral portions 60 , 62 form an angle with the center line 15 of between about 3 degrees and about 45 degrees, and more preferably between about 10 degrees and about 20 degrees. As explained above, this ensures that the edges of a media sheet (not shown) do not contact the side of a support finger, which can urge the media sheet laterally out of alignment as it travels through the fusing nip 20 and potentially cause media wrinkling and/or a media jam.
In an important aspect of the present invention, the support fingers 38 - 44 in the center portion 64 /envelope transport structure 19 are each canted toward the media path center line 15 . Preferably, each of the support fingers 38 - 44 form an angle with the center line 15 of between about 3 degrees and about 45 degrees, and more preferably between about 10 degrees and about 20 degrees. With reference now to FIG. 4, as an envelope 28 travels over the envelope transport structure 19 with the envelope flap 29 on the underside of the envelope, the flap rides over the top of the support fingers 38 and 40 . The flap 29 and support finger 38 initially create an acute angle 41 that allows the flap to ride over the top of the support finger.
With reference now to FIG. 3, the long edges 31 , 32 of the envelope 28 travel between the first lateral portion 60 and the center portion 64 of support fingers, and between the second lateral portion 62 and center portion 64 of support fingers, respectively. In the preferred embodiment, the distance between the first end 38 ′ of support finger 38 and the first end 44 ′ of support finger 44 is less than the length of the short edge 35 of the envelope 28 . Additionally, the distance between the first end 36 ′ of support finger 36 and the first end 46 ′ of support finger 46 is greater than the length of the short edge 35 of the envelope 28 . It will be appreciated that standard letter envelopes have a long edge length of between about 9.5 inches (241 mm.) and 9.8 inches (250 mm.), and a short edge length of about 4.0 inches (102 mm).
In the preferred embodiment, the support fingers 38 and 40 on a first side of the center line 15 are substantially parallel. Similarly, the support fingers 42 and 44 on the opposite side of the center line 15 are substantially parallel.
While the invention has been described above with references to specific embodiments thereof, it is apparent that many changes, modifications and variations in the materials, arrangements of parts and steps can be made without departing from the inventive concept disclosed herein. Accordingly, the spirit and broad scope of the appended claims is intended to embrace the use of these other inks and all other changes, modifications and variations that may occur to one of skill in the art upon a reading of the disclosure. All patent applications and patents cited herein are incorporated by reference in their entirety.
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A media transport unit includes an envelope transport structure that utilizes support fingers directly under the envelope. The support fingers are canted toward the center line of the paper path. The envelope flap passes over the support fingers at an angle that prevents the envelope flap from catching a support finger and potentially causing envelope wrinkling or a jam. The support fingers on either side of the area over which the envelope passes are canted away from the center line of the paper path to prevent the edges of full width media from catching the surface of a support finger.
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BACKGROUND OF THE INVENTION
The present invention relates to a method of inhibiting corrosion of ferrous metals in oil and gas-field applications, in particular in situations where they may come into contact with the natural environment e.g. by discharge of produced water, and to a method of inhibiting corrosion using these materials. In one aspect, the invention relates to a method which employs a low toxicity corrosion inhibitor.
In order to preserve metals, and particularly ferrous metals, in contact with corrosive liquids in gas- and oil-field applications, corrosion inhibitors are added to many systems, e.g. cooling systems, refinery units, pipelines, steam generators and oil production units, formation treating fluids (e.g. acidizing fluids). A variety of corrosion inhibitors are known. For example, GB-A-2009133 describes the use of a composition which comprises an aminecarboxylic acid such as dodecylamine propionic acid, and a nitrogen-containing compound containing an organic hydrophobic group, such as N-(3-octoxypropyl) propylenediamine or a cyclic nitrogen containing compound such a morpholine, cyclohexylamine or an imidazoline.
U.S. Pat. No. 3,445,441 describes amino-amido polymers which are the reaction product of a polyamine and an acrylate-type compound, which polymers may be cross-linked. The polymers have several uses including use as corrosion inhibitors.
Although corrosion inhibitors of many types are known, the materials which have been found most effective in practice have the disadvantage of toxicity to the environment. Toxicity to the marine or freshwater environment is of particular concern. In gas and oil field applications, much work is done off shore or on the coast. If a corrosion inhibitor enters the sea or a stretch of fresh water, then, even at relatively low concentrations, the corrosion inhibitor can kill microorganisms, fish, shrimp, or other aquatic life, causing an imbalance in the environment. Attempts have therefore been made to identify materials which are successful corrosion inhibitors but at the same time are less toxic to the environment than known inhibitors.
U.S. Pat. Nos. 5,300,235 and 5,322,630 discloses dialkyl/fatty/carboxylic acid adducts for use in oil field operations and which exhibit low toxicity. The adducts of fatty amine derivative, e.g. a fatty imidazoline, and an unsaturated acid, and in which the product contains preferably no primary amino groups and, more preferably no secondary groups, has a lower toxicity to the environment (referred to as ecotoxicity), than many known corrosion inhibitors.
SUMMARY OF THE INVENTION
As mentioned above, the method of the present invention employs a corrosion inhibitor which exhibits low toxicity and improved corrosion inhibition. The corrosion inhibitor comprises two components:
(A) mercaptocarboxylic acid having from 2 to 6 carbon atoms (straight chain or branched), and (B) a dialkyl/fatty acid/carboxylic acid adduct having the following formula 1: ##STR1## where
R is a C 6-20 hydrocarbon;
R 4 is an alkyl group having from 2 to 6 carbon atoms; and
n is an integer of 1 to 6;
Y is one of the following:
(a) --NR 1 -- where n is 1, 2, or 3;
(b) --CO--NH-- where n is an integer 1-6;
(c) ##STR2## in which X is an alkalene group of 2 to 6 carbon atoms and n is an integer of 1 to 6;
R 1 is independently H, or -- (CH 2 ) p ! COOH or a C 6-20 hydrocarbon, or a C 6-20 hydrocarbon carbonyl;
R 2 is H, or (CH 2 ) p ! COOH or a C 6-20 hydrocarbon or C 6-20 hydrocarbonyl, where R1 is the same or different from R 2 , and p is an integer ranging from 1 to 4,
where the compound contains at least one (CH 2 ) p COOH group or salt thereof and no primary amines.
As used herein, term C 6-20 hydrocarbon carbonyl means a group having the following formula: ##STR3## where R 3 is a C 5 -C 19 hydrocarbon.
The mercaptocarboxylic acid component preferably mercaptoacetic acid and beta-mercaptopropionic acid, with the former being most preferred. These acids are water soluble and available commercially in various concentrations in water. From 1 to 20 wt. % solutions of mercaptoacetic acid are preferred for use in the method of the present invention, with 2 to 10 wt. % solutions being most preferred.
The Component B adduct is prepared by (a) reacting a fatty amine with (an unsaturated) carboxylic acid or (b) reacting a fatty acid with an amine to form an amide or imidazoline and then reacting this product with an unsaturated carboxylic acid. The final compound contains no primary amines and preferably no secondary amines.
As described in U.S. Pat. No. 5,300,235, the component (B) adducts have favorable ecotoxicity levels in marine or freshwater environments. The ecotoxicity decreases with increasing substitutions on the N atoms present i.e. it appears that tertiary groups are less toxic than secondary groups which are in turn less toxic tan primary groups. Preferably, therefore, each amine group is secondary or tertiary, most preferably tertiary.
Use in a marine or freshwater environment is intended to mean use in an environment in which the corrosion inhibitor in normal usage may come into contact with an area of seawater or fresh water or land.
Components (A) and (B) may be introduced separately in the liquid, but preferably are used in a formulation. The weight ratio (actives) of components (A) and (B) may range from 1:100 to 100:1, preferably from 1:5 to 5:1, and most preferably from 2:1 to 1:2. The concentration of the two component corrosion inhibitors in the liquid may range from 1 to 200 ppm, preferably from 1 to 100 ppm, and most preferably 5 to 50 ppm.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a plot comparing corrosion inhibition of the two component corrosion inhibitor with each component separately.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Each of the components used in the method of the present invention are described below:
Component (A)
As mentioned above water soluble mercaptocarboxylic acid having from 2 to 6 carbon atoms is commercially available. For example, 96 to 100 wt. % of the mercaptoacetic acid can be obtained from Elf Atochem North America under the trade designation of thioglycolic acid.
Component (B)
Component B, have the general formula I above, has two preferred embodiments: Formula IA and Formula IB described below.
The corrosion inhibitor of FORMULA IA where Y is--NR 1 --and R 2 =R 1 may be represented as follows: ##STR4## where, R 4 and n are as described in FORMULA I, and R 1 is H, -- (CH 2 ) p ! COOH, or C 6-20 hydrocarbon wherein the compound contains at least one (CH 2 ) p COOH or salt thereof and no primary amines.
The hydrocarbon group or groups of from 6 to 20 carbon atoms of FORMULA IA and IB (described below) may be straight or branched, saturated or unsaturated, and may be aliphatic or may contain one or more aromatic groups. Preferably the hydrocarbon group is straight chain aliphatic and is saturated, optionally with up to 20% of the chains being unsaturated. Preferably the hydrocarbon contains 12 to 20 carbon atoms, more preferably 16 to 20 carbon atoms. It is preferred that R is the hydrocarbon residue of a naturally occurring fatty acid, which is optionally hydrogenated e.g. the residue of caproic, caprylic, capric, lauric, myristic, palmitic, stearic, palmitoleic, oleic, linoleic or linolenic acid. The amines used in the present invention can conveniently be formed by the reaction of a fatty amine and an unsaturated acid in which case R corresponds to the fatty part of the amine. Fatty amines are readily available in which the fatty portion is a mixture of hydrocarbon groups. For example, the amine, diamine or triamine of hydrocarbon residue of tall oil, coconut oil or tallow oil are readily available.
When R 1 of FORMULA IA is a hydrocarbon it may be the residue of a naturally occurring fatty acid as described above for R, or it may be an artificially synthesized hydrocarbon. If R 1 is a hydrocarbon, it is preferably a residue of a naturally occurring fatty acid.
However, R 1 is preferably H or -- (CH 2 ) p !COOH, and most preferably -- (CH 2 ) p ! COOH. The alkyl group may be straight chain or branched. Conveniently the compound of FORMULA IA is produced by adding acrylic acid to a fatty amine, which results in a compound in which R 1 is --CH 2 --CH 2 COOH.
The C 2-6 alkyl group R 4 linking the fatty hydrocarbon and amino groups in the compound of FORMULA IA may be straight or branched. Conveniently it is a propylene or hexylene group since the starting amines are either available commercially or can be readily synthesized.
The amine of FORMULA IA may contain 1, 2, 3 or 4 amino groups. It is preferred for it to contain 2 amino groups since the tests carried out so far suggest that such compounds provide the optimum in terms of ease of production and handling, good corrosion inhibition properties and low ecotoxicity. Diamine compounds correspond to compounds of the FORMULA IA in which n is 1.
The amine may be present in the form of a salt, for example an alkali metal salt such as sodium or potassium, an alkaline earth metal salt such as magnesium or calcium, or an ammonium salt.
Preferred amines of FORMULA IA include those of FORMULA IIA: ##STR5## in which tallow indicates the reside of an acid found in beef tallow, and each R 1 is independently (a) H or (b) --R 4 COOH and salts thereof. Preferably R 1 is -- (CH 2 ) p !COOH, conveniently CH 2 CH 2 COOH. Thus a particularly preferred compound is of FORMULA IIIA; ##STR6##
Compounds of the FORMULA IA in which R1 is H, a C6-20 hydrocarbon or --(CH 2 ) p COOH may conveniently be produced by reacting an amine of the FORMULA IVA ##STR7## where R and n are as defined above and R 1 is H or C 6-20 hydrocarbon, with an acid of FORMULA VA
CH.sub.2 ═CR'--(CHR').sub.m --COZ tm (VA)
in which m is 0, 1 or 2, each R' is hydrogen or when m is 1, R' may be methyl, and Z is OH or alkyl. To produce a compound in which R 1 is H, a C 6-20 hydrocarbon, or -- (CH 2 ) p !COOH, the amine of FORMULA IVA may be reacted with chloro acid or FORMULA VIA
C1-- (CH.sub.2).sub.p !COOH (VIA)
The molar ratio of acid of FORMULA VA or VIA to amine of FORMULA IVA should be chosen to ensure the desired level of substitution takes place. Typically therefore to avoid the presence of primary amine groups the molar ratio will be at least 2:1, more preferably 3:1, more preferably 4:1 when the starting amine is a triamine and so on. A slight molar excess (e.g. about 10%) of acid is generally used, e.g. for a dismine the acid may be used in a molar ratio of about 3.3:1.
Preferably the compounds of FORMULA IA are made by reacting the compounds of FORMULA IVA and VA since if the chloro acid is used as a starting material, it is generally difficult to remove all the chlorine-containing material from the product, and chlorine-containing compounds can damage the environment. Preferably the acid is acrylic acid.
The reaction of acrylic acid with the primary amine yields predominantly the B-amine propionic acid derivative directly. Depending on the distance between the amino group and the acid group, the product may be a cyclic internal salt.
The reaction may be carried out by heating a solution of the amine in a suitable solvent, conveniently an alcohol such as isobutanol or isopropanol or water. The required quantity of the acid is gradually introduced. The temperature at which the reaction is carried out is generally from 50° C. up to the reflux temperature of the reaction mixture, typically 60° to 100° C.
The compounds tend not to be soluble in water or brine, but are dispersible to some extent in water.
The corrosion inhibitor of FORMULA IB may be represented as follows: ##STR8## Y' is the group represented in (b) and (c) of FORMULA I; and where n, R, R 1 , R 2 and R 4 are described in FORMULA I and wherein the compound contains at least one (CH 2 ) p COOH group and no primary amines. R 2 is preferably H, or the carboxylic acid group, or the carbonyl group.
The amine derivative (Y 1 ) may contain a heterocyclic group of the formula ##STR9##
In this formula X may be an alkylene group of 2 to 6 carbon atoms e.g. ethylene or propylene. When X is ethylene, the heterocyclic group is imidazoline. X may be straight chain or may be branched, such that the heterocyclic ring is substituted by an alkyl of up to 4 carbon atoms.
The derivative of FORMULA IB may contain one or more amido groups.
R 1 in the derivative of FORMULA IB is preferably H or a carboxylic acid group of 2 to 5 carbon atoms. Tests currently appear to indicate tertiary groups are less toxic than secondary amino groups, which are in turn less toxic than primary amino groups. If a heterocyclic ring is present the nitrogen atoms in the ring re considered tertiary. In view of the favorable results shown for N-substitution it is preferred that each R1 is a carboxylic acid group. Conveniently, R 1 is derived from acrylic acid, in which case R1 in FORMULA IB is --CH 2 CH 2 COOH. R 2 is similarly conveniently derived from acrylic acid and is therefore preferably --CH 2 CH 2 COOH or H.
The derivative may optionally contain 1 or more alkyl amino groups between the group Y 1 and the group R 2 . Each amino group may be optionally substituted by an acid group or a C 6-20 hydrocarbon or C 6-20 hydrocarbon-carbonyl. Preferably the derivative contains 2 or 3 amino groups i.e. n is 2 or 3.
The C 2-6 alkyl group linking the group Y 1 and each amino group may be a straight or branched alkyl group. Conveniently, it is an ethylene, propylene or hexylene group since the starting amines to produce such compounds are either available commercially or can be readily synthesized.
The derivative may be present in the form of a salt, for example an alkali metal salt such as sodium or potassium, an alkaline earth metal salt such as magnesium or calcium, or an ammonium sale.
Particularly preferred derivatives are those of FORMULA (IIB). ##STR10## where each R 1 is H or (CH 2 ) 2 COOH.
Compounds of the FORMULA IB may conveniently be produced by reacting an amine or a heterocyclic compound with an unsaturated acid. This may be represented as reacting a compound of the FORMULA (IIIB): ##STR11## in which R, R 4 Y and n are as defined above and each R 1 ' is independently H, C 6-20 hydrocarbon, or C 6-20 hydrocarbon-carbonyl with an acid of the FORMULA (IVB):
CH.sub.2 ═CR'--(CHR').sub.m --COZ (IVB)
in which m is 0, 1 or 2, each R' is hydrogen or, when m is 1, R' may be methyl, and Z is OH or alkoxy. If Z is alkoxy the product is hydrolysed to produce the corresponding acid.
The salt, if desired, may be formed using processes known in the art.
The amine derivatives may also be produced by reacting a compound of the FORMULA IIIB as defined above with an acid of the FORMULA VB:
Q-- (CH.sub.2).sub.p !--COOH (VB)
where Q is halogen, preferably chloro, and optionally forming a salt thereof.
The molar ratio of acid of FORMULA IVB or VB to form the compound of FORMULA IIIB should be chosen to ensure that the desired level of N-substitution takes place. N-atoms which are part of an amide group will not react with the acid but any other --NH-- groups will react. Typically, therefore, to avoid the presence of primary amino groups the molar ratio will be at least 1:1 when n is 1 and R'1 is H. A slight molar excess (e.g. about 10%) of acid is generally used, e.g. for n=1 and R 1 =H, the acid is preferably used in a molar ratio of about 2.2:1.
Preferably the compounds of FORMULA IB are made by reacting the compounds of FORMULA IIIB and IVB since if the chloro acid is used as a starting material it is generally difficult to remove all the chlorine-containing material from the product, and chlorine-containing compounds can damage the environment. Preferably, the compound of FORMULA IVB is acrylic acid.
The reaction of compounds of FORMULA IIIB and IVB or BV may be undertaken by dissolving the compound of FORMULA IIB in a convenient solvent, e.g. secondary butanol, adding the acid and heating the mixture until the reaction is complete. The reaction may be carried out at temperatures of from room temperature up to the reflux temperature of the reaction mixture, typically 60° C. to 120° C.
The starting compounds of FORMULA IIIB may be synthesized by reacting a fatty acid with an alkyl amine. Suitable fatty acids as described above, with respect to the derivation of R. In particular, tall oil fatty acid (TOFA) and oleic acid are suitable starting materials. The acid and amine initially react to produce an amide i.e. a compound of the FORMULA IIIB in which Y is --CO--NH-- Dehydrolysis of the amide results in cyclisation to give compound of the FORMULA IIIB in which Y is a heterocyclic ring. An incomplete cyclisation reaction results in a mixture of compounds of FORMULA IIIB in which Y is an amide group and those in which Y is a heterocyclic ring. Some starting material and some mono-, di- or polyamides may also be present, depending on the starting amine in the system. This mixture may be used to produce a successful corrosion inhibitor.
The alkyl amine is chosen to give the appropriate heterocyclic ring and/or amide group(s) and, if desired, alkyl amine group attached to the heterocyclic ring or amide. Suitable alkyl amines include e.g. ethylene diamine, diethylenetriamine (DETA), triethylenetetramine (TETA) and tetraethylenepentamine (TEPA).
The reaction of the fatty acid and alkyl amine may be carried out by heating the reactants in a suitable solvent e.g. an aromatic hydrocarbon. The reaction may be carried out initially at the reflux temperature of the mixture, e.g. 140° to 180° C., and the temperature may be increased to e.g. 200° to 230° C. to form the heterocyclic ring.
Operation
As mentioned above, the method of the present invention employs mercaptocarboxylic acid (Component A) and an amine corrosion inhibitor of FORMULA I (Component B) in oil field operations. The two component corrosion inhibitor may be added to the oil filed liquids in the form of a solution or dispersion in water or an organic solvent. Examples of suitable solvents are alcohols such as methanol, ethanol, isopropanol, isobutanol, secondary butanol, glycols and aliphatic and aromatic hydrocarbons. The solubility of the compounds in water can be improved by forming a salt e.g. a sodium, potassium, magnesium or ammonium salt.
The amount of active ingredient in the composition required to achieve sufficient corrosion protection varies with the system in which the two-component inhibitor is being used. Methods for monitoring the severity of corrosion different systems are well known, and may be used to decide the effective amount of active ingredient required in a particular situation. The compounds may be used to impart the property of corrosion inhibition to a composition for use in an oil or gas field application and which may have one or more functions other than corrosion inhibition, e.g. scale inhibition.
In general it is envisaged that the corrosion inhibitor used in amounts of up to 1000 ppm, but typically within the range of 1 to 200 ppm, preferably from 5 to 50 ppm.
The two component corrosion inhibitor may contain the materials which it is known to include in corrosion inhibiting compositions e.g. scale inhibitors and/or surfactants. In some instances, it may be desirable to include a biocide in the composition.
The two component corrosion inhibitor may be used in a variety of petroleum operations in the gas and oil industry. They can be used in primary, secondary and tertiary oil recovery and be added in a manner known per se. Another technique is primary oil recovery where they can be used is the squeeze treating technique, whereby they are injected under pressure into the producing formation, are adsorbed onto the strata and absorbed as the fluids are produced. They can further be added in the water flooding operations of secondary oil recovery as well as be added to pipelines, transmission lines and refinery units. They may also be used to inhibit acid solution in well acidizing operations.
EXAMPLES
Shrimp Kill Tests
LC 50 Evaluation
Tests were carried out to determine the minimum concentration of chemical to achieve the death of 50% of a population. Shrimp was selected as the test organism because of its higher sensitivity. Thus the toxicity test results on shrimp are indicative of toxicity of the chemical on fish.
The test procedure used in the toxicity tests were in accordance with approved EPA methods described in EPA Publication EPA 600 4-90 027 (September 1991) entitled "Methods for Measuring the Acute Toxicity of Effluents and Receiving-Waters to Freshwater and Marine Organisms" (Fourth Edition), the disclosure of which is incorporated herein by reference.
The LC 50 Tests were carried out for 48 hours on the following chemicals:
Sample A: a 5% aqueous solution of a quaternary amine;
Sample B: a 5% aqueous solution of a quaternary amine; and
Sample C: a 5% aqueous solution of mercaptoacetic acid.
The EPA reference toxicant was CdCl using Mysidopsis Bahia. The results are presented in Table I which indicates the concentration of each sample to achieve the 50% death o the shrimp:
TABLE 1______________________________________ LC 50 ppm______________________________________ Sample A 17.28 Sample B 84.55 Sample C 2915.43______________________________________
The results demonstrate that Sample C (mercaptoacetic acid) was far less toxic than Samples A or B (quaternary amine corrosion inhibitor).
Corrosion Inhibition Tests
Corrosion inhibition was measured using an RCE bubble test.
The RCE "bubble test" apparatus consists of several 1 liter cylindrical pyrex glass vessels. Brine (600 ml) is added to each pot and carbon dioxide gas bubbled into the system while heating to 90° C. After oxygen has been removed (e.g. half an hour at 90° C.), cylindrical mild steel probes re inserted into the hot brine and kerosene (200 ml) carefully poured on top of the aqueous phase. Other hydrocarbons e.g. crude oil can be used instead of kerosene. If a "sweet" test is required, the system is now sealed. Corrosion rate readings (in mpy) are now initiated using a linear polarisation meter and recorder. Readings are then taken throughout the course of an experimental run. After three hours, the rate of corrosion has usually achieved equilibrium and a blank corrosion rate is taken. Ten ppm or corrosion inhibitor is then injected into the hydrocarbon phase of the system to test the water partitioning properties of each chemical.
The samples tested were as follows:
Sample A: a 25% aqueous solution of ethylenetetraamine/tall oil fatty acid/acrylic acid adduct;
Sample B: a 23.75% aqueous solution fatty acid/acrylic acid adduct and a 5% aqueous solution of mercapto acetic acid (total actives 28.75 wt. %); and
Sample C: a 5% aqueous solution of mercaptoacetic acid.
FIG. 1 presents plots of the tests on the 3 samples. The plots show a synergistic effect of the mixture of the adduct and mercaptoacetic acid. Sample B inhibitor stabilized at 30 mpy at about 8 hours whereas Sample A provided a minimum corrosion rate of 50 mpy and Sample C provided a minimum corrosion rate of 85 mpy.
Additional tests were carried out on the 3 samples at 10 ppm and 25 ppm. Table II presents these date after 20 hours of testing for 10 ppm treatment. At 20 hours and additional 15 ppm inhibitor was added and readings were taken after 3 more hours for a total of 23 hours.
______________________________________ Corrosion Rate (mpy) 10 ppm 25 ppm______________________________________Sample A 90 42Sample B 40 20Sample C 70 42______________________________________
Note that Samples A and C gave less protection at 25 ppm than the two component corrosion inhibitor (Sample B) at 10 ppm.
The above test data, coupled with the test data presented in U.S. Pat. No. 5,300,235, demonstrate that the two component corrosion inhibitor (a) possesses low toxicity properties, and (b) exhibits synergistic corrosion inhibition properties.
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A low toxic corrosion inhibitor comprises (A) mercaptocarboxylic acid having from 2 to 6 carbon atoms, and (B) a polyamine/fatty acid/carboxylic acid adduct. The preferred combination of (A) and (B) includes mercaptoacetic acid and ethylenetetramine/tall oil acd/acrylic acid adduct.
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PRIORITY CLAIM
[0001] This is a continuation-in-part of U.S. application Ser. No. 13/838,563, titled “Method and Apparatus for Displaying Periodic Signals Generated by a Medical Device” and filed on Mar. 15, 2013, which is incorporated herein by reference in its entirety.
TECHNICAL FIELD
[0002] A method and apparatus for displaying periodic signals generated by a medical device is disclosed. A method and apparatus for displaying quasi-periodic signals generated by a medical device also is disclosed.
BACKGROUND OF THE INVENTION
[0003] Electrocardiogram (EKG, also known as ECG) devices are well-known in the prior art. They measure the electrical activity of the human heart using electrodes and create tracings of the activity on paper or on a visual display.
[0004] FIG. 1 depicts a prior art medical device 10 along with output 20 . In this particular exemplary depiction, medical device 10 is an EKG device and output 20 is EKG data. Notably, output 20 comprises either a graph printed on a scroll of paper or a graphical display on a screen that scrolls in real-time as the electrical activity is measured. Using prior art device 20 , a doctor or medical professional must read the scroll of paper or watch the tracings on a screen in real time. This can be a tedious and challenging exercise that contains the inherent risk that the doctor or medical professional will miss an important change in the monitored activity.
[0005] Many medical devices create periodic signals as well that represent activity within the human body. For example, medical devices exist in the areas of electromyography (EMG) (to monitor muscle activity), electroencephalography (EEG) (to monitor brain activity), polysomnography (to monitor breathing activity during sleep), and other areas in which periodic signals are generated and monitored in real-time by a doctor or medical professional.
[0006] In the electrical engineering field, oscilloscopes and other tools are well-known for displaying electrical signals on a screen. One technique used by such tools is to create an “eye diagram” for periodic signals. The technique involves superimposing the signal from one period over the signal from the next period and the next period, and so on. An exemplary eye diagram 30 is shown in FIG. 2 . This allows the user to physically see multiple periods of the signal at one time in a limited amount of space and to readily view any differences or deviations in the signals.
[0007] What is needed is a device for generating an eye diagram for periodic signals generated by medical devices and to identify any excursions from the mean values, expected values, or other thresholds. What is further needed is the ability to examine an excursion in more detail and to quickly see the data before and after the excursion occurred.
[0008] What is further needed is the ability to apply these concepts to quasi-periodic signals generated by medical devices.
SUMMARY OF THE INVENTION
[0009] The aforementioned problem and needs are addressed through an embodiment for generating an eye diagram of a periodic signal output from a medical device and for examining an excursion in more detail. Another embodiment provides the same benefit for quasi-periodic signals.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 depicts a prior art medical device and its output.
[0011] FIG. 2 depicts a prior art eye diagram.
[0012] FIG. 3 depicts an embodiment for generating an eye diagram using a periodic signal from a medical device.
[0013] FIG. 4 depicts an embodiment for identifying and capturing one or more periods of data from a periodic signal from a medical device.
[0014] FIG. 5 depicts an embodiment for generating an eye diagram using a periodic signal where the eye diagram shows an excursion in the signal.
[0015] FIG. 6 depicts an embodiment for displaying an expanded version of the periodic signal in response to a user instruction after viewing the eye diagram of FIG. 5 .
[0016] FIG. 7 depicts an embodiment for generating an eye diagram using a quasi-periodic signal from a medical device.
[0017] FIG. 8 depicts an embodiment for generating an eye diagram using a quasi-periodic signal where the eye diagram shows an excursion in the signal.
[0018] FIG. 9 depicts an embodiment for displaying an expanded version of the quasi-periodic signal in response to a user instruction after viewing the eye diagram of FIG. 8 .
[0019] FIG. 10 depicts various display options for the eye diagram.
[0020] FIG. 11 depicts an embodiment of display eyewear.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0021] An embodiment will now be described with reference to FIG. 3 . Medical device 10 is the same prior art device described previously with reference to FIG. 1 . The output of medical device 10 is provided as an input to processing device 40 . In this particular example, the output is EKG data, but the same principles apply to any periodic data collected from a medical device.
[0022] In one embodiment, processing device 40 is a computing device (such as a desktop, notebook, server, tablet, mobile device, or other computer) comprising a processor, memory, non-volatile storage (such as a hard disk drive or flash memory array), I/O connection (such as a USB connection) for communicating with a medical device, and an I/O connection for sending output to a display, printer, or other device. Optionally, processing device 40 can itself include a display (as might be the case if processing device 40 is a tablet or mobile device). Processing device 40 comprises software code for performing the functions described herein.
[0023] Processing device 40 receives the periodic signal generated by medical device 10 and generates an output 50 that comprises an eye diagram of the signal by superimposing one period of the signal on top of another period of the signal, and so on. One of ordinary skill in the art will appreciate that output 50 is much easier to read and analyze than output 20 shown in FIG. 1 .
[0024] The periodic signal generated by medical device 10 can be either analog or digital. If the periodic signal is an analog signal, processing device 40 will perform analog-to-digital conversion using known techniques. If the periodic signal already is a digital signal, then no conversion is needed.
[0025] FIG. 4 depicts a method for generating an eye diagram as shown in FIG. 3 . Processing device 40 stores digital data in a buffer (step 200 ), where the buffer is contained within memory. The digital data is the data received from medical device 10 (if the data is digital) or is the digitized version of the data received from medical device 10 (if the data is analog). In the example of EKG data, the digital data represents the electrical impulses coming out of the heart Processing device 40 identifies peak values within a sequence of digital data stored in the buffer (step 210 ). This can be done simply by comparing all data points received within a time period t 1 that is several times larger than the expected period of a normal heartbeat. For example, t 1 can be 5 seconds. The peak value of each heartbeat will be approximately the same. Processing device 40 determines the number of data points B between peak values to determine the period of the data (step 220 ). The value of B will depend upon the patient's heart and the sampling rate of medical device 10 (if it generates digital data) or the sampling rate of the analog-to-digital converter of processing device 40 (if medical device 10 generates analog data). Processing device 40 optionally resamples the data to collect N data points per period (step 230 ). This might be desirable, for instance, if B is not a power of 2 (which is likely). For example, if B is 1157 (representing 1157 data points per period), one could choose N to be 1024, where 1024 data points are collected by resampling the B data points using known digital sampling techniques. Processing device 40 displays R periods of data on output 50 (step 240 ), where R is any integer value that represents the number of periods of data displayed in the eye-diagram at any given time. R optionally can be a very large number such that all of the data will be displayed on the eye-diagram.
[0026] A baseline sequence representing one heart beat can be utilized. The baseline sequence can represent an ideal heart beat that is stored in non-volatile storage of processing device 40 , or the baseline sequence can be determined based on data collected from the patient's heart beat. For example, once processing device 40 has stored multiple periods of data for the patient's heart beat, it can determine the mean value for each data location within the sequence of data in one period over X periods of data. If X=50 and N=1024, for instance, processing device 40 will determine the mean value at each data location a i (where i ranges from 1 to N or 1024 in this example) within 50 periods of data. The resulting sequence a will represent the baseline heartbeat.
[0027] Once a baseline is determine, excursions can be automatically identified in the data obtained from medical device 10 . If we assume N is 1024, then each period will have 1024 data points, and the baseline sequence a i will also have 1024 data points. A threshold L can be set, where L is a percentage of deviation. Each data point d hi (where h ranges from 1 to T and T represents the number of periods of data captured to date, and i ranges from 1 to N, and i represents the location within the sequence as is the case with a i ) is compared to a i . If d hi is 1% greater or less than a i , then d hi represents an excursion.
[0028] All data points representing excursions are recorded or flagged by processing device 40 . For example, processing device 40 can maintain a data structure for each data point d hi that includes a flag bit, where a 0 represents no excursion and a 1 represents an excursion. In the alternative, processing device 40 can maintain a list of each data point d hi that is an excursion.
[0029] An embodiment is now shown in FIG. 5 . FIG. 5 is similar to FIG. 3 except output 50 shows an graphical excursion 60 in one period of the signal. Graphical excursion 60 represents a deviation from the “norm” as shown in the eye diagram and comprises data points d hi that were determined to be excursions, for example, by using the method described above. One of ordinary skill in the art will understand that graphical excursion 60 is much easier to identify than it would have been in the traditional tracings on a scroll of paper or tracings displayed on a screen that scrolls in real-time.
[0030] Optionally, when an excursion is identified, processing device 40 can generate alert 70 . Alert 70 can appear on the display as part of output 50 , or it can be sent over email, SMS or MMS message, a phone call, a web-based message, etc. Processing device 40 can generate alert 70 based on any of the following: identification of an excursion as described above; statistically significant deviation from the mean value of the periodic signal at that location within the period; significant deviation from the expected value of the signal for a healthy individual; or a value above a pre-determined threshold specified by the user or programmed into processing device 40 .
[0031] Optionally, processing device 40 can enable a user to request more information regarding graphical excursion 60 or any other portion of the eye diagram contained in output 50 . Such requests can be made through a mouse click on a display, through a keyboard, or using a voice command.
[0032] If a user requests further information regarding graphical excursion 60 (such as by clicking on it using a mouse and a display), then optionally a traditional view will be created as shown in FIG. 6 .
[0033] In FIG. 6 , processing device 40 generates output 70 , which resembles a traditional display of periodic signal. Graphical excursion 60 is shown, and the selected period 80 in which graphical excursion 60 appears is highlighted for the user, such as by drawing a box around the relevant portion of the signal as shown in FIG. 6 , altering the color or brightness of that portion of the signal, or otherwise changing the appearance of that portion of the signal. The amount of data to be displayed before and after the excursion can be user controlled. Less amount of data display can lead to faster viewing whereas larger amount of data can be slower and appear cluttered on a limited viewing screen.
[0034] One of ordinary skill in the art will understand that this combination of the prior art medical devise with the prior art eye diagram technique yields an invention that will enhance the ability of doctors and other medical professionals to analyze periodic signal from medical devices, such as EKG or ECG data, and to quickly identify any troublesome excursions in the data.
[0035] The embodiments described thus far have utilized periodic signals generated by medical device 10 . Many of the same principles can be applied to quasi-periodical signals generated by medical device 15 . A quasi-periodic signal is a signal that represents measurements that are not periodic by nature (such as blood pressure, weight, blood sugar, etc.) but which are captured on a periodic basis (such as a measurement taken daily at 8 am or every few hours in a day).
[0036] An embodiment is shown in FIG. 7 . In FIG. 7 , medical device 15 captures data from a patient that is not periodic in nature. Examples of medical device 15 include a scale to measure weight, a sphygmomanometer to measure blood pressure, a glucometer to measure blood sugar levels.
[0037] Medical device 15 transmits data to processing device 40 , which is the same processing device 40 described with reference to other embodiments. Processing device 40 records the data, which in this example, comprises date/time and value information. For example, if medical device 15 is a scale, the data might be: 5-28-13 at 0801, 155 pounds. Over time, processing device 40 organizes the data into quasi-periodic groups. For instance, if processing device 40 receives a certain type of reading at approximately the same time each day, it will organize the data into a data structure and can optionally generate output 55 that depicts the readings of, for example, a patient's weight at 8 am on a daily basis. Even if the data is not obtained on a completely regular basis, for example at 8 am on one day, 10 am on another day etc., the dataset will still be assumed to be quasi-periodic. When the number of readings becomes too large to display on a single screen, the data can be shown as an eye-diagram as shown in FIG. 7 .
[0038] As with previous embodiments, a baseline can be generated (for example, by averaging the first F values), and processing device 40 can identify excursions from the baseline. The same methodology described previously can be used. This is depicted in FIG. 8 , where graphical excursion 60 is shown in output 75 .
[0039] With reference to FIG. 9 , as with previous embodiments, a user can request further information about graphical excursion 60 , and once this occurs, the graphical excursion 60 and data that preceded and followed the graphical excursion will be displayed as output 75 , and the graphical excursion 60 can be highlighted for the user.
[0040] FIG. 10 depicts various mechanisms for a user to view output 50 , output 55 , output 70 , output 75 , and other output that can be utilized for the embodiments described previously with reference to FIGS. 3-9 . These mechanisms include a display 100 (such as an LCD), mobile device 110 (such as a tablet or mobile phone), and eyewear 120 .
[0041] FIG. 10 depicts an example of eyewear 120 . Eyewear 120 comprises lenses 122 and frame 121 (just as with normal glasses). But it also includes display unit 130 and processing and transmission unit 140 (embedded within the frame 121 ).
[0042] An example of eyewear 120 was recently announced by Google as the “Google Glass” product. Eyewear 120 , such as the Google Glass, comprises a display unit 130 that displays data that you could otherwise display on an LCD or other display. Display unit 130 can be used to display the eye diagrams discussed previously.
[0043] The possible uses of eyewear 120 by physicians in conjunction with the display of periodic signals discussed above are numerous. For example, a physician could: (a) view a periodic signal during a patient examination, during a remote consultation, or during a collaborative session with a fellow physician (e.g., two physicians viewing the same EKG); (b) look at the patient in the physician's office while the display unit 130 displays a periodical signal; or (c) apply physical pressure to the patient or perform other techniques or tests and get instant visual feedback regarding the effect on heartbeat, etc.
[0044] References to the present invention herein are not intended to limit the scope of any claim or claim term, but instead merely make reference to one or more features that may be covered by one or more of the claims. Materials, processes and numerical examples described above are exemplary only, and should not be deemed to limit the claims. It should be noted that, as used herein, the terms “over” and “on” both inclusively include “directly on” (no intermediate materials, elements or space disposed there between) and “indirectly on” (intermediate materials, elements or space disposed there between). Likewise, the term “adjacent” includes “directly adjacent” (no intermediate materials, elements or space disposed there between) and “indirectly adjacent” (intermediate materials, elements or space disposed there between). For example, forming an element “over a substrate” can include forming the element directly on the substrate with no intermediate materials/elements there between, as well as forming the element indirectly on the substrate with one or more intermediate materials/elements there between.
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A method and apparatus for displaying periodic signals generated by a medical device is disclosed. A method and apparatus for displaying quasi-periodic signals generated by a medical device also is disclosed.
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RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No. 60/045,918 filed May 7, 1997.
TECHNICAL FIELD OF THE INVENTION
This invention relates generally to the field of optical tomography and more particularly to a method and system for frequency encoded ultrasound-modulated optical tomography of dense turbid media.
BACKGROUND OF THE INVENTION
Breast cancer is the most common malignant neoplasm and the leading cause of cancer deaths among women in the United States. Early detection is critical to the successful treatment of this disease. Currently the most common methods of detections are mammography and ultrasound. Mammography is considered the only reliable means of detecting nonpalpable breast cancers. A drawback of mammography is that it uses ionizing radiation. Also, breast tissue can be radiologically dense, making detection difficult. Ultrasound is used primarily as either a first screening tool or as a supplement to mammography.
Other techniques for the detection of breast cancer are under investigation. Magnetic Resonance Imaging (MRI) is a technique which is superior to mammography in that it can distinguish solid lesions from cystic lesions. However, MRI is expensive, has inferior spatial resolution as compared to mammography and can not image micro calcifications. Breast cancer tomography has been investigated but is expensive, has poor spatial resolution and involves the use of intravenous injected iodinated materials.
A relatively new and active field is the use of non-ionizing laser light to detect breast cancer. The optical properties of normal and diseased breast tissue typically varies. Therefore, it is possible to detect breast cancers based on the optical differences of the tissue. This is due to the fact that cancerous tissues manifest a significant change at the cellular and sub-cellular level. For example, the scattering coefficient of fibrocystic tissue (600 cm -1 ) is approximately 50 percent higher than that of normal glandular breast tissue (400 cm -1 ) or 100% higher than normal breast adipose tissue (300 cm -1 ) in the wavelength of 500-1000 nm.
One laser technique is called "early photon imaging." Since breast tissue is an optically turbid medium, light is quickly diffused inside tissue as a result of scattering. Light in tissue takes one of three forms: ballistic light, which travels straight through tissue without scattering; quasi-ballistic light, which experiences some scattering; and diffuse light, which is almost completely scattered inside tissue. This technique uses pulses of light and attempts to detect only the first light that is transmitted through the tissue. Because early photon imaging only detects ballistic light, this technique is mainly useful for thin tissues. Diffuse light is needed to detect thick tissues (5 cm).
In order to increase the incidence of early detection of breast cancer, it is desirable to have a system which can detect small abnormalities with good resolution at low cost and without the use of ionizing radiation.
SUMMARY OF THE INVENTION
In accordance with the present invention, a method and system for frequency encoded ultrasound-modulated optical tomography of dense turbid media is provided.
In one aspect of the present invention, an apparatus for frequency encoded ultrasound-modulated optical tomography of dense turbid medium is provided. The apparatus includes a function generator which produces a frequency sweep signal. An ultrasonic transducer receives the frequency sweep signal and converts it into an ultrasonic wave which is propagated in a turbid medium. A laser sends a coherent beam of light through the turbid medium where it is modulated by the ultrasonic wave. The modulated light is detected by a photomultiplier tube which sends the signal to an oscilloscope for determination of where an object or abnormality is located in the turbid medium.
The present invention provides various technical advantages over conventional techniques to locate objects in a turbid medium, such as cancerous tissue. For example, one technical advantage is that it uses non-ionizing radiation. Another technical advantage is that it is a low cost/cost effective system. Another technical advantage is that it has better resolution than other optical techniques. Further advantages include high acquisition speed and better optical resolution along the ultrasonic axis. Other technical advantages may be readily apparent to one skilled in the art from the following figures, descriptions and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
For a more complete understanding of the present invention and for further features and advantages, reference is now made to the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 illustrates a system for frequency swept ultrasonic modulated optical tomography;
FIG. 2 illustrates a sample frequency sweep;
FIG. 3 illustrates a list of possible mechanisms for ultrasonic modulation of light;
FIG. 4 illustrates an alternative embodiment of an invention using phased arrays of ultrasonic transducers; and
FIG. 5 illustrates a handheld embodiment of the tomography system.
DETAILED DESCRIPTION OF THE INVENTION
The preferred embodiment of the present invention and its advantages are best understood by referring to FIGS. 1-5 of the drawings, where like numerals are used for like and corresponding parts of the various drawings.
FIG. 1 illustrates a system 10 for frequency encoded ultrasound-modulated optical tomography. System 10 consist of a pulse generator 12 coupled to a function generator 14 which is coupled to a power amplifier 16. Pulse generator 12 is also coupled to a delay generator 34 that couples to an oscilloscope 30. Function generator 14 couples to a power amplifier 16 and is also coupled to a transformer 36 that couples to a modulated photo-multiplier tube (PMT) 24. Power amplifier 16 is coupled to a transformer 18 that couples to an ultrasound transducer 20. The ultrasound transducer 20 is preferably in contact with a turbid medium 21 for best wave propagation. A laser 22 is located on one side of the turbid medium, roughly normal to the position of the ultrasound transducer. Laser 22 sends a coherent beam of light 23 into turbid medium 21. Modulated PMT 24 receives any light which is transmitted through turbid medium 21. Modulated PMT 24 is coupled to a band pass filter 26 which couples to an amplifier 28 and an oscilloscope 30 and finally to a computer 32.
In operation, pulse generator 12 triggers function generator 14 to produce a frequency sweep signal 15. Frequency sweep signal 15 is a signal of linearly varying frequency that has a finite period. An example of the frequency variation in a sample frequency sweep is illustrated in FIG. 2. Frequency sweep signal 15 is amplified in power by power amplifier 16. The signal is then amplified in amplitude by transformer 18. The amplified signal is applied to ultrasound transducer 20 to generate an ultrasonic wave 25 in turbid medium 21.
Laser 22 sends a beam of coherent light 23 into the turbid medium. The diffuse light from beam of light 23 is modulated by the ultrasonic wave 25, which adds spatial information to the diffuse light. Because light travels much faster than ultrasonic wave 25, the ultrasonic-modulated optical signal reflects the instantaneous frequencies of ultrasonic wave 25.
Prior to transformer 18, the signal from power amplifier 16 is fed into transformer 36 to amplify the amplitude of the signal to form a modulation signal 37. This signal is sent to the modulated PMT 24 where it mixes with the modulated optical signal coming out of the turbid medium 21. While a PMT is illustrated in the primary embodiment, any device capable of detecting light, such as a photo diode, can be used. Band-pass filter 26 selects the signal from a zone of interest along the ultrasonic axis based on the frequency sweep rate and the time of ultrasonic propagation. The filtered signal is amplified for detection by an oscilloscope 30. Oscilloscope 30 is triggered by delay generator 34 which triggers the oscilloscope after the ultrasonic wave has had sufficient time to propagate in the turbid medium 21. Oscilloscope 30 takes and may average the results over a number of sweeps in order to increase the signal to noise ratio. Computer 32 then analyzes the signal from the oscilloscope and performs fast Fourier Transform (FFT).
The frequency spectrum will yield imaging information for the zone of interest as selected by band-pass filter 26. The frequency in the spectrum corresponds to the instantaneous frequency of the different axial positions in the zone of interest minus the instantaneous frequency of the modulation signal sent to PMT 24 and equals the frequency sweep rate times the ultrasonic propagation time from the ultrasonic transducer 20 to different positions in the zone of interest. The frequency in the spectrum can be converted into the ultrasonic propagation time from the ultrasonic transducer 20 to different positions in the zone of interest. The propagation times multiplied by the speed of the ultrasound in the medium yields the distance from the ultrasound transducer 20 to the point in the zone of interest. There is a one-to-one correspondence between the frequency in the spectrum and the position in the zone of interest. The frequency spectrum can be converted into a position spectrum, which is a one-dimensional image of the turbid medium 21 along the ultrasonic axis. Movement of the apparatus along a line perpendicular to the ultrasonic axis results in a two dimensional image while movement along a plane results in a three dimensional image.
The saw-tooth function in the frequency sweep may be replaced with a triangle function to avoid abrupt change in the instantaneous frequency. The frequency sweep may also be produced using an arbitrary wave form generator. Two function generators may also be used to deliver two frequency sweep signals. There may be a time delay and/or a frequency shift between the two frequency sweep signals.
FIG. 3 lists possible mechanisms for ultrasonic modulation of light. The first mechanism starts with the ultrasonic wave generating a pressure variation in the medium at step 64. This induces a density change in the medium at step 66. The optical absorption at step 78, scattering coefficient at step 70, and index of refraction at step 72 vary with density. The changes in these parameters lead to the modulated light in step 62.
Another possible mechanism is particle displacement. The ultrasonic wave generates particle displacement at step 56. This causes optical path lengths to change at step 58. Changes in optical path length leads to speckles forming in the medium at step 60, which leads to a change in light intensity at step 62.
A third mechanism is phonon-photon interaction. In step 50, the ultrasonic wave is considered to act like a phonon. The phonons interact with the photons from the laser 22 causing a Doppler shift at step 52 of the optical frequency by the ultrasonic frequency. The optical detector functions as a hetereodyning device at step 54 between the Doppler shifted light and unshifted light and produce a signal of the ultrasonic frequency.
The single ultrasonic generator 20 may be replaced by a one or two dimensional sequenced array of ultrasonic transducer elements 20. Each element is driven by a different frequency sweep signal 15 in such a way as that the frequency at any two points in time is not the same. Additionally, all or some of the ultrasonic elements 20 may be excited at the same time. If a group of elements are excited sequentially, a two dimensional image can be made from a linear ultrasonic array. A two dimensional array would yield a three dimensional image if the elements are excited sequentially. If an entire linear array is excited simultaneously, a two dimensional image along the ultrasonic axes is obtained. If a two dimensional array of elements is excited simultaneously, a three dimensional image along the ultrasonic axes is obtained.
FIG. 4 illustrates ultrasonic generation using phased arrays. In this embodiment, the single ultrasonic generator 20 is replaced by a one or two dimensional phased array ultrasonic transducer 20 elements that are connected to electronic delay lines 80. In this manner, a single frequency sweep signal 15 will be delayed and then applied to each element. By adjusting the delays, the ultrasonic focus can be adjusted. By changing the curvature of the wavefront, the depth of the focus can be adjusted. The focus can be moved horizontally by changing the symmetry of the wavefront.
FIG. 5 illustrates a handheld embodiment of the present invention. Input optical fiber 90 sends a coherent source of light into tissue 92. An ultrasonic array 93 (consisting of one or more ultrasonic generators, one or more function generators, and other electronic components) produces an ultrasonic wave in tissue 92. An output optical fiber 94 transports modulated-light for analysis.
This disclosed technique may be modified to conduct imaging using sonoluminescent light. The laser is not needed in sonoluminescence imaging. Sonoluminescent chemicals are mixed into the turbid medium. The medium is excited using ultrasound to generate ultrasound-induced light (sonoluminescent light). A similar data detection and analysis as described above would generate an image of the medium in terms of its sonoluminescent characteristics.
While the preferred embodiment has been discussed in terms of the detection of breast cancer, it is apparent from the above discussion that this apparatus can be used to detected abnormalities in other bodily locations as well as acquire images of different structures located in other turbid mediums wholly outside of the medical field such as underwater detection, atmosphere optics and other fields involving turbid mediums. It should be understood that various changes, substitutions and alterations may be readily apparent to those skilled in the art and may be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
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An apparatus (10) for frequency encoded ultrasound modulated optical tomography is provided. A function generator (12) produces a frequency sweep signal which is applied to an ultrasonic transducer (20). The ultrasonic transducer (20) produces ultrasonic wave (25) in a turbid medium (21). Coherent light from a laser (22) is passed through turbid medium (21) where it is modulated by the ultrasonic wave (25). A photomultiplier tube (24) detects the light which passes through the turbid medium (21). The signal from the photomultiplier tube (24) is fed to an oscilloscope (30) and then to a computer (32) where differences in light intensity at different frequencies can determine the location of objects in the turbid medium (21).
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TECHNICAL FIELD
The present invention relates to a working vehicle having an electric motor driven by a battery as the drive power source.
TECHNICAL BACKGROUND
In conventional working vehicles the drive power source is normally an engine. However, in circumstances in which an engine cannot be used, such as in an underground construction site, construction machinery with an electric motor as the power source is used (see for example Japanese Patent Application Laid-open No. 2004-225355). The power source for the electric motor is a commercial power supply, or a battery on the construction machinery that is charged from a commercial power supply.
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
However, in this type of working vehicle when the electric motor is driven by a battery, there is the problem that if it is necessary to frequently charge the battery, the operation efficiency becomes poor. Therefore it is necessary to operate the working vehicle without charging the battery during a working period of at least one day.
With the foregoing in mind, it is an object of the present invention to provide a working vehicle constituted to prevent consumption of electric power from the charged battery when the hydraulic actuator of the like is not being operated.
Means to Solve the Problems
To resolve the above problem, the working vehicle according to the present invention (for example, the crawler type power shovel 1 according to the embodiments) is a working vehicle operated by a hydraulic actuator, the working vehicle comprising: a hydraulic pump that outputs hydraulic oil for operating the hydraulic actuator; an electric motor that drives the hydraulic pump; a main battery that supplies direct current electric power; an inverter that operates the electric motor by converting the direct current electric power from the main battery into alternating current electric power and supplying the alternating current electric power to the electric motor; an electric motor relay for making and breaking the connection between the main battery and the inverter (for example, the second relay 47 according to the embodiments); an operating device for operating the hydraulic actuator; a controller which is operated by the direct current electric power from the main battery, and which controls the operation of the hydraulic actuator and the inverter in accordance with operation signals output from the operation device, and makes and breaks the connection between the main battery and the inverter in use of the electric motor relay; a controller relay for making and breaking the connection between the main battery and the controller (for example, the first relay 46 according to the embodiments); a power source monitoring controller that monitors the state of the main battery, and that makes and breaks the connection between the main battery and the controller using the controller relay; an oil pressure sensor for measuring the output oil pressure of the hydraulic oil output from the hydraulic pump; and a current sensor for measuring the value of the load current flowing from the main battery to the inverter. For the working vehicle, configuration is employed to execute: a first step in which the controller, when determination is made that there has been no variation in the magnitude of the output oil pressure measured by the oil pressure sensor and the load current measured by the current sensor within a set period of time, breaks the connection between the main battery and the inverter and stops the motor in use of the electric motor relay; a second step in which the controller, when determination is made that the state where no operating signal has been output from the operating device has continued during a predetermined set period of time, transmits a command signal to the electrical power monitoring controller; and a third step in which the power source monitoring controller, when the transmitted signal is received, breaks the connection between the main battery and the controller in use of the controller relay, and stops the controller.
In the working vehicle according to the present invention, preferably the controller has a motor start up switch, and in the second step, the controller, when determination is made that the motor start up switch has been operated, connects the main battery and the inverter in use of the electric motor relay, and starts the electric motor in order to return to the first step.
Also, in the working vehicle according to the present invention, preferably the power source monitoring controller has a power supply switch, and in the third step, after stopping the controller, the power source monitoring controller, when determination is made that the power supply switch has been operated, connects the main battery to the controller and the inverter using the controller relay and the electric motor relay in that order
Advantageous Effects of the Invention
When the working vehicle according to the present invention is constituted as described above, the supply state of hydraulic oil to the hydraulic actuator and the manipulation state of the operating device are monitored by the controller, and when oil pressure is not necessary the electric power supply to the inverter is stopped, and further the electric power supply to the controller is stopped, so unnecessary power consumption from the main battery is minimized and it is possible to lengthen the time that the power shovel can carry out work without charging the main battery unit. Even when the power supply to the inverter and the controller is stopped in this way, by pressing the motor start up switch or the power supply switch, it is possible to simply supply electric power to the inverter and the controller.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective diagram showing the constitution of a crawler type power shovel as an example of a working vehicle according to the present invention;
FIG. 2 is a block diagram showing the constitution of the hydraulic unit and power supply unit in the above power shovel;
FIG. 3 is a flowchart showing the electric power start up process of the power supply unit; and
FIG. 4 is a flowchart showing the electric power saving control in the power supply unit.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following is an explanation of the preferred embodiments of the present invention with reference to the drawings. First, a crawler type power shovel 1 is explained as an example of a working vehicle according to the present invention, using FIG. 1 . This power shovel 1 is intended to be used in comparatively enclosed spaces such as underground and the like, and operates by using electrical power from a battery (hereafter referred to as a main battery 50 a ). The power shovel 1 includes a travel bogey 4 that forms a travel device 2 , a blade 9 provided to the rear of the travel bogey 4 that is capable of swiveling vertically, a rotation platform 11 that is capable of rotating provided above the travel bogey 4 , a power shovel mechanism 13 swivelably connected to the front of the rotation platform 11 , and an operator's cabin 15 provided above the rotation platform 11 .
The travel device 2 includes the approximately H-shaped travel bogey 4 , and a travel mechanism 3 provided on the left and right of the travel bogey 4 . The travel mechanism 3 includes a drive sprocket wheel 5 provided to the front and an idler wheel 6 (on occasions the drive sprocket wheel 5 and the idler wheel 6 will be referred to collectively as the “crawler wheels”) provided to the rear on the left and right of the travel bogey 4 , and a pair of left and right crawler tracks 7 wound around the two wheels 5 , 6 . Each of the drive sprocket wheels 5 is driven by left and right drive motors (hydraulic motors), which are not shown on the drawings, so that the power shovel 1 can move. Also, the rotation platform 11 can be rotated relative to the travel bogey 4 by a rotation motor (hydraulic motor), which is not shown on the drawings.
The power shovel mechanism 13 includes a boom 16 swivelably connected to the front of the rotation platform 11 so that the boom 16 can be freely raised and lowered, an arm 17 swivelably connected to the top of the boom 16 so that the arm 17 can be freely swiveled vertically in the plane of vertical movement of the boom 16 , and a bucket 18 connected to the top of the arm 17 so that the bucket 18 can be freely swiveled. The boom 16 is raised and lowered by a boom cylinder 21 , the arm 17 is swiveled by an arm cylinder 22 , and the bucket 18 is swiveled by a bucket cylinder 23 . The cylinders and the drive motors referred to above and the rotation motor are driven by hydraulic oil supplied from a hydraulic unit 30 , as shown in FIG. 2 , so in the following explanation, these are collectively referred to as the “hydraulic actuator 20 ”. Also, operation of the power shovel mechanism 13 is carried out using an operating device 14 provided within the operator's cabin 15 .
The hydraulic unit 30 includes an electric motor 31 , a hydraulic pump 32 that is driven by the electric motor 31 and that outputs hydraulic oil at a specific oil pressure and flow rate, a tank 33 in which hydraulic oil accumulates, a control valve (electromagnetic proportional valve) 34 that controls the supply of hydraulic oil output from the hydraulic pump 32 to the hydraulic actuator 20 in a supply direction and supply flow rate in accordance with the manipulation of the operating device 14 , and an oil cooler 35 that cools the hydraulic oil whose temperature has risen. Operation signals output from the operating device 14 are input to a controller 42 , which is described later, and the controller 42 outputs command signals to the control valve 34 in accordance with the operation signals such that the control valve 34 is controlled.
Direct current electric power supplied from the main battery unit 50 is converted into alternating current electric power having a predetermined voltage and frequency by an inverter 43 and supplied to the electric motor 31 . A main battery unit 50 is constituted by a lithium ion battery, and includes a main battery 50 a capable of outputting direct current high voltage (for example, direct current 336V), and a protective circuit 50 b that obtains the status of and protects the main battery 50 a.
Next, a power supply system 40 that supplies electrical power to the electric motor 31 using the main battery unit 50 is explained. The power supply system 40 includes a power source monitoring controller 41 that monitors the output voltage and status of the main battery unit 50 , and a controller 42 that controls the inverter 43 and the control valve 34 to operate electric motor 31 and hydraulic actuator 20 , as well as connecting and disconnecting the electric power supplied to the inverter 43 .
In order to operate the power source monitoring controller 41 when starting the power shovel 1 , the power supply system 40 includes a backup battery 44 that is constituted by a lithium ion battery that outputs a direct current voltage (for example, 12.6V direct current) for operating this the power source monitoring controller 41 , and the backup battery 44 and the power source monitoring controller 41 are connected and disconnected by a key switch (main power supply switch) 45 provided within the operator's cabin 15 . The power source monitoring controller 41 supplies electric power from the backup battery 44 to the protective circuit 50 b of the main battery unit 50 , and obtains the status of the main battery 50 a from the protective circuit 50 b.
The main battery 50 a of the main battery unit 50 is connected to and supplies electric power to the controller 42 and the inverter 43 . The main battery 50 a and the controller 42 are connected by a first contact point 46 a of a first relay 46 , so the connection between the main battery 50 a and the controller 42 is made and broken by the first relay 46 . Also, the main battery 50 a and the inverter 43 are connected by a contact point 47 a of a second relay 47 , so the connection between the main battery 50 a and the inverter 43 is made and broken by the second relay 47 . The controller 42 includes a DC-DC converter 48 that converts high voltage direct current voltage supplied from the main battery 50 a into a low voltage direct current voltage (the voltage for operating the power source monitoring controller 41 ), the output of the DC-DC converter 48 is connected between the backup battery 44 and the key switch 45 via a protective diode 51 , in other words, connected to the power source monitoring controller 41 and the backup battery 44 , and these connections are made and broken by a second contact point 46 b of the first relay 46 .
The first and second contact points 46 a, 46 b of the first relay 46 are connected and disconnected by the control of the controller 41 . The first and second contact points 46 a , 46 b are normally maintained disconnected (OFF state), and when a voltage is applied to the first relay 46 from the power source monitoring controller 41 the first and second contact points 46 a , 46 b are turned ON, and when the contact points 46 a and 46 b are connected, the main battery 50 a and the controller 42 , as well as DC-DC converter 48 and the power source monitoring controller 41 and a backup battery 44 are connected. When the second contact point 46 b of the first relay 46 is connected, electric power is supplied to the DC-DC converter 48 by the power source monitoring controller 41 , and the backup battery 44 is charged. Also, the contact point 47 a of the second relay 47 is connected and disconnected by the control of the controller 42 . The contact point 47 a is normally in the disconnected state (OFF state), and when a voltage is applied to the second relay 47 from the controller 42 the contact point 47 a is turned ON, the contact point 47 a is connected, and the main battery 50 a and the inverter 43 are connected.
The output values of a hydraulic pressure sensor 36 that measures the output pressure of the hydraulic pump 32 provided in the hydraulic unit 30 , and the measured values of a current sensor 49 that measures the load current supplied to the inverter 43 from the main battery 50 a are input to the controller 42 . Also, the power source monitoring controller 41 includes a first pilot lamp 41 a that indicates the ON state of the first relay 46 , in other words, the state in which electric power is being supplied to the controller 42 , and a power supply switch 41 b that turns the first relay 46 ON when pressed while the first relay 46 is in the OFF state, and a warning pilot lamp 52 for notifying that a fault has arisen in the main battery unit 50 . Further, the controller 42 includes a second pilot lamp 42 a that indicates the ON state of the second relay 47 , in other words, indicates that electric power is being supplied to the inverter 43 , and a motor start up switch 42 b which when pressed while the second relay 47 is in the OFF state turns the second relay 470 N. The first and second pilot lamps 41 a , 42 a , the warning pilot lamp 52 , the electric power switch 41 b , and the motor start up switch 42 b are disposed within the operator's cabin 15 .
Next, control of the electric power supply by the power supply system 40 is explained using FIG. 3 . First, the power supply start up process is explained. When the operator positioned in the operator's cabin 15 turns on the key switch 45 , which is disposed within the operator's cabin 15 , electric power is supplied from the backup battery 44 to the power source monitoring controller 41 , and the power source monitoring controller 41 starts up (step S 100 ). The power source monitoring controller 41 first supplies electric power to the protective circuit 50 b of the main battery unit 50 to start up the protective circuit 50 b , and the protective circuit 50 b starts and obtains the status of the main battery 50 a (step S 110 ). Then the power source monitoring controller 41 obtains the status of the main battery 50 a from the protective circuit 50 b (step S 120 ), and determines whether the main battery 50 a can be used or not (step S 130 ). For example, if the main battery 50 a is excessively discharged or the like, it is determined that the main battery 50 a cannot be used, so the power source monitoring controller 41 lights the warning pilot lamp 52 , and the power supply start up process is terminated (step S 160 ).
On the other hand, when it is determined that the main battery 50 a is in the normal state and can be used, the power source monitoring controller 41 turns the first relay 46 ON, and electric power is supplied from the main battery 50 a to the controller 42 , so the controller 42 is started, and the first pilot lamp 41 a is lit (step S 140 ). As stated above, when the first relay 46 is in the ON state, electric power is supplied from the DC-DC converter 48 to the power source monitoring controller 41 and the backup battery 44 , and subsequently the power source monitoring controller 41 operates with electric power supplied from the DC-DC converter 48 , and charging of the backup battery 44 starts.
Finally, when the controller 42 has started, the controller 42 turns the second relay 470 N, electric power is supplied from the main battery 50 a to the inverter 43 , the inverter 43 is controlled to supply the electric motor 31 with alternating current electric power at a predetermined voltage and frequency, the electric motor 31 starts up, the second pilot lamp 42 a is lit (step S 140 ), and the electric power startup process of the power supply system 40 is terminated.
Next, the electric power saving control by the power supply system 40 is explained using FIG. 4 . The electric power saving control is a control to prevent waste of electric power in the charged main battery 50 a when it is not necessary to supply hydraulic oil to the hydraulic actuator 20 , by stopping the electric motor 31 , and stopping the controller 42 . FIG. 4 shows the control by the controller 42 , and when the power supply start up process has terminated as described above, the electric power saving control is started. Also, the symbol A enclosed within a circle appealing after step S 240 in FIG. 4 means go to and connect with the symbol A enclosed within a circle appearing immediately after Start.
The controller 42 measures the output oil pressure and the load current using the hydraulic pressure sensor 36 and the current sensor 49 (step S 200 ). Then, it is determined whether within a set period of time (for example, five seconds) the output pressure or the load current have varied (step S 210 ), if there is a variation, the procedure returns to step S 200 and repeats this process. On the other hand, when there is no variation in the output pressure and the load current within the set period of time, the controller 42 turns the second relay 47 off, so the power supply to the inverter 43 is disconnected, the electric motor 31 stops, and the second pilot lamp 42 a is turned off (step S 220 ).
Next, the controller 42 determines whether the motor start up switch 42 b is turned ON or not (step S 230 ). When it is determined that the motor start up switch 42 b is ON, the second relay 47 is turned ON, the electric motor 31 is started by supplying electric power to the inverter 43 , and the second pilot lamp 42 a is lit (step S 240 ). Then, the procedure returns to step S 200 , and the above process is repeated. At step S 230 , when it is determined that the motor start up switch 42 b is not on, the controller 42 obtains the state of manipulation of the operating device 14 or the like (step S 250 ), determines whether within a set period of time there has been a state of no manipulation or control (step S 260 ), and when there has not been a state of no manipulation or control the procedure returns to step S 230 and this process is repeated.
At step S 230 , when it is determined that the state of no manipulation or control has continued during the set period of time, the controller 42 transmits a command signal to the power source monitoring controller 41 (step S 270 ). Then, when the power source monitoring controller 41 receives the command signal from the controller 42 , the first relay 46 is turned off, the electric power supply to the controller 42 is turned off and the controller 42 is stopped, first pilot lamp 41 a is turned off, the electric power supply to the protective circuit 50 b of the main battery unit 50 is stopped, and the sleep mode is activated.
When the sleep mode is activated, the power source monitoring controller 41 stops operation except for monitoring whether the power supply switch 41 b has been pressed, so the electric power consumption of the backup battery 44 is minimized as much as possible. Then, when it is detected that the power supply switch 41 b has been pressed, the power source monitoring controller 41 terminates the sleep mode, implements the process from step S 110 in the power supply start up process shown in FIG. 3 , the first and second relays 46 , 47 are turned on, electrical power is supplied to the controller 42 and the inverter 43 , and the electric motor 31 is started.
In this way, by providing the power source monitoring controller 41 that controls the supply of electric power to the inverter 43 separately from the controller 42 , monitors the main battery unit 50 , as well as controls the supply of electric power to the controller 42 , and the backup battery 44 that allows the power source monitoring controller 41 to operate even when electric power is not supplied from the main battery unit 50 , even if a fault arises in the main battery 50 a , this fault is detected by the power source monitoring controller 41 and it is possible to provide a warning using the warning pilot lamp 52 or the like, so it is possible to make the operator that is operating the power shovel 1 immediately aware of the fault in the main battery unit 50 .
At this time, the process when electric power is turned ON as described above is capable of turning on the power supply in turn starting with the power source monitoring controller 41 , so it is possible to simplify the process and constitution of the power source monitoring controller 41 and the controller 42 . Also, when electric power is supplied to the controller 42 when the main battery 50 a is in a normal state, and at the same time the power source monitoring controller 41 is operated by the main battery 50 a and the backup battery 44 is charged, if a fault arises in the main battery 50 a , the power source monitoring controller 41 can be operated by the backup battery 44 .
Further, the supply state of hydraulic oil to the hydraulic actuator 20 and the manipulation state of the operating device 14 are monitored by the controller 42 , and when oil pressure is not necessary the electric power supply to the inverter 43 is stopped, and further the electric power supply to the controller 42 is stopped, so unnecessary power consumption from the main battery 50 a is minimized, and it is possible to lengthen the time that the power shovel 1 can carry out work without charging the main battery unit 50 . Even when the power supply to the inverter 43 and the controller 42 is stopped in this way, by pressing the motor start up switch 42 a or the power supply switch 41 a , it is possible to simply supply electric power to the inverter 43 and the controller 42 .
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A power shovel vehicle including a hydraulic pump that outputs hydraulic oil for operating a hydraulic actuator, an electric motor for driving the hydraulic pump, a main battery for supplying direct current electric power, an inverter for converting the direct current electric power into alternating current electric power and operating the electric motor, a second relay for making and breaking the connection between the main battery and the inverter, an operating device for operating the hydraulic actuator, a controller for controlling operation of the hydraulic actuator and inverter, and turning on and off the second relay, a first relay for making and breaking the connection between the main battery and the controller, a power source monitoring controller for monitoring conditions of the main battery and turning on and off the first relay, a hydraulic sensor for detecting the discharge pressure of the hydraulic pump, and an electric current sensor for measuring a load current flowing into the inverter.
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This application is a continuation of, and claims the benefit of the priority date of, prior application Ser. No. 09/957,526, filed Sep. 19, 2001 now U.S. Pat. No. 6,863,678.
BACKGROUND OF THE INVENTION
This invention generally relates to catheters, and particularly intravascular catheters for use in percutaneous transluminal coronary angioplasty (PTCA) or for the delivery of stents.
In a typical PTCA procedure, a dilatation balloon catheter is advanced over a guidewire to a desired location within the patient's coronary anatomy where the balloon of the dilatation catheter is positioned within the stenosis to be dilated. The balloon is then inflated with radiopaque liquid at relatively high pressures (generally 4-16 atmospheres) to dilate the stenosed region of the diseased artery. One or more inflations may be needed to effectively dilate the stenosis. Additionally, a stent may be implanted within the artery, typically by delivery to a desired location within the artery in a contracted condition on a balloon of a catheter which is similar in many respects to a balloon angioplasty catheter, and expansion to a larger diameter by inflation of the balloon.
An essential step in effectively performing a PTCA procedure is properly positioning the balloon catheter at a desired location within the coronary artery. To properly position the balloon at the stenosed region, the catheter must have good pushability and flexibility, to be readily advanceable within the tortuous anatomy of the patient's vasculature.
What has been needed is a catheter which is highly trackable within the patient's anatomy, with improved flexibility and pushability. The catheter of the present invention provides these and other advantages.
SUMMARY OF THE INVENTION
The invention is directed to a catheter having an multilayered shaft section with a first layer formed of a polyimide first material and a second layer formed of a second material. In a presently preferred embodiment, the polyimide material is a thermoset polyimide. However, in alternative embodiments, a thermoplastic polyimide is used. The thermoset polyimide has a very high glass transition temperature (Tg) of approximately 400° C. (as measured by differential scanning calorimetry), and excellent dimensional stability at the processing temperature of polyamides commonly used in catheter components. As a result, during formation and assembly of the catheter, production of a thin polyimide layer with controlled dimensions is facilitated. The polyimide has a high modulus and provides a thin walled yet highly pushable shaft section, while the second layer provides kink resistance.
In one embodiment, the second material is selected from the group consisting of a polyamide and a polyurethane. In one presently preferred embodiment, the second material is a polyamide, and the polyamide is selected from the group consisting of a nylon and a copolyamide such as polyether block amide (PEBAX). Although discussed below for convenience primarily in terms of a polyamide second layer, it should be understood that other materials such as a polyurethane may be used for the second layer in other embodiments. The polyimide first material is not compatible with the second material (e.g., polyamide or polyurethane), and consequently, the polyimide material is not fusion (i.e., thermal) bondable to the second material. The polyimide material is a high strength material preferably having a higher Shore durometer hardness than the polyamide layer. The high strength of the polyimide material allows the wall thickness of the polyimide first layer to be small for improved shaft flexibility and low profile. The polyamide layer provides a bonding layer which can be fusion bonded to polymeric materials compatible therewith and conventionally used for other catheter components, such as nylon, PEBAX, and polyurethane. Additionally, the polyamide layer contributes to the kink resistance of the catheter. In a presently preferred embodiment, the polyamide second layer is an outer layer forming an outer surface of the multilayered shaft section, and the polyimide first layer is an inner layer forming an inner surface of the multilayered shaft section.
In a presently preferred embodiment, the catheter is a balloon catheter generally comprising an elongated shaft having a proximal portion and a distal portion, with a balloon on the distal portion of the shaft. The balloon catheters of the invention may comprise a variety of suitable balloon catheters, including coronary and peripheral dilatation catheters, stent delivery catheters, drug delivery catheters, and the like.
The catheter shaft typically has an outer tubular member with a lumen therein which, in the case of a balloon catheter, is an inflation lumen in fluid communication with the balloon interior. The shaft also has an inner tubular member disposed at least in part within a portion of the outer tubular member lumen, with a lumen therein which is typically a guidewire receiving lumen. At least a section of the outer tubular member is the multilayered section in accordance with the invention. The multilayered shaft section of the invention may extend the full length of the outer tubular member, or alternatively, it may be a distal shaft section, a proximal shaft section, or a midshaft section bonded to an adjacent shaft section(s).
In one embodiment, the catheter is a rapid exchange type catheter, having a guidewire receiving lumen in a distal section of the catheter shaft. Rapid exchange catheters generally have a distal guidewire port in the distal end of the catheter, a proximal guidewire port spaced a relatively short distance proximally from the distal guidewire port and a relatively long distance from the proximal end of the catheter shaft, and a relatively short guidewire receiving lumen extending therebetween. In an alternative embodiment, the catheter is an over-the-wire type catheter having an elongated shaft with proximal and distal ends, a guidewire port in the proximal end, a guidewire port in the distal end, and a guidewire lumen extending therein from the distal end to the proximal end of the catheter shaft.
In a presently preferred embodiment, the polyamide second layer is in direct contact with the polyimide first layer around a circumference thereof. Thus, unlike catheter shafts having a braid layer between a first and second layer, the first layer and the second layer of the multilayered shaft section are not in whole or in part separated from one another by a braid, mesh or other layer.
In a presently preferred embodiment, the polyimide first layer is formed by a solution process, and not by melt extrusion. In a suitable solution forming process, a polyimide solution is dip, or otherwise, coated onto a neckable mandrel, as described in U.S. Pat. Nos. 4,826,706 and 4,659,622, and the Manufacturing Process section of the Phelps Dodge High Performance Conductors brochure, A Primer on Polyimide Tubing, pp. 1, incorporated herein by reference in their entireties, and then separated intact from the mandrel, to thereby produce a tubular member. The dip coated mandrel can be passed through dies to control the outer dimension of the polyimide layer, and the diameter of the removable mandrel determines the inner diameter of the polyimide tube. Similarly, the polyamide or polyurethane second layer is preferably applied as a solution onto the polyimide layer, in order to provide good contact and adhesion between the polyimide layer and the polyamide or polyurethane layer. Thus, although the polyimide material is not fusion bondable to the polyamide or polyurethane material, the solution coating process provides well adhered layers which remain together during component assembly and under the high inflation pressures used during inflation of the catheter balloon. As a result, a separate adhesive or compatibilizing layer is not required between the polyimide first layer and the second layer, and, consequently, the multilayered shaft section of the invention has excellent flexibility, manufacturability, and low profile.
The catheter of the invention is highly pushable, flexible, and kink resistant due to the synergy of the materials used in the multilayered shaft section. The polyimide material has a high modulus which allows for a very thin walled yet high strength shaft. The high flexural modulus of the polyimide layer provides excellent push transmission along the shaft length during advancement within the patient's vasculature and across a lesion. Moreover, the high modulus polyimide layer provides the ability to be inflated to high inflation pressure without rupturing during balloon inflation. The thin walled shaft section provides a low profile shaft without sacrificing lumen size. Additionally, the polyamide layer provides an outer layer which is readily fusion bondable with polymeric materials commonly used in other catheter components such as balloons or shaft sections. Thus, the flexible and pushable distal shaft section provides a catheter with excellent trackability, and allows easy advancement over a guidewire and maneuvering within the patient's tortuous anatomy, to position the operative portion of the catheter at a desired location within the patient. These and other advantages of the invention will become more apparent from the following detailed description of the invention and the accompanying exemplary drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevational view of a catheter which embodies features of the invention.
FIG. 2 is an enlarged view, partially in section, of the portion of the catheter shown in FIG. 1 , taken within circle 2 .
FIG. 3 is a transverse cross sectional view of the catheter shown in FIG. 2 , taken along line 3 - 3 .
FIG. 4 is a transverse cross sectional view of the catheter shown in FIG. 2 , taken along line 4 - 4 .
FIG. 5 is an elevational view of an alternative embodiment of a catheter which embodies features of the invention, having a rapid exchange distal guidewire lumen.
FIG. 6 is a transverse cross sectional view of the catheter shown in FIG. 5 , taken along line 6 - 6 .
FIG. 7 is a transverse cross sectional view of the catheter shown in FIG. 5 , taken along line 7 - 7 .
DETAILED DESCRIPTION OF THE INVENTION
FIGS. 1-4 illustrate an over-the-wire type balloon catheter 10 embodying features of the invention. Catheter 10 generally comprises an elongated catheter shaft 11 having a proximal end, a distal end, a proximal shaft section 12 , a distal shaft section 13 , an outer tubular member 14 , and an inner tubular member 15 . Inner tubular member 15 defines a guidewire lumen 16 adapted to sliding receive a guidewire 17 , and the coaxial relationship between outer tubular member 14 and inner tubular member 15 defines annular inflation lumen 18 (see FIGS. 3 and 4 , illustrating transverse cross sections of the catheter 10 of FIG. 1 , taken along lines 3 - 3 and 4 - 4 , respectively). An inflatable balloon 19 is disposed on the distal shaft section 13 , having a proximal skirt section sealingly secured to the distal end of outer tubular member 14 , and a distal skirt section sealingly secured to the distal end of inner tubular member 15 , so that its interior is in fluid communication with inflation lumen 18 . An adapter 20 at the proximal end of the shaft is configured to provide access to guidewire lumen 17 , and to direct inflation fluid through arm 21 into inflation lumen 18 . Balloon 19 has an inflatable working length located between tapered sections of the balloon. FIG. 1 illustrates the balloon 19 in an uninflated configuration prior to inflation. The distal end of catheter may be advanced to a desired region of a patient's body lumen in a conventional manner, and balloon 19 inflated to perform a procedure such as dilatation of a stenosis.
In the embodiment illustrated in FIGS. 1-4 , the outer tubular member has a proximal section 25 , and a distal section 26 . As best illustrated in FIG. 2 , showing an enlarged longitudinal cross sectional view of the section of the catheter 10 shown in FIG. 1 , taken within circle 2 , the proximal section 25 is multilayered with a first layer 27 of a polyimide material and a second layer 28 of a material which is different from the first material, and which is preferably a polyamide material or a polyurethane. A presently preferred polyimide for the first layer is available from Phelps Dodge High Performance Conductors. Preferably, the polyimide is a thermoset polyimide with excellent dimensional stability, which thus has a cross linked 3-dimensional network maintained a high temperatures. A presently preferred polyamide for the second layer is PEBAX, available from Elf Autochem. A presently preferred polyurethane for the second layer is polyurethane N, available from Phelps Dodge High Performance Conductors. The second layer 28 is on an outer surface of the first layer 27 . As illustrated in the figures, the second layer 28 is a solid-walled layer, which is in direct contact with the first layer 27 around a circumference of the first layer 27 . Thus, the second layer 28 is not separated from the first layer 27 by an intermediate layer or braid, and is not itself a braid or mesh.
In the embodiment of FIGS. 1-4 , the second layer 28 of the proximal section 25 forms an outer surface of the multilayered section of the outer tubular member 14 . Thus, although a coating such as a lubricious coating conventionally used on catheter shafts may optionally be provided on at least a section of an outer surface of the multilayered shaft section, a structural or reinforcing layer is not on an outer surface of the second layer 28 in the embodiment of FIG. 1 . The first layer 27 forms an inner surface of the multilayered section of the outer tubular member 14 . An optional lubricious inner liner such as a PTFE or HDPE layer may be provided on an inner surface of the first layer 27 , as conventionally known for catheter shafts.
In the embodiment illustrated in FIG. 1 , the distal section 26 of the outer tubular member 14 comprises a single layered tubular member 29 , with a proximal end bonded to a distal end of the proximal section 25 of the outer tubular member 14 . In a presently preferred embodiment, the distal section 26 is formed of a polymeric material, such as polyether block amide (PEBAX), which is compatible with a polyamide material such as PEBAX and nylon, forming the second layer 28 of the proximal section 25 , to allow for fusion bonding the two sections together. However, a variety of suitable methods of bonding can be used including adhesive bonding. Additionally, although a lap joint is illustrated in FIG. 2 between the proximal and distal sections 25 / 26 , a variety of suitable joints may be used including a butt joint, or a lap joint in which the outer diameter of the proximal section 25 is reduced at the joint so that the distal section 26 is flush with the proximal section.
In an alternative embodiment (not shown), the multilayered section of the outer tubular member 14 is the distal section 26 , and the balloon proximal skirt section is fusion bonded to the second layer 28 of the outer tubular member 14 multilayered distal section.
FIGS. 5-7 illustrate an alternative embodiment of the invention, in which the balloon catheter 50 is a rapid exchange catheter with an outer tubular member 54 having a multilayered distal section 56 . A illustrated in FIG. 5 , catheter 50 generally comprises an elongated catheter shaft 51 having a proximal end, a distal end, a proximal shaft section 52 , a distal shaft section 53 , an outer tubular member 54 , and an inner tubular member 55 . Inner tubular member 55 defines a guidewire lumen 56 adapted to slidingly receive a guidewire 57 . Inflation lumen 58 is defined by the outer tubular member 54 . An inflatable balloon 59 is disposed on the distal shaft section 53 , having a proximal skirt section sealingly secured to the distal end of outer tubular member 54 , and a distal skirt section sealingly secured to the distal end of inner tubular member 55 , so that its interior is in fluid communication with inflation lumen 58 . An adapter 60 at the proximal end of the shaft is configured to direct inflation fluid into inflation lumen 58 .
In the embodiment illustrated in FIG. 5 , the outer tubular member 54 comprises a proximal section 61 , a distal section 62 , and a midshaft section 63 having a proximal end bonded to the proximal section 61 and a distal end bonded to the distal section 62 . A guidewire proximal port 64 in a side wall of the midshaft section 63 is in fluid communication with the lumen 56 of the inner tubular member 55 , and with a distal guidewire port in the distal end of the shaft. As shown in FIG. 5 , the guidewire 57 exits the catheter proximally from the guidewire proximal port 64 and extends alongside and exteriorly of the proximal section 61 to the proximal end of the catheter 50 . Although the guidewire proximal port 64 is in the midshaft section, in an alternative embodiment (not shown) it is located in the proximal section 61 or the distal section 63 . Additionally, in an alternative embodiment of rapid exchange catheter 50 , the outer tubular member 54 comprises the proximal section 61 directly bonded to the distal section 62 , without a midshaft section therebetween (not shown). A support mandrel 65 is disposed in the inflation lumen 58 , with a distal end distal to the guidewire proximal port 64 . The mandrel is typically a metal member, such as a stainless steel or NiTi member, enhancing the pushability of the catheter 50 .
In the embodiment illustrated in FIG. 5 , the distal section 62 of the outer tubular member 54 is a multilayered section with a first layer 67 of a polyimide material and a second layer 68 of a material which is different from the first material, and which is preferably a polyamide material. The multilayered distal section 62 is similar to the multilayered section of the catheter 10 discussed above in relation to the embodiment of FIGS. 1-4 , and the discussion above relating to the first layer 27 and second layer 28 of the multilayered proximal section 25 of catheter 10 applies as well to first and second layers 67 / 68 of the multilayered distal section 62 of catheter 50 . In a presently preferred embodiment, the second layer 68 of the multilayered distal section 62 of the outer tubular member 54 is a polyether block amide (PEBAX) material on the polyimide first layer 61 , providing a highly kink resistant and pushable rapid exchange catheter. Balloon 59 has a proximal skirt section bonded to the second layer 68 of the distal section 62 of outer tubular member 54 .
When the catheter of the invention is used in an angioplasty procedure, the balloon catheter of the invention is advanced over the guidewire until the balloon is properly positioned across the stenosis. The balloon can be inflated in a conventional manner by introducing inflation fluid through the inflation lumen. After one or more inflations, the balloon is deflated and the catheter removed from the patient. A similar procedure is used when the balloon has a stent (not shown) mounted thereon for implanting the stent in the body lumen.
The length of the dilatation catheter is generally about 137 to about 145 centimeters, and typically about 140 centimeters for PTCA. The outer tubular member 14 / 54 distal section has an outer diameter (OD) of about 0.028 to about 0.036 inch (0.70-0.91 mm), and an inner diameter (ID) of about 0.024 to about 0.035 inch (0.60-0.89 mm), and the outer tubular member 14 / 54 proximal section has an OD of about 0.017 to about 0.034 inch (0.43-0.87 mm), and an inner diameter (ID) of about 0.012 to about 0.022 inch (0.30-0.56 mm). The inner tubular member 15 / 55 has an OD of about 0.017 to about 0.026 inch (0.43-0.66 mm), and an ID of about 0.015 to about 0.018 inch (0.38-0.46 mm) depending on the diameter of the guidewire to be used with the catheter. In one embodiment, the polyimide layer is about 0.0005 inches (0.0127 mm) to about 0.0015 inches (0.038 mm) thick, and preferably about 0.0005 inches (0.0127 mm) to about 0.00075 inches (0.019 mm) thick, and the second layer (e.g., of polyamide or polyurethane) is about 0.00075 inch (0.019 mm) to about 0.00125 inches (0.03 mm) thick, preferably about 0.001 (0.025 mm) to about 0.00125 inches (0.03 mm) thick. In a presently preferred embodiment, the polyimide first layer has a smaller thickness than the second layer.
While the present invention has been described herein in terms of certain preferred embodiments, those skilled in the art will recognize that modifications and improvements may be made without departing form the scope of the invention. For example, while the catheter illustrated in the figures has coaxial inner and outer tubular members, other conventional catheter shaft configurations can be used along at least a section of the catheter, such as side-by-side, dual lumen configurations. Moreover, while individual features of one embodiment of the invention may be discussed or shown in the drawings of the one embodiment and not in other embodiments, it should be apparent that individual features of one embodiment may be combined with one or more features of another embodiment or features from a plurality of embodiments
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A catheter having an multilayered shaft section with a first layer formed of a polyimide first material and a second layer formed of a second material. In a presently preferred embodiment, the polyimide material is a thermoset polyimide. However, in alternative embodiments, a thermoplastic polyimide is used. The thermoset polyimide has a very high glass transition temperature (Tg) of approximately 400° C. (as measured by differential scanning calorimetry), and excellent dimensional stability at the processing temperature of polyamides commonly used in catheter components. As a result, during formation and assembly of the catheter, production of a thin polyimide layer with controlled dimensions is facilitated. The polyimide has a high modulus and provides a thin walled yet highly pushable shaft section, while the second layer provides kink resistance. In one embodiment, the second material is selected from the group consisting of a polyamide material and a polyurethane material.
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BACKGROUND OF THE INVENTION
The present invention relates to carbonless copy paper and coatings therefore containing load bearers and to methods for producing such coatings. More particularly, it relates to a coating slurry containing microencapsulated load bearers having a non-rupturable core material, which are produced in situ so as to be interspersed among rupturable, dye precursor-containing microcapsules and designed in such a way that when the slurry is coated onto the surface of a sheet of carbonless copy paper, a uniform, even distribution of rupturable and non-rupturable microcapsules results which, in turn, promotes a clear, sharp image on the copy paper.
The use of load bearers interspersed with rupturable, dye precursor-containing microcapsules on the CB (coated back) side of carbonless copy paper, or in self-contained carbonless systems, to prevent premature rupture of the dye precursor-containing microcapsules is well known. This technique prevents unwanted smudging and discoloration of the paper due to low pressures applied thereto during storage, transportation, and routine handling. Many attempts have been made to develop a suitable load bearer capable of protecting the dye precursor-containing microcapsules from premature rupture under low pressures yet able to avoid interfering with the production of a clear, sharp image upon the application of direct pressure to the paper substrate, such as from a pen or typewriter key, by not prohibiting the dye-precursor from flowing from the intentionally crushed microcapsule on the CB sheet to the CF (coated front) sheet directly below. The CB sheet is superimposed on top of the CF sheet and the CF sheet is coated thereon with a layer of color-developer which reacts with the dye-precursor to form an image. To the extent that this reaction mechanism is interfered with, the image thus produced will be blurred or broken.
The current approach to the problem of premature rupture is to add inert particles to the microcapsule slurry prior to coating. These particles, which serve as load bearers, are much larger than the microcapsules to give protection thereto from low pressures. Starch balls and cellulose floc are the most common materials chosen. This approach is represented by U.S. Pat. Nos. 3,996,061; 4,280,718; and 4,404,251. Other materials have also been tried. For example, Sandberg in U.S. Pat. No. 2,655,453 teaches the use of glass beads, rounded white silica sand, casein particles, and vinyl acetate polymer as load bearing materials.
Myers et al in U.S. Pat. No. 4,211,437 discloses the use of large agglomerates of kaolin as stilt material. While he refers to his invention as a kaolincontaining "capsule", it is not, in fact, a capsule but rather is an agglomeration of kaolin particles bound together in a very large coacervated mass (see FIG. 2). These agglomerates of kaolin are 2 to 12 times larger than the microcapsules used therewith (col. 2, lines 50-57), have 1/5 to 1/3 the weight of the microcapsules (col. 4, lines 23-26), and are produced in an entirely separate process from that used to produce the microcapsules.
Matsushita et al in U.S. Pat. No. 4,411,451 discloses the use of a wax coating on the CB sheet to improve the transferability of dye-precursor from the CB sheet to the CF sheet (by preventing the dye-precursor from being absorbed onto the CB paper substrate). However, Matsushita does not teach the use of wax for load bearing purposes. Rather, Matsushita states that traditional materials such as starch balls are used for load bearing purposes (col. 3, lines 23-29).
These traditional approaches to the problem of premature rupture have major disadvantages. Differences in density, particle size, and colloid stability between the microcapsules and the load bearers result in their separation or classification during storage, application, and drying. The separation of the microcapsule/load bearer slurry results in uneven coating on the CB sheet. Such uneven coating in turn reduces the clarity or sharpness of the image produced and/or results in a broken image.
In the case of starch, whose density equals 1.4 and particle size is 18 microns, the ratios of its density and particle size to that of the typical microcapsule, whose density equals 0.98 and size is 3 to 6 microns, are 1.4 and 6 to 3, respectively. As a result, on storage the starch particles tend to settle while the capsules remain suspended or float. The slurry must be thoroughly mixed before use, and the stirring maintained throughout the coating operation to ensure a uniform mixture. The large size ratio between the particles also means a strong tendency towards separation during application and drying. This characteristic is generally recognized as the result of velocity differences (different mobilities) among the differently sized particles in the coating currents produced during application and drying. The large particles collect in regions of little flow, and the smaller particles in regions of high flow. A poor coating pattern can easily result. This pattern in turn can reduce the clarity or sharpness of the image produced by the CB.
This separation can be further exacerbated by a second type of separation induced by differences in the flocculation rates between the two types of particles present. Since the microcapsule and the starch ball have different surface characteristics in terms of their chemical nature and polarity, their colloidal stabilities in a given binder solution at a specific viscosity are not identical. A different colloidal stability means different flocculation rates resulting in the formation of larger flocculants of one particle compared to those of the second type of particle. This non-uniformity again produces a poor coating pattern. Void spaces due to starch flocculants can occur which in turn produce a broken image, and an overall deterioration in image quality similar to those mentioned previously.
Unrelated to the problem of premature rupture is U.S. Pat. No. 4,416,966 to Sanders et al. This patent discloses the use of photohardenable compositions contained within rupturable microcapsules. Upon exposure to radiation, those microcapsules thus exposed become hardened and non-rupturable. This feature is used to facilitate the imaging process whereby discrete portions of an imaging sheet containing photohardenable microcapsules are exposed to radiation. The entire sheet is then subjected to a uniform rupturing force so that only the unexposed microcapsules rupture and thereby produces a desired image. U.S. Pat. No. 4,554,235 to Adair et al relates to an improvement to the Sanders et al invention by further producing a high gloss image. Neither of these patents teaches the use of hard microcapsules as load bearers. Rather, the Sanders et al and Adair et al inventions teach the use of hardened microcapsules as part of the imaging process. By the time the Sanders et al and Adair et al microcapsules are hardened, they have already been coated onto the CB sheet and those sheets have already been handled, transported, stored, etc. If a load bearing function were to take place in the Sanders et al or Adair et al inventions, the hard microcapsules would have had to have been present much earlier.
The need thus remains for an improved load bearer having similar size, density, and surface characteristics as the rupturable microcapsules slurried therewith so that a uniform, evenly distributed CB coating can be achieved which in turn promotes a clear, sharp image.
SUMMARY OF THE INVENTION
That need is met by the present invention which provides a carbonless copy paper and coating therefore containing microencapsulated load bearers and also provides a unique in situ method for producing such coatings. The method of the present invention produces microencapsulated load bearers which are sufficiently similar to the rupturable, dye precursor-containing microcapsules randomly coated therewith on a CB sheet, so that a uniform, evenly distributed CB coating of rupturable and non-rupturable microcapsules is achieved.
The present invention eliminates the deficiencies of the prior art by using hardened, non-rupturable microcapsules as load bearers instead of using a foreign material for this purpose. Such load bearing microcapsules can be created by dispersing an oil-wettable core material of the appropriate particle size into an oily solution, i.e. an oil/dye-precursor mixture which in the preferred microencapsulation method has a reactant dissolved therein. This mixture is known as, and will become, the internal phase of the resultant microcapsules. The preferred core material to be used is wax. The internal phase is next emulsified as droplets into an aqueous solution, known as the external phase, which may include emulsifier(s) and protective colloid(s) and in the preferred method a coreactant for interfacial polymerization with the reactant. The emulsion thus formed contains two types of droplets. The first type of droplet consists of the oil/dye precursor mixture while the second type consists of a core particle surrounded by a film of the oil/dye precursor mixture. The size distribution of these droplets can be controlled to achieve a specified value by varying the flow rate of the internal phase through the emulsifier (dwell time), speed of the emulsifier (frequency), and the inlet/outlet pressures of the internal phase through the emulsifier.
Since the droplets containing the core material can only be reduced to a size approaching the primary particle size of the core particle, a binary distribution of droplets can be achieved containing oil/dye precursor at one size, and another size of droplets containing a core particle covered with a thin film of oil/dye precursor. Thus, by selecting appropriately sized core Particles and by varying the aforementioned parameters, the size difference between the two droplet types can be controlled so that the soon-to-be-formed load bearing microcapsules are only slightly larger than their accompanying oil/dye precursor-containing microcapsules. Preferably, the load bearing microcapsules are 1 to 2 times and most preferably about 1.5 times the size of the dye precursor-containing microcapsules. Preferably the microencapsulated load bearers have a diameter of between 3 and 12 microns while the core particle has a diameter of around 1-10 microns. By sizing the load bearing microcapsules to be only slightly larger than the dye precursor-containing microcapsules, the aforementioned problems associated with binary mixtures having large size differences between particles (separation during application and drying) are greatly minimized. This feature of the present invention thus represents an improvement over the prior art.
The microencapsulation process is performed on the droplets using any of the known methods of the prior art such as complex coacervation (illustrated by U.S. Pat. No. 2,800,456), interfacial polymerization (see, e.g., U.S. Pat. No. 3,432,327), or in situ polymerization (see, e.g., U.S. Pat. No. 4,089,882). Regardless of which method is employed, a microcapsule wall is formed at the oil/water interface of each droplet. A slurry of microcapsules are thus produced which can be classified into two types: a rupturable microcapsule containing therein a oil/dye precursor solution and a second larger, non-rupturable microcapsule containing therein a hardened core particle. These load bearing microcapsules are non-rupturable during storage, transportation, and handling of CB sheets coated thereon with the load bearing microcapsules due to the mechanical strength of the core material augmenting the strength of the wall.
As stated above, the preferred core material for the microencapsulated load bearers is wax. However, other oil-wettable materials such as polystyrene or silica may be used provided they can be readily dispersed into the internal phase without dissolving. Preferably, the core particle is selected such that its density matches or closely approximates that of the oil/dye precursor mixture. In the case of wax, for example, its density is approximately 0.94 and the density of a typical dye precursor solution is approximately 0.96. In this instance, the densities of the load bearing and dye precursor-containing microcapsules will be nearly equal. As hereinabove stated, one of the shortcomings associated with the load bearers found in the prior art is that the density differences between these load bearers and the microcapsules used therewith results in the stratification of the product during storage. Thus, the present invention provides another improvement over the prior art by providing load bearers with densities similar to those of the dye precursor-containing microcapsules slurried therewith so that a slurry consisting of the two particles will not stratify during storage.
The microencapsulated load bearers are made in situ with about 1 to 20% by weight of core material dispersed in the oily solution. That is to say, the microencapsulated load bearers and the dye precursor-containing microcapsules are concurrently encapsulated in the same process. Thus, the microcapsule wall material of both particles is identical. The surface characteristics of both types of microcapsules are therefore identical as well. Since the surface characteristics of the two microcapsules are the same, their colloidal stabilities and therefore rates of flocculation in solution will also be the same. Equal flocculation rates mean that the microencapsulated load bearers of the present invention and dye precursor-containing microcapsules will not group together in a slurry to form separate flocculants of like particles (which produces an uneven coating pattern and results in a broken image). Rather, the microencapsulated load bearers evenly distribute themselves in the solvent vehicle among dye precursor-containing microcapsules and thereby promote an evenly distributed CB coating. The result is a clean, unbroken image. This feature of the present invention represents yet another improvement over the prior art.
The present invention thus provides an improved load bearer capable of preventing the premature rupture of dye precursor-containing microcapsules while promoting, rather than interfering with, an evenly distributed CB coating of rupturable and non-rupturable microcapsules. Moreover, no particle separation or classification is likely to occur during storage, application onto a support sheet, or drying. The final result of the present invention, then, is a carbonless copy paper wherein production of a clear, sharp image free from smudging and discoloration is enhanced.
Accordingly, it is an object of the present invention to provide an improved carbonless copy paper sheet in the form of a support having thereon a coating containing microencapsulated load bearers, to provide a unique coating for producing such carbonless copy paper, and to provide a method for producing the coating.
These and 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 and the appended claims.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
To make microencapsulated load bearers of the present invention, appropriately sized core particles are dispersed into the oily solution of the internal phase prior to emulsification. The internal phase preferably consists of an oily solvent, a colorless, chromogenic dye precursor and a reactant such as a cross-linking agent, all as disclosed in copending application Ser. No. 141,633 filed Jan. 7, 1988, the disclosure of which is hereby incorporated by reference. A suitable concentration of the core particles in the internal phase is 1 to 20% by weight of the internal phase. An emulsifier is then used to disperse the internal phase into the external phase as droplets. The external phase is preferably an aqueous solution which may include protective colloid(s) and emulsifier(s) (if any), and a coreactant of the type also disclosed in application Ser. No. 141,633. While the interfacial polymerization encapsulation materials and material disclosed in Ser. No. 141,633 are preferred, other encapsulation systems such as complex coacervation and in situ polymerization may also be used.
As disclosed in Ser. No. 141,633, the microcapsules are formed using a polyelectrolyte complex or a polysalt consisting of 1) a high molecular weight polyanion, i.e., an alkali-soluble polymer with repeating units containing carboxylic, phosphoric, or sulfonic acid groups and/or amino acid groups, such as casein, sodium caseinate, zein, soya protein, polyacrylic acids, acrylic acid copolymers, maleic acid copolymers, and maleic anhydride copolymers and 2) a low molecular weight polycation having a molecular weight of less than 1200 such as a polyamine with a functionality of at least 3. The preferred polycation is a polycationic polyamine such as diethylene triamine and the preferred polyanion is casein.
An internal phase containing the dispersed core particles and an oily solution including a dye precursor and containing a crosslinking agent is dispersed into an aqueous solution of the polyanion. The crosslinking agent may be a polyisocyanate, a polyacid polychlorofoamate, or a polyaldehyde. The preferred crosslinking agent is a polyisocyanate. The polycation may be added before or after such dispersing steps. The crosslinking agent reacts with the polyamine-polyanion complex to form a strong, thick-walled capsule. Heat treatment accelerates the crosslinking. A denatured crosslinked layer of polyanion builds up around the droplet, thus producing a tough, thick capsule wall.
The key to the present invention is the dispersion of a hardenable core material in the internal phase. The preferred material to be used for core particles is wax. Examples of suitable waxes include micronized polyolefin waxes made from polyethylene or polytetraflouroethylene, microcrystalline wax, and Fischer-Tropsch waxes. Other oil-wettable materials such as polystyrene or silica may also be used provided they can be readily dispersed into the internal phase without dissolving.
Regardless of the type of material chosen for the core particles, the size of said core particles lies in the 1 to 10 micron range and is based on the desired size of the rupturable microcapsules used therewith. Specifically, the size of the core particles is slightly larger than the desired size of the oil/dye precursor droplets (whose size can be controlled by varying the emulsifier dwell time, frequency, and inlet/outlet pressures as hereinabove described) so that a load bearing microcapsule to rupturable microcapsule size ratio of 1-2 is achieved. The preferred load bearing microcapsule to rupturable microcapsule size ratio is 1.5.
As with size, the density of the core particles is also a function of the rupturable microcapsules used therewith. Core particles are selected such that the density thereof equals or approximately equals the density of the oil/dye precursor mixture. After microencapsulation of the core particle and dye precursor droplets, then, the densities of the two microcapsules will be equal or nearly equal.
The microencapsulated load bearers of the present invention and the dye precursor-containing microcapsules made therewith may be combined with an aqueous binder solution (i.e., the preferred solvent vehicle) and coated on a support to form a carbonless copy paper sheet which is preferably a CB sheet but may also be a self-contained or CFB sheet. When used as such, said load bearing microcapsules are evenly interspersed with said dye precursor-containing microcapsules on the carbonless copy paper sheet such that the dye precursor-containing microcapsules are protected by the load bearing microcapsules from premature rupture during routine storage, transportation, and handling of the carbonless copy paper sheets. In this manner, load bearing microcapsules thus prevent the carbonless copy papers from becoming smudged or discolored. The main advantage of the present invention over traditional load bearers is that a clear, sharp image, free from broken lines, is produced when the dye precursor-containing microcapsules are intentionally ruptured, as with a pen or typewriter key. The microencapsulated load bearers of the present invention facilitates such a clear image by promoting a uniformly distributed slurry of load bearing and dye precursor- containing microcapsules during the storage, CB coating, and drying thereof. Such a uniform distribution is made possible due to the similarity of the microencapsulated load bearers of the present invention and the dye precursor- containing microcapsules slurried therewith.
The following non-limiting example will more clearly define the invention.
EXAMPLE 1
A. Internal Phase. In a 2L beaker containing 682 g of disopropyl naphthalene, 66.0 g of Pergascript Green I-2GN, 35.6 g Pergascript Red I-6B, and 62.09 g Pergascript I-BR Black (all dye-precursors from Ciba-Geigy of Greensboro, North Carolina) were dissolved. The mixture was heated to 115° C. and 217g of Norpar 13 Special (an aliphatic solvent from Exxon of Baytown, Tex.) was added. The mixture was then cooled to room temperature. Dispersed into this solution was 44.1 g of MP 22 XF wax particles (primary particle size 3 m average and 8 m maximum from Micro Powders Corporation of Yonkers, New York). 72.0 g of Desmodur N-3200 (a biuret containing polyisocyante from Mobay Chemical Corporation of Pittsburgh, Pa.) was added and stirred until it dissolved.
B. External Phase. In a 4 L beaker containing 1064 g of water, 90 g of PVP-K30 (polyvinyl pyrrolidone with a molecular weight of 40,000), 555 g of methyl glucoside, and 13.5 g of borax was dissolved at room temperature. Into this clear solution, 90 g of casein was dispersed and heated to 65° C. After 30 minutes at 65° C., the casein dissolved and the solution was cooled to room temperature.
C. Encapsulation. The aqueous solution (B) was placed in a Waring blender connected to a Variac. With the blender set on low and the Variac at 60%, the oily solution (A) was poured into the vortex within a period of 30 seconds. After the addition was complete, the Variac was set to 90%, and the blender was allowed to run for an additional 30 seconds. The emulsion was then transferred to the 4 L beaker and stirred moderately to produce a slight vortex. Then, 14.9 diethylene triamine in 14.9 g of water was added to the emulsion. The mixture was heated to 60° C. and held at that temperature for 2 hours.
When coated at 0.5#/R (17×22), the CB coating produced an intense black image upon rupture of the microcapsules and remained free of discoloration with normal handling.
It will be obvious to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.
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Microencapsulated load bearers to prevent the premature rupture of dye precursor-containing microcapsules are formed concurrently in the same microencapsulation process in which oil/dye precursor-containing microcapsules are formed by emulsifying an oily mixture, containing therein a dye-precursor solution and non-rupturable core particles, as droplets into an aqueous solution. The core particle and oil/dye precursor droplets are then microencapsulated to form a binary microcapsule mixture consisting of microencapsulated load bearers and oil/dye precursor-containing microcapsules, respectively. This binary microcapsule mixture in an appropriate solvent vehicle may be used as a coating for the preparation of carbonless copy paper.
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FIELD OF INVENTION
The invention relates to a bridge intended in particular for crossing a channel of a waterway and having a part in the form of a span, which can be moved by vertical translation between a low position for crossing the channel, in which the span rests on stationary support parts of the bridge, and a high position for opening the channel, and a support structure for the span during its movement as well as some means for lifting the span.
BACKGROUND
Bridges of this type that are known have the major disadvantage of having a complex structure requiring much space, inasmuch as they have, on each side of the channel, a support structure that requires extensive installation work particularly when the structure is in the water, and that must be equipped with lifting means that must be powered and perfectly coordinated, which requires sophistication in the design of these means.
SUMMARY OF THE INVENTION
The present invention provides a bridge that does not have the disadvantages just set forth.
To attain this aim, a bridge according to the invention has only one support structure, provided with lifting means, which is arranged on just one side of the channel to be crossed.
According to one characteristic of the invention, the lifting means entails a traction cable, one end of which is attached to the span and the other end of which is connected to a traction device, running over pulleys that are part of the support structure.
According to another characteristic of the invention, the two lifting cables are attached to each side of the span and run over a pulley mounted on the support structure in a vertical plane passing through the middle of the span.
According to yet another characteristic of the invention, the support structure has two girder support pylons each provided at its free end with a pulley over which cables for lifting the span run.
According to yet another characteristic of the invention, the pylons and the girders are provided with reinforcement elements such as girders or stay cables.
According to yet another characteristic of the invention, the means for lifting the span entail a balance arm mounted to pivot on a support structure from one end of which the span is suspended, whereas some pivoting actuation means are connected at the other end.
According to yet another characteristic of the invention, the span is a self-supporting structure suspended from the end of the balance arm by suspension cables.
According to yet another characteristic of the invention, the span has a lightened structure, borne by a multiple of stay cables, in a low position for crossing the channel as well as in a high position for opening the channel, the stay cables being suspended from end of the balance arm.
According to yet another characteristic of the invention, a balance arm includes two levers with two arms that are both mounted to pivot on a pylon while being connected, if necessary, by a crosspiece.
According to yet another characteristic of the invention, the weight of the span is at least partially counterbalanced by counterweights.
BRIEF DESCRIPTION OF DRAWING FIGURES
The invention will be better understood, and other aims, characteristics, details and advantages of it will appear more clearly in the course of the following explanatory description in reference to the appended drawings given only as examples illustrating two embodiments of the invention and in which:
FIGS. 1 and 2 are perspective views of a first embodiment of a bridge according to the invention, the bridge occupying its low position for crossing the channel of a waterway;
FIGS. 3 and 4 are perspective views of the embodiment according to FIGS. 1 and 2 but show this bridge in its high position for opening the channel;
FIGS. 5 and 6 are perspective views of two different versions of the bridge according to FIGS. 1-4 ;
FIGS. 7 and 8 are perspective views illustrating a second embodiment of a bridge according to the invention in its position for crossing the channel;
FIG. 9 is a perspective view of the bridge according to FIGS. 7 and 8 but shows the bridge in its high position for opening the channel;
FIG. 10 is a perspective view of a bridge with two spans according to FIGS. 7-9
FIGS. 11 and 12 are perspective views of another version of the second embodiment of a bridge according to the invention, illustrating the bridge in its position for crossing the channel;
FIG. 13 is a perspective view of the bridge according to FIGS. 11 and 12 but illustrating the bridge in its high position for opening the channel;
FIG. 14 is a perspective view of a version of the second embodiment of a bridge according to the invention, which has two mobile spans, one of which is represented in its position for crossing the channel and the other of which is represented in its high position for opening the channel;
FIG. 15 is a top view of the bridge according to FIG. 14 , but where the two spans occupy their position for crossing the channel, and
FIG. 16 is a diagrammatic side view of yet another embodiment of the invention.
DETAILED DESCRIPTION
As illustrated by the figures, a lifting bridge 1 according to the invention, intended for enabling one to cross channel 2 of a maritime waterway, has a roughly horizontal mobile part in the form of span 3 , which can be moved by translation roughly vertically between a low position for crossing channel 2 and a high position for opening the channel, and stationary parts 4 , 5 on both sides of span 3 and on which the latter is supported at 7 and 8 by its two ends 9 and 10 in position for crossing. The bridge also has structure 12 for support of span 3 during its movement between its two positions for crossing the channel and for opening the channel, and some means 14 controlling the movement of the span, hereafter called lifting means.
As seen in the figures, lifting bridge 1 according to the invention has just one support structure 12 and just one lifting control device 14 , which are mounted on just one side of channel 2 to be crossed, namely, in the example represented, on stationary part 5 . This stationary support part, in the examples represented, is on one of the banks of the waterway but could also be provided in the waterway.
According to a first embodiment represented in FIGS. 1-6 , support structure 12 is stationary and essentially includes, on each lateral side of span 3 , vertical pylon 16 anchored at its lower end in stationary bank part 5 and which bears, at its upper end, girder 17 extending from the pylon, inclined upward, up to approximately the middle of span 2 , and girder 18 extending upward at approximately a right angle with respect to girder 17 .
Span 3 is suspended mainly during lifting from the free end of each girder 17 by the intermediary of two lifting cables 20 , 21 fastened through an end of span 3 and running over pulley 23 mounted on the end of girder 17 , along this girder, over another pulley 24 situated at the top of the pylon, and then inside of pylon 16 to traction device 25 arranged at the foot of this pylon. This device could be a winch for winding or unwinding of lifting cables 20 , 21 , or any other suitable traction device such as a jack. In order to ensure the horizontal position of span 3 , each lifting cable 20 , 21 is attached to span 3 at one end of the span.
Given that the span is thus suspended from the free ends of girders 17 , the end of each girder is held by stay cable 27 that extends between this end and the free end of holding girder 18 , on one hand, and between these ends and stationary part 5 of the bridge on which it is attached at 28 an appropriate distance from the foot of pylon 16 in the plane formed by this pylon and suspension girder 17 and holding girder 18 . In order to reinforce the support structure of the span, the upper end of each pylon 16 is held in position by reinforcing leg 30 that extends between the upper end of the pylon and the stationary part in the above-mentioned plane, as seen in FIGS. 1-4 , or by two stay cables 32 according to FIG. 5 . FIG. 6 shows yet another version of the device for reinforcing the support structure, which, in the extension of the suspension girder 17 , beyond pylon 16 , has girder part 36 whose end is held to stationary part 5 by stay cables 37 and which also serves as anchoring place for stay cable 27 for holding the free end of suspension girder 17 . Of course, girders could also be used in place of stay cables 27 and 37 .
It is observed that support structure 12 can possibly consist of framing members situated on the side of span 3 , which are independent or connected by any type of connection. In general, any geometry can be applied to this structure.
The weight of span 3 suspended from support structure 12 can be 1 to varying degrees balanced by counterweights acting continually or only during lifting. These counterweights, such as those indicated at 39 , for example, are placed in the traction cables and, like these cables, are thus inside the pylons. Of course, any other suitable solution for the counterweights and traction cables can be considered. The counterweights could in particular be “disengaged” and the cables relaxed when the span is in position for crossing the channel.
Span 3 can be a self-supporting structure of the lattice, box, Warren girder or Bow string type or the like.
It should also be noted that the span, during its movement, is held at its corresponding end in contact with pylons 16 and is thus guided at just one end.
FIGS. 7-15 illustrate several versions of a second embodiment of a bridge according to the invention.
This second embodiment is characterized by the fact that the lifting of span 3 is ensured by the tilting of balance arm 42 mounted so as to pivot at the top of pylons 16 . The pivoting of the balance arm takes place on rotational bearings, pivot pins, hard bearing or any other tilting mechanism. This balance arm is formed by two two-armed levers 43 connected together, for example, by crosspiece 45 at the ends of front arms 44 , from which span 3 is suspended by suspension cables 46 , whereas at each free end of rear arm 44 ′, whose length can be different from that of the front arm, traction cables 48 are connected, actuated by a traction device of any appropriate nature such as winches or jacks 50 . This traction device can be associated with a device for anchoring of the balance arm in stationary part 5 , such as cables, bars, or portals, which immobilizes the tilting of the balance arm when the span is in position for crossing the channel and which does not hinder the action of the traction device during lifting. In order to counterbalance the weight of the span at least partially, counterweight 52 can be inserted between the end of the edge of lever 44 ′ and each cable 48 . Each two-armed lever 43 has, at the site of the tip of support pylon 16 , transverse girder 54 that projects upward and makes it possible to prevent bending of the lever due to stay cables 56 and 57 attached between the end of girder 54 and the ends of suspension arm 44 and traction arm 44 ′ of levers 43 .
Given that during its movement under the effect of the tilting of balance arm 42 , between its two positions for crossing channel 2 and for opening the channel, the span describes a slight arc of circle in the vertical plane, each pylon 16 has guide path 59 consequently curved on which the adjacent end of span 3 rests. A device for horizontal movement of the mechanism for pivoting the balance arm during lifting could enable one to avoid the curvature of this guide path.
FIG. 10 shows a bridge structure that has two separate and independently lifted spans 3 , 3 ′. Each span is suspended from balance arm 42 as described in the preceding. The two balance arms could be mounted on two pairs of pylons 16 or on a device with three pylons of which the central pylon indicated by 16 ′ in FIG. 10 would then be shared by the two balance arms.
In reference to FIGS. 11-15 , a particularly advantageous implementation version of the embodiment of the bridge, with lifting of the spans by tilting of a balance arm, will be described hereafter. In this implementation version, span 3 is a cable-stayed structure, that is to say borne by multiple stay cables 62 in position of operation, that is to say in its position for crossing represented in FIGS. 11 and 12 , as well as in lifting position according to FIG. 13 , which allows simplification of the structure of the span, and particularly lightening of the weight, as emerges from the FIGS. since the span no longer needs to be self-supporting. A reduction of the weight of the span is thus obtained.
As illustrated by FIG. 14 , this implementation version of the span in the form of a cable-stayed span can also be applied to a bridge with two spans, according to FIG. 9 .
Another very advantageous embodiment is represented in FIG. 16 . In this embodiment, the span is suspended from balance arm 42 by the intermediary of the suspension device indicated by 64 not at its center of gravity symbolized by arrow 65 , but rather from a site offset from center 65 in the direction of pylons 16 , so that when the span is lifted, it has a tendency to tilt in the direction of arrow 66 . The amplitude of this offsetting identified in the figure by the letter “a” is determined as a function of the maximum wind effects that can possibly act on the system,
Rotation thus brought about by the span, when it is lifted, in the direction of arrow 66 , is prevented by pulling the span downward on its end on the pylon side 68 by means of a pair of cables 69 each of which can be wound on winch 70 or unwound from the winch. Each winch 70 arranged at the foot of pylon 16 unwinds its cable as the lifting of the span progresses in order to follow its position and to ensure its stability regardless of the wind conditions. During the lifting, the span is thus stabilized in all directions both by its suspension from the balance arm and by the follower cable that regulates the rotation of the suspension/span assembly under the balance arm while preventing any untimely pendular motion. For this purpose, the unwinding or winding movements of winches 50 are under the control of the tilting of the balance arm.
It should be noted that the tilting in the direction of arrow 66 could also be occasioned by a weight added at the end of the span away from the pylons, as diagrammatically indicated at 71 . This version has the advantage that the suspension of the span can take place at its center of gravity.
Of course, multiple modifications can be made to the bridge as represented in the figures. Thus, the support structures can be designed differently, while taking care that the constitutive elements of these structures are preferably acted upon by traction or compression. The counterweights could be placed differently, integrated or not in the support structures, for example, integrated in the balance arms. In this way also, any type of arrangement for the sheets of stay cables and particularly their number can be considered.
It should be noted that the invention allows the execution of bridges with very long spans whose length can possible reach 100 m or more.
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A bridge for crossing a passage of a navigation channel includes a section in the form of a single span, which may be displaced by vertical translation between a base position spanning the passage, in which the span rests on fixed support sections of the bridge, and a raised position, for opening the passage, and a support structure for the span on displacement of the span, and a drive for lifting the span. The bridge has only one support structure, with the drive, located on one side of the passage to be spanned.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of German patent application DE 10 2010 022 211.9, filed May 20, 2010, herein incorporated by reference.
FIELD OF THE INVENTION
[0002] The invention relates to a yarn sluice for sealing a yarn treating chamber under excess pressure.
BACKGROUND OF THE INVENTION
[0003] It is known to subject yarns, for example after twisting or after cabling, to a thermal treatment and to thus achieve an improvement in the yarn quality. A thermal treatment of this type stabilizes the state of the yarns after the twisting or cabling and frees the yarns from inner torsional forces. Moreover, a thermal treatment of this type leads to a shrink bulking of the yarns, which brings about an increase in the volume of the yarn.
[0004] Various methods and mechanisms for the thermal treatment of yarns are described in the patent literature. It has been known, for a long time in this connection, for example, to send yarn wound on bobbins or cops in batches for thermal treatment into steam systems, so-called autoclaves and to thus simultaneously set a large number of bobbins or cops. These known setting devices, however, have the drawback that they require a relatively large amount of space and are also comparatively expensive to acquire. Moreover, qualitative losses of the yarn treated can often not be avoided in these setting devices.
[0005] Furthermore, yarn treating devices are known, which are arranged directly in the region of the workstations of twisting machines and with which setting can be carried out on the traveling yarn. There has been success in making the setting process of yarns more economical and efficient using yarn treating devices of this type described, for example, in European Patent Publication EP 1 348 785 A1 or in German Patent Publication DE 103 48 278 A1.
[0006] The known devices generally in each case have a yarn treating chamber, into which a gaseous or steam-like treating medium under pressure is blown, the subsequent process of cooling leading to the setting of the yarn. Yarn treating chambers of this type are also equipped with opposing yarn inlet and yarn outlet openings, in the region of which respective sealing devices are installed which seal the yarn treating chamber relative to the environment.
[0007] The yarn treating device described in European Patent Publication EP 1 348 785 A1, for example, has sealing devices, which have various rollers, with which pressure losses being produced when the yarn is running into or out of the yarn treating chamber are to be minimised. These sealing devices preferably have drivable outer sluice rollers and inner sealing rollers, which are in each case equipped with a resilient plastics material ring, into which the yarn is pressed when passing the sealing devices.
[0008] However, the comparatively wear-sensitive plastics material rings of the sealing rollers are disadvantageous in these sealing devices. The relatively short service life of the plastics material rings requires short service intervals, which has a very negative effect on the efficiency of the yarn treating device.
[0009] A yarn treating device is described in German Patent Publication DE 103 48 278 A1, in which the yarn treating chamber, in the region of its yarn inlet and yarn outlet opening, in each case has a yarn sluice with wear-resistant yarn guide elements. In a first embodiment of the yarn sluice, the latter is equipped with two identical, in each case semi-circular, yarn guide elements, which are pressed against one another by a spring element and have, in the region of a common centre longitudinal axis, recesses which form a yarn guide channel. The cross-section of the yarn channel is, in this case, precisely matched to the mean thickness of the yarn to be treated, in other words during operation, the yarn guide channel is sealed by the traveling yarn. When there is a yarn thickening, the yarn guide elements are pressed outwardly against the force of the spring element, so the yarn with the yarn thickening can also pass through the yarn sluice.
[0010] In a further embodiment also described in German Patent Publication DE 103 48 278 A1, the yarn guide elements of the yarn sluice are configured in such a way that one of the yarn guide elements is rotatably mounted in the manner of a revolver. In other words, by corresponding positioning of the rotatably mounted yarn guide element, the cross-section of the yarn guide channel can be adjusted. The configuration and arrangement of the yarn guide elements in this case allows a selection to be made between four different cross-sections of the yarn guide channel. In this embodiment as well, one of the yarn guide elements, preferably the rotatably mounted yarn guide element, is arranged in such a way that it can move aside when a yarn thickening occurs.
[0011] However, it is disadvantageous in the known yarn sluices that adaptation of the cross-section of the yarn guide channel to the respective thickness of the yarn is often relatively complex or an exact adaptation of the cross-section of the yarn guide channel to the respective yarn diameter is frequently not possible. In other words, in the first embodiment, in the event of a batch change, in which a change is made to a yarn with a different mean thickness, the yarn guide elements also generally have to be replaced, in other words, the installed yarn guide elements have to be replaced in a time-consuming manner by new yarn guide elements which fit the mean thickness of the new yarn.
[0012] In the second embodiment as well, in which a selection can be made by the rotatably mounted yarn guide element between four yarn guide channel sizes, difficulties can occur when the yarn has a mean thickness which does not correspond precisely to one of the adjustable yarn guide channel sizes. In other words, in a case such as this, problems are also often produced with regard to a proper sealing of the yarn treating chamber. It has moreover been shown that with the known yarn sluices, in particular with yarn sluices with a rotatably mounted yarn guide element, difficulties occasionally occur when yarn thickenings run through, because, for example, the mounting of the rotatably mounted yarn guide element cannot react sufficiently resiliently to yarn thickenings of this type. Difficulties of this type often result in damaging tensile force increases and problems in the sealing of the yarn guide channel.
SUMMARY OF THE INVENTION
[0013] Proceeding from the aforementioned prior art, the invention is based on the object of developing a yarn sluice, with which, under all operating conditions, in other words, regardless of the mean thickness of the yarn and the virtually inevitable yarn thickenings, a reliable sealing of a yarn treating chamber can always be ensured during the thermal setting of a yarn.
[0014] This object is addressed according to the invention by a yarn sluice for sealing a yarn treating chamber under excess pressure, in which a traveling yarn is thermally treated. The yarn sluice comprises in the region of a yarn inlet opening and a yarn outlet opening of the yarn treating chamber yarn guide elements forming a yarn guide channel which is sealed by the traveling yarn in the operating state. At least one of the yarn guide elements is positionable for adaptation to the mean thickness of the traveling yarn in various, predetermined positions. Means is provided which allows temporary adaptation of the yarn guide channel cross-section to yarn defects. According to the invention, at least one of the first and second yarn guide elements forming the yarn guide channel is steplessly adjustably mounted for adaption to the mean thickness of the yarn to be processed, and a sealing element, which can be placed on the first and the second yarn guide element, extends along the yarn guide channel for closing the yarn guide channel and for reacting resiliently to defects in the traveling yarn.
[0015] The configuration of the yarn sluice according to the invention has the advantage that because of the steplessly displaceably mounted first guide element, an exact adaptation of the width of the yarn guide channel to the mean thickness of the yarn to be processed is possible and it is also ensured by the resilient sealing element resting on the yarn guide elements that yarn thickenings can pass through the yarn sluice without causing a notable pressure loss in the yarn treating chamber under excess pressure. In other words, the sealing element resting on the yarn guide elements ensures, on the one hand, that the yarn guide channel is securely closed during operation over its entire length and, on the other hand, the sealing element reacts resiliently to defects in the traveling yarn immediately. By using the resilient sealing element, it is therefore ensured that yarn defects, such as, for example, neps or splices, when running through the yarn sluices, do not lead to a significant tensile force increase nor do sealing problems occur. The sealing element is, in each case, only resiliently deformed by a yarn defect in the region of the yarn defect and, in the process, slightly spaced apart from the yarn guide elements, which merely leads to very small, virtually insignificant pressure losses.
[0016] With a yarn sluice configured according to the invention, a secure sealing of the yarn treating chamber, which is under excess pressure, relative to the environment is therefore ensured in all operating states.
[0017] In an advantageous embodiment it is provided that the steplessly adjustably mounted first yarn guide element is connected to a drive, which can be activated in a defined manner and is in turn connected to a control and/or a regulating device. A configuration of this type does not only allow a sensitive, very precise positioning of the first yarn guide element and therefore a very precise adjustment of the width of the yarn guide channel to the mean thickness of the yarn, but also good reproducibility of the process, as the yarn guide element at each adjusting process can always be positioned in a precisely predeterminable position that is optimal for the process.
[0018] This good reproducibility of the adjustment can be easily realised, in particular when the drive of the yarn sluice is configured as a stepping motor and a sensor device, with which the zero position of the stepping motor can be controlled, is present in the region of the drive.
[0019] Stepping motors of this type, as is known, require only a relatively small control outlay with respect to the precise adjustment of their angle of rotation.
[0020] In an alternative embodiment, however, it is in principle also possible to manually position the steplessly adjustably mounted yarn guide element. A manual positioning of this type is in fact very economical, but poses the risk of incorrect adjustments occurring. Moreover, a manual positioning of the displaceably mounted yarn guide element is time-consuming.
[0021] The steplessly adjustably mounted first yarn element is configured, in an advantageous embodiment, as a yarn guide wedge, which is displaceably mounted in an also wedge-shaped recess of a sluice insert of the yarn sluice. The sluice insert, in this case, also forms the fixed second yarn guide element of a yarn guide channel. As the yarn guide wedge can only move along the oblique contact line of the wedge-shaped recess, it is ensured by a configuration and arrangement of this type that the yarn guide elements forming the yarn guide channel are always oriented parallel to one another, in other words, it is always ensured that the yarn guide channel, in each position of the yarn guide wedge, adopts a width which is the same over the entire length of the yarn guide channel.
[0022] The yarn sluice may have a sealing element, which is configured and arranged in such a way that the system pressure prevailing in the yarn sluice acts on the sealing element and keeps it abutting on the yarn guide elements during the yarn treating process.
[0023] This ensures that the sealing element over the entire yarn guide channel length is resiliently positioned on the yarn guide channel with a uniform contact pressure.
[0024] If necessary, in particular to thread and unthread a yarn into or from the steam setting device, the sealing element of the respective yarn sluice can be positioned without problems spaced apart from the yarn guide elements of the yarn guide channel of the yarn sluice in that an angle lever carrying the sealing element is pneumatically pivoted from its working position into a threading position located slightly spaced apart from the yarn guide elements.
[0025] The sealing element resting on the yarn guide elements, which is equipped with a flexible, low-wear sealing band made of a metallic material and has a resilient intermediate insert made of a temperature-resistant resilient material, for example, foam, rubber, silicone rubber or the like, and arranged below the sealing band, during the yarn treatment ensures, on the one hand, that the yarn guide channel is properly closed and, on the other hand, yarn thickenings, such as neps or splices, which are located in the traveling yarn, cannot lead to a tensile force increase, as the resilient intermediate layer of the sealing element when running through a yarn thickening of this type, automatically resiliently moves away in the region of the yarn thickening. In other words, even a yarn which has a yarn thickening can pass through the yarn sluice without problems. As the resilient moving away of the intermediate layer always only takes place in the direct region of the yarn thickening and the sealing band protecting the intermediate layer is held in a sealing manner on the yarn guide elements over the remaining yarn guide channel length by the intermediate layer, the pressure loss of the relevant yarn sluice caused by a yarn thickening is extremely small.
[0026] In a particularly advantageous embodiment, the sealing element is configured as a slotted strip, in the receiving slot of which is fixed an H-shaped, resilient intermediate insert, with play. The intermediate insert is also covered here by a flexible, wear-resistant sealing band and thus protected against wear by the traveling yarn. The configuration of the sealing element as a slotted strip, in conjunction with the configuration of the intermediate layer as an H-shaped component, leads to an easily assembleable and very flexible sealing unit, which ensures good sealing of the steam setting device both during regular operation and also during the occurrence of yarn thickenings and, in the process, also prevents tensile force increases occurring on the traveling yarn.
[0027] It may be provided that sensors, which monitor the physical variables prevailing in the interior of the yarn treating chamber, such as temperature and/or pressure, are additionally connected to the control and/or the regulating device of the yarn sluice, which inter alfa activates the drive, which can be activated in a defined manner for the steplessly adjustably mounted first yarn guide element. The control and/or the regulating device has a control loop, which by corresponding positioning of the steplessly adjustably mounted first yarn guide element ensures that during the yarn treading process, virtually constant conditions are always maintained in the yarn treating chamber. It is thus ensured that a steam setting device equipped with yarn sluices according to the invention always optimally treats the yarn running through and quality deviations are practically ruled out.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] Further details of the invention will be described below with the aid of embodiments shown in the figures, in which:
[0029] FIG. 1 shows a schematic diagram of a workstation of a twisting machine with a steam setting device, the yarn treating chamber of the steam setting device being sealed by yarn sluices according to the invention,
[0030] FIG. 2 shows the electric motor drive and a part of an associated reducing gear of a yarn sluice,
[0031] FIG. 3A shows a front view of a sluice insert of a yarn sluice with a recess for receiving a displaceably mounted yarn guide element,
[0032] FIG. 3B shows a perspective view of the sluice insert according to FIG. 3A with a steplessly displaceably mounted first yarn guide element arranged in the recess,
[0033] FIG. 4 shows a side view, partially in section, of a yarn sluice according to the invention,
[0034] FIG. 5 shows a rear view of the sluice insert of a yarn sluice with a gear arrangement for converting the rotational movement of the electric motor drive into a translatory movement to displace the steplessly displaceably mounted first yarn guide element,
[0035] FIG. 6 shows a first embodiment of a sealing element,
[0036] FIG. 7 shows a further, preferred embodiment of a sealing element.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0037] FIG. 1 sketches a schematic view of a workstation 29 of a twisting machine. Textile machines of this type generally have a large number of structurally identical workstations 29 of this type located next to one another. As shown, in the present embodiment, each of the workstations 29 has a steam setting device 1 , which is used to thermally set the yarn 14 drawn off from a twisting device 15 .
[0038] The workstations 29 also have a control and/or a regulating device 13 , which is used to control or regulate the various work components of the workstation 29 . As can be seen, a creel thread 18 is fed to a thread 17 drawn off from a twisting pot of the twisting device 15 and is twisted with the latter to form a yarn 14 . The yarn 14 arrives via a draw-off device 16 and deflection means 22 at the steam setting device 1 , in which, as already indicated above, the yarn 14 is thermally set.
[0039] The steam setting device 1 , as conventional, substantially consists of a yarn treating chamber 21 , which is in turn divided into a central zone 5 and two end zones 6 and 7 . The central zone 5 is, in this case, supplied via a connection 8 with a hot, gaseous medium, preferably saturated steam or hot steam, while a cool gaseous medium, for example compressed air, is blown into the end zones 6 and 7 , in each case via connections 9 A or 9 B.
[0040] The central zone 5 also has a connection 10 , by means of which steam or condensate can be removed. The yarn treating chamber 21 furthermore has a yarn inlet opening 2 in the region of the end zone 6 and a yarn outlet opening 3 in the region of the end zone 7 . Arranged in the yarn inlet opening 2 and the yarn outlet opening 3 is, in each case, a yarn sluice 23 A or 23 B, which seals the yarn treating chamber 21 under excess pressure relative to the environment.
[0041] The yarn 14 thermally set in the steam setting device 1 is guided by a draw-off device 11 and deflection means 12 to a winding device 24 of the workstation 29 and wound there to form a cross-wound bobbin 20 . The cross-wound bobbin 20 is rotably held here in a pivotable creel (not shown) and rests on a winding roller 19 , by means of which it is driven by frictional engagement and is made to rotate in order to wind on the yarn 14 .
[0042] The hot gaseous medium is fed to the yarn treating chamber 21 of the steam setting device 1 by a steam line (not shown) of the twisting machine. The feeding of the steam may, in this case, be metered by a shut-off device 4 configured as a steam valve and be interrupted if necessary.
[0043] As also shown in FIG. 1 , the steam setting device 1 is also equipped, in each case, with a supply mechanism 37 or a supply mechanism 38 in the region of the yarn inlet opening 2 and in the region of the yarn outlet opening 3 , said supply mechanisms being used to feed the yarn 14 to be treated or to remove the treated yarn 14 . For this purpose, the two supply mechanisms 37 , 38 are driven in such a way that the yarn 14 running through the steam setting device 1 is held substantially constantly without tension between the supply mechanisms 37 , 38 .
[0044] The steam setting device 1 is furthermore equipped with a sensor device, the sensors 40 , 41 , 42 , 43 of which are connected by signal lines 39 to the control and regulating device 13 . The control and/or regulating device 13 is also connected by control lines 44 to the drives 30 of the yarn sluices 23 A and 23 B and by signal lines to sensor devices 31 (not shown in FIG. 1 ) installed in the region of the drives 30 .
[0045] FIG. 2 shows one of the yarn sluices 23 A, 23 B, in the embodiment, the yarn sluice 23 B located downstream in the yarn running direction, the superstructure of which, as can be seen, is surrounded by a housing 51 . The yarn sluice 23 B, on the inlet side, has a connection piece 54 , with which it is fixed in the yarn outlet opening 3 of the yarn treating chamber 21 and, on the output side, has an injector device 56 , which can be loaded with compressed air via a connection 50 and allows a pneumatic threading of the yarn 14 through the entire steam setting device 1 . In other words, an airflow, which allows the yarn transportation within the steam setting device 1 , can be initiated within the steam setting device 1 via the compressed air connection 50 .
[0046] By means of a compressed air connection 49 , the yarn sluice 23 B can also be loaded with a system pressure which, as will be explained below, acts on a sealing element 28 and ensures that the sealing element 28 is properly positioned on the yarn guide channel 25 of the yarn sluice 23 B during the yarn treating process.
[0047] A pneumatic cylinder, which ensures during loading that the sealing element 28 during the threading of a yarn 14 can be raised from the yarn guide channel 25 , is simultaneously connected to the compressed air connection 50 .
[0048] As can also be seen from FIG. 2 , the yarn sluice 23 B also has an electric motor drive 30 , preferably a stepping motor, which is connected by a gear arrangement and a link guide (not shown in FIG. 2 ) to the steplessly adjustable first yarn guide element 26 of the yarn sluice 23 B. In other words a pinion 45 fastened to the motor shaft of the stepping motor 30 meshes with an intermediate toothed wheel 46 , which in turn drives a relatively large external toothed wheel 47 . The external toothed wheel 47 , as can be seen in particular from FIG. 4 , is a component of a sleeve-like structural component of the yarn sluice 23 B, this structural component 55 furthermore having a small, coaxially arranged pinion 52 , which meshes with the pinion 64 of a link spindle 53 . Also arranged in the region of the external toothed wheel 47 is a sensor device 31 which preferably consists of a permanent magnet insert 31 A and a Hall element 31 B and monitors the zero position of the drive 30 configured as a stepping motor. The drive 30 is connected by a control line 44 to the control and/or regulating device 13 .
[0049] FIGS. 3A and 3B show, in a front view or in a perspective view, a sluice insert 32 arranged within a yarn sluice 23 , FIG. 3A showing the sluice insert 32 without the installed, steplessly adjustably mounted first yarn guide element 26 and FIG. 3B showing the sluice insert 32 with said yarn guide element 26 .
[0050] As can be seen from FIG. 3A , the sluice insert 32 , on its front side, is configured as a plate-like component, into which a wedge-shaped recess 57 is worked. The plate-like component of the sluice insert 32 , during operation, in this case forms, with its side face 58 pointing to the recess 57 , a fixed second yarn guide element 27 of a yarn guide channel 25 . The opposing side face 59 arranged in a wedge shape of the sluice insert 32 forms a guide for the steplessly adjustably mounted first yarn guide element 26 , not shown in FIG. 3B , of the yarn sluice 23 . As can be seen from 3 A, the rear of the recess 57 also has a groove 60 , which is arranged parallel to the side face 59 of the recess 57 and in which a connector 61 , as is described in more detail below with the aid of FIG. 5 , is guided.
[0051] As shown in FIG. 3B , the displaceably mounted first yarn guide element 26 is connected by means of a screw bolt 62 to the connector 61 and is guided by the connector 61 in the groove 60 of the sluice insert 32 . The outside 63 of the displaceably mounted first yarn guide element 27 facing the side face 58 of the fixed second yarn guide element 27 , in conjunction with the side face 58 , forms a yarn guide channel 25 . By corresponding positioning, indicated by the arrow H, of the displaceable first yarn guide element 26 , the width B of the yarn guide channel 25 can be steplessly adjusted.
[0052] The rear of the yarn guide channel 25 is formed by the rear wall of the recess 57 of the sluice insert 32 , while a sealing element 28 acts as the front wall of the yarn guide channel 25 , said sealing element resting resiliently on the yarn guide elements 26 , 27 during operation and it being possible to raise it pneumatically from the yarn guide channel 25 to thread in a new twisted yarn 14 .
[0053] FIG. 4 shows a side view, partially in section, of a yarn sluice 23 which, as already indicated above in conjunction with FIG. 2 , has a sleeve-like structural component 55 with an external toothed wheel 47 and a small, coaxially arranged pinion 52 , which meshes with the pinion 64 of a link spindle 53 . The link spindle 53 has a link guide 65 , to which is connected, by means of a ball head 66 , a guide slide 67 which, as can be seen in particular from FIG. 5 , is vertically displaceably mounted in the region of the rear of the sluice insert 32 and is secured here by a guide plate 68 .
[0054] It can clearly be seen here from FIG. 5 , showing a rear view of the yarn sluice 23 , how the guide slide 67 is connected by a ball head 66 , which is mounted at the end of a connection lever 67 , to the link guide 65 of the link spindle 53 . The guide slide 67 in turn has a slide link 70 , in which the connector 61 , to which the displaceably mounted first yarn guide element 26 is connected, is horizontally displaceably guided. The connector 61 engages, as already indicated above, through the groove 60 , which is worked into the base of the recess 57 parallel to the side face 59 running in a wedge shape, of the recess 57 of the sluice insert 32 .
[0055] Also arranged in the region of the connector 61 is a flexible support disc (not shown), which, in connection with a corresponding sealing film, ensures sealing, in other words, the sealing film prevents the system pressure of the yarn sluice 23 prevailing in the region of the yarn guide elements 26 , 27 and the sealing element 28 from being able to be reduced via the groove 60 .
[0056] Two embodiments are shown in FIGS. 6 and 7 for a sealing element 28 , which in each case forms the fourth, resilient limiting wall of the yarn guide channel 25 of the yarn sluice 23 A or 23 B.
[0057] According to the embodiment of FIG. 6 , the sealing element 28 has a resilient intermediate layer 34 , which is fastened to the sealing element 28 , and a thin, planar, wear-resistant sealing band 33 , which covers the intermediate layer 34 . The intermediate layer 34 is in this case preferably produced from a temperature-resistant, resilient material, for example foam or the like, while the sealing band 33 is produced from a metal or another abrasion-resistant material. In the embodiment according to FIG. 6 , the sealing band 33 is mounted at the top in the sealing element 28 and non-positively positioned on the intermediate layer 34 , for example by permanent magnet inserts (not shown), which are arranged in corresponding receivers of the sealing element 28 . As shown, for example, in FIG. 4 , the sealing element 28 is movably mounted to a limited extent within the yarn sluice 23 by means of a pivot pin 71 on an angle lever 72 , which is in turn connected by a pivot pin 73 to a holder 74 . Arranged within the holder 74 is a spring element (not shown) which loads the angle lever 72 by means of a short lever arm in such a way that the angle lever 72 is pivoted in the direction of the yarn guide channel 25 and the sealing element 28 is thereby positioned on the yarn guide channel 25 , where the sealing element 28 is also loaded with the system pressure of the yarn sluice 23 .
[0058] The lever arm of the angle lever 72 can, however, also be loaded by a small pneumatic cylinder against the force of the spring element. The pneumatic cylinder then ensures that the sealing element 28 is raised from the yarn guide channel 25 , which considerably facilitates the threading in of a new twisted yarn.
[0059] FIG. 7 shows a further preferred embodiment of a sealing element 28 . As shown in the upper half of FIG. 7 , the sealing element 28 is configured here as a slotted strip 28 A. The intermediate layer 34 A formed in an H-shape and shown in the lower half of FIG. 7 can be threaded into the slot of the strip 28 A and is fitted with a relatively large amount of play. The intermediate layer 34 A is in turn covered with a metallic sealing band 33 and thereby protected against abrasion by the traveling yarn 14 .
[0060] The sealing element according to FIG. 7 , as described above in connection with FIG. 6 , is also movably mounted to a limited extent on an angle lever 72 and, for this reason, has a bearing device 75 , which has a corresponding pivot pin 71 .
[0061] Functioning of the yarn sluice according to the invention:
[0062] Before the beginning of the thermal treatment process of a yarn 14 provided by the twisting device 15 in the steam setting device 1 , the latter firstly has to be put into its operating state, in other words, the steam setting device 1 has to be heated. Moreover, the width B of the yarn guide channel 25 of the yarn sluices 23 A and 23 B has to be adjusted in accordance with the mean thickness of the yarn 14 to be processed.
[0063] The control and/or regulating device 13 , for this purpose, activates the stepping motors 30 of the yarn sluices 23 A and 23 B in such a way that the adjustably mounted first yarn guide elements 26 of the yarn sluices are positioned in an optimal position for the mean thickness of the yarn to be treated. Furthermore, by actuating corresponding pneumatic cylinders present in the yarn sluices, the sealing elements 28 of the yarn sluices 23 A and 23 B are raised from the associated yarn guide channels 25 .
[0064] An injector device 56 is then loaded with compressed air at the yarn sluice 23 B located downstream in the yarn running direction, the yarn 14 is pneumatically threaded through the two yarn sluices 23 A and 23 B and the yarn treating chamber 21 located in between and transferred to the winding device 24 .
[0065] In the next step, the yarn sluices 23 A and 235 are loaded via the connections 49 with a system pressure and simultaneously the pneumatic cylinders at the angle levers 72 of the sealing elements 28 are switched to be without pressure, with the result that the sealing elements 28 are resiliently placed on the yarn guide elements 26 , 27 and therefore form yarn guide channels 25 , the cross-section of which is optimally adapted to the mean thickness of the yarn 14 to be treated. In other words, the yarn 14 located in the yarn guide channels 25 prevents, for example, hot steam being able to leave the yarn treating chamber 21 and go into the environment via the yarn guide channels 25 of the yarn sluices 23 A and 23 B. This optimal sealing by the yarn sluices 23 A and 235 is also provided when the workstation is then started and a traveling yarn 14 is then thermally treated in the steam setting device 1 .
[0066] The seal is obviously also maintained when the traveling yarn 14 has a yarn thickening, for example in the form of a nep or a splice and this yarn thickening runs through one of the yarn sluices 23 A or 235 . In a case such as this, the resilient intermediate layer 34 of the sealing element 28 resting on the yarn guide channel 25 is pressed back slightly by the yarn thickening, so the yarn thickening, without problems, in other words without a significant increase in tensile force, can run through the relevant yarn sluice 23 . As the sealing band 33 of the sealing element 28 protecting the intermediate layer 34 is in each case only loaded in the direct region of the yarn thickening, a reliable seal continues to be provided in the remaining regions of the yarn guide channel 25 not affected by the yarn thickening, in other words before and after the yarn thickening, so the pressure loss when a yarn thickening runs through is minimal. The yarn treating chamber 21 is consequently always reliably sealed relative to the environment under all conditions.
[0067] It will therefore be readily understood by those persons skilled in the art that the present invention is susceptible of broad utility and application. Many embodiments and adaptations of the present invention other than those herein described, as well as many variations, modifications and equivalent arrangements, will be apparent from or reasonably suggested by the present invention and the foregoing description thereof, without departing from the substance or scope of the present invention. Accordingly, while the present invention has been described herein in detail in relation to its preferred embodiment, it is to be understood that this disclosure is only illustrative and exemplary of the present invention and is made merely for purposes of providing a full and enabling disclosure of the invention. The foregoing disclosure is not intended or to be construed to limit the present invention or otherwise to exclude any such other embodiments, adaptations, variations, modifications and equivalent arrangements, the present invention being limited only by the claims appended hereto and the equivalents thereof.
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A yarn sluice for sealing a pressurized yarn treating chamber in which a traveling yarn is thermally treated, comprises yarn guide elements in the region of a yarn inlet and outlet openings of the treating chamber forming a yarn guide channel sealed by the traveling yarn during operation. At least one of the guide elements is positionable for adaptation to the mean thickness of the traveling yarn in various predetermined positions. Means is provided for temporary adaptation of the yarn guide channel to yarn defects. At least one of the guide elements ( 26, 27 ) is steplessly adjustably mounted for adaption to the mean thickness of the traveling yarn ( 14 ). A sealing element ( 28 ), which can be placed on the first and the second yarn guide element ( 26, 27 ), extends along the yarn guide channel ( 25 ), for closing it and for reacting resiliently to defects in the traveling yarn ( 14 ).
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to film sheets for use in projection by an overhead projector (hereinafter abbreviated as “OHP”) which is used in a meeting, conference or the like.
2. Description of the Related Art
As transparent film sheets for use with OHPs, transparent film sheets formed of polyesters such as polyethylene terephthalate are being widely used.
These polyester films have surface properties and heat-resisting properties which permit characters and/or pictures to be easily printed thereon by dry copying techniques such as xerography and, moreover, have high strength and excellent shelf stability.
In recent years, the spread of personal computers has made it easy to prepare materials for presentation in a conference or meeting. In particular, even diversely colored materials may be easily prepared.
Recently, there are some cases in which materials prepared with a personal computer are used for purposes of presentation by direct projection by a liquid crystal projector or the like. However, it is still common practice to prepare materials for use with an OHP by printing colored materials on common white paper with a printer of the ink-jet printing type and then copying them onto special-purpose polyester film sheets by means of a color copying machine, or by printing characters and/or pictures directly on such polyester film sheets by means of a printer designed for direct printing thereon. The reason for this is that polyester film sheets cannot be directly printed with a jet printing ink. Recently, a multilayer transparent film obtained by forming a polyvinyl alcohol-containing layer receptive to a jet printing ink over a polyester film is available. This film makes it possible to prepare materials for use with an OHP directly by means of an ink-jet printer which is less expensive than color copying machines.
As described above, such films formed of a polyester alone have high transparency and excellent shelf stability. However, when it is desired to dispose of the films having become unnecessary after use, highly secret materials must be treated by shredding or the like. Thus, they must be disposed of in a way different from recycling waste such as materials prepared from common white paper.
SUMMARY OF THE INVENTION
The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide transparent film sheets for use in projection by an OHP which can be used both in dry copying and in the ink-jet printing of characters and/or pictures, can be directly printed with a jet printing ink without the intervention of a layer receptive to the jet printing ink, can be disposed of in a state capable of maintaining secrecy after use without the necessity of being shredded, and can be disposed of as a class of recycling waste like common white paper.
As a result of intensive investigations carried out with a view to solving the above-described problems, the present inventors have now found that film sheets formed of a cellulose ether derived from cellulose which is the basic component of common paper can be printed with characters and/or pictures by means of either an ink-jet printer or a dry copying machine, are not liable to curling during use, enable the projection of sharp images because of direct printing with a jet printing ink without the intervention of a layer receptive to the jet printing ink, and are stable because of their low hygroscopicity. The reason why the OHP film sheets formed of a cellulose ether can be directly subjected to ink-jet printing is believed to be that a cellulose ether generally has a surface-active effect owing to the balance between the ether substituent groups and the hydrophilic and hydrophobic groups inherently present in the molecule of the cellulose and, therefore, a film formed of the cellulose ether exhibits an improvement in the adhesion of an ink. Moreover, it has also been found that, when the sheets have become unnecessary after use, they can be dipped in water to make the printed characters and/or pictures undiscernible, and then disposed of, and that the sheets can be disposed of as a class of combustible or recycling waste like paper, because an aqueous solution of a water-soluble cellulose does not constitute a source for BOD (biochemical oxygen demand) upon disposal. The present invention has been completed on the basis of these findings.
The OHP film sheets of the present invention can be printed with characters and/or pictures by means of either an ink-jet printer or a dry copying machine, are not liable to curling during use, enable the projection of sharp images because of direct printing with a jet printing ink without the intervention of a layer receptive to the jet printing ink, and are stable because of their low hygroscopicity. Moreover, since cellulose which is the basic component of paper is used as a raw material, the sheets which have become unnecessary after use can be dipped in water to make the printed characters and/or pictures undiscernible, and then disposed of. On that occasion, the sheets can be disposed of as a class of combustible or recycling waste like paper, because an aqueous solution of a water-soluble cellulose does not constitute a source for BOD upon disposal. Furthermore, conventional OHP film sheets are inconvenient in that only the surface-treated side must be chosen and used. In contrast, the OHP film sheets of the present invention have the advantage that either side may be chosen and used, depending on the manner of use.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is more specifically described hereinbelow. However, it is to be understood that the present invention is not limited to the embodiments described below.
Preferred examples of the cellulose ether used in the present invention include, but are not limited to, alkylcelluloses such as water-soluble methylcellulose (MC); hydroxyalkyl alkylcelluloses such as hydroxypropyl methylcellulose (HPMC), hydroxyethyl methylcellulose (HEMC) and hydroxyethyl ethylcellulose (HEEC); hydroxyalkyl celluloses such as hydroxypropyl cellulose (HPC) and hydroxyethyl cellulose (HEC); and carboxymethylcellulose sodium (CMC-Na). There may be used any cellulose ether that is derived by etherifying cellulose to make it water-soluble and can be formed into a film by casting an aqueous solution thereof to a certain thickness and then drying it.
Specifically, useful alkylcelluloses include, for example, methylcellulose having 19 to 33% by weight of the methoxyl group, and ethylcellulose having 7 to 25% by weight of the ethoxyl group.
Useful hydroxyalkyl alkylcelluloses include, for example, hydroxypropyl methylcellulose having 19 to 30% by weight of the methoxyl group and 13 to 20% by weight of the hydroxypropoxyl group, hydroxyethyl methylcellulose having 19 to 30% by weight of the methoxyl group and 9 to 20% by weight of the hydroxyethoxyl group, and hydroxyethyl ethylcellulose having 11 to 21% by weight of the ethoxyl group and 40 to 57% by weight of the hydroxyethoxyl group.
Useful hydroxyalkyl celluloses include, for example, hydroxypropyl cellulose having 50 to 70% by weight of the hydroxypropoxyl group, and hydroxyethyl cellulose having 30 to 60% by weight of the hydroxyethoxyl group.
A useful example of carboxymethylcellulose sodium (CMC-Na) is that having 15 to 53% by weight of the carboxymethoxyl group.
The contents of the methoxyl, ethoxyl, hydroxypropoxyl and like groups can be determined according to the methods described in the Pharmacopoeia of Japan. On the other hand, the content of the hydroxyethoxyl group can be determined according to the method described in P. W. Morgan, Eng. Chem. Anal. Ed., 1946, 18, pp. 500-504 or in Merz, Z. Anal. Chem., 1967, 232, pp. 82-93.
The film prepared from a cellulose ether according to the present invention needs to have high transparency. If its transparency is low, the film will have a problem in that the images projected by an OHP may not be sharp. Such a cellulose ether may be prepared by mixing cellulose with NaOH or the like to form a homogeneous alkali cellulose, and reacting it with an etherification reagent until a degree of ether substitution required to making it water-soluble is achieved.
If the cellulose ether has an insufficient degree of substitution or is not uniformly substituted, a lot of undissolved fibrous matter having a length of 8 to 200 μm will remain when it is dissolved in water.
The amount of such undissolved fibrous matter may be determined by dissolving the cellulose ether in ISOTON II (an aqueous electrolyte solution for use with Coulter counters; manufactured by Coulter, Inc.) within a thermostatic chamber at 20° C. so as to give a 0.1 wt % aqueous solution, and counting the number of undissolved fibers present in 2 ml of the solution and having a length of 8 to 200 μm by means of a Model TAII Coulter Counter (manufactured by Coulter, Inc.) or multisizer using an aperture tube having a diameter of 400 μm.
For a cellulose ether capable of forming a film with which very sharp images can be projected when it is used for purposes of projection by an OHP, it is preferable that the number of undissolved fibers determined in the above-described manner be not greater than 1,000 (inclusive of zero).
Preferably, the cellulose ether used in the present invention is characterized in that, when 100 g of the cellulose ether is shaken on a sieve having an opening of 150 μm, the amount of cellulose ether remaining on the sieve is not greater than 25% by weight. If the amount is greater than 25% by weight, the solubility of the cellulose ether may be reduced to cause an increase in the amount of undissolved fibers and, therefore, the transparency of the resulting film sheet may be reduced.
Specifically, using a Model 429 Low-Tap Sieve Shaker (manufactured by Kansai Kana-Ami Co., Ltd.) fitted with a No. 100 standard sieve (having an opening of 150 μm) as prescribed by JIS Z8801, 100 g of the cellulose ether is shaken for 30 minutes under conditions including 200 shakes per minute, 156 strokes per minute, and an amplitude of 50 mm. Thereafter, the amount of residue on the sieve is weighed.
No particular limitation is placed on the molecular weight of the cellulose ether used. However, it is generally preferable that a 2 wt % aqueous solution of the cellulose ether have a viscosity of not less than 3 mPa.s at 20° C. This viscosity corresponds to a weight-average molecular weight of not less than 10,000 which can provide a film-forming ability. The aforesaid viscosity can be measured according to the viscosity measuring method described in the Pharmacopoeia of Japan.
A film of the cellulose ether described herein may be formed by casting a solution of the cellulose ether and then drying it, or by extruding a thick solution of the cellulose ether into a film and then drying it, as described in Japanese Patent Publication (JP-B) No. 45-2116/'70.
In the case of alkylcelluloses and hydroxyalkyl alkylcelluloses which are not soluble in water having a high temperature, films thereof may be formed by dispersing a powdered cellulose ether in hot water at a high concentration, casting this dispersion, cooling it to dissolve the cellulose ether, and then drying it to form a film.
No particular limitation is placed on the thickness of the OHP sheet of the present invention. However, if the sheet is unduly thin, it may have poor durability, and if the sheet is unduly thick, it may have low transparency and be hard to handle. Accordingly, its thickness is preferably in the range of 5 to 200 μm and more preferably about 10 to 100 μm.
Moreover, various additives may be added to the cellulose ether, so long as they do not interfere with the objects of the present invention and they permit the cellulose ether to be formed into a film. Such additives include inorganic fillers such as ceramics; colorants such as Food Red, Methyl Orange and Methyl Red; polyhydric alcohol type plasticizers and surfactants such as glycerol; organic binders such as polyvinyl alcohol, sodium polyacrylate and polyacrylamide; and the like.
The present invention is more specifically explained with reference to the following examples and comparative example. However, these examples are not to be construed to limit the scope of the invention.
EXAMPLE 1
A 3 wt % aqueous solution of hydroxypropyl methylcellulose (60SH-50; manufactured by Shin-Etsu Chemical Co. Ltd.) containing 29% by weight of the methoxyl group and 9% by weight of the hydroxypropoxyl group and having a viscosity of 50 mPa's as measured by a 2 wt % solution at 20° C. was prepared. This hydroxypropyl methycellulose is characterized in that the powder remaining on a sieve having an opening of 150 μm is 10% by weight when measured under the above-described conditions, and in that the number of undissolved fibers present in a 0.1 wt % aqueous solution is 600 when counted with a Coulter counter is described previously. 27 g of this solution was poured into a 30 cm×22 cm mold made of glass, and dried at 70° C. for 10 hours to form a film. The resulting 10 μm thick film was stripped from the mold.
This film was set on a BJC-35v Ink-Jet Printer (manufactured by Canon Inc.). Thus, numerical tables and graphs having red, yellow and blue colors were printed thereon and projected by an OHP. The projected images were sharp, and their definition was similar to that of images obtained by providing a sheet of white paper having characters and pictures printed thereon, copying them onto a polyester film by means of a dry color copying machine (PIXEL; manufactured by Canon Inc.), and projecting them.
Moreover, when a hydroxypropyl methylcellulose film formed in the above-described manner was used in place of the polyester film and subjected to dry color copying, the resulting sheet permitted similarly sharp images to be projected.
After projection, the sheets were dipped in water, so that the sheet surface was partially dissolved to make the printed images undiscernible. When the sheets were recovered from water and dried, they were wrinkled, but could be disposed of as a class of waste like newspapers.
EXAMPLE 2
A film was formed in the same manner as in Example 1, except that methyl cellulose having 29% by weight of the methoxyl group (manufactured by Shin-Etsu Chemical Co. Ltd.) was used. When characters and pictures printed thereon were projected by an OHP, the definition of the projected images was the same as that achieved in Example 1. Since the printed images became undiscernible in water as described in Example 1, the sheet could be directly disposed of.
EXAMPLE 3
A film was formed and evaluated in the same manner as in Example 1, except that hydroxypropyl cellulose having 65% by weight of the hydroxypropoxyl group (manufactured by Nippon Soda Co. Ltd. under the trade name of L) was used. The results of evaluation were the same as those of Example 1.
COMPARATIVE EXAMPLE 1
In the same manner as in Example 1, transparent films having a thickness of about 10 μm were formed from a 3 wt % aqueous solution of polyvinyl alcohol (PA05S; manufactured by Shin-Etsu Chemical Co. Ltd.) and used to print characters and pictures thereon. The sheets were greatly curled, whether characters and/or pictures were printed thereon by an ink-jet printer or by a dry color copying machine. Moreover, these sheets made it difficult to project sharp images by an OHP. Furthermore, when these sheets were allowed to stand, they became soft and showed an increase in stickiness, so that fingerprints tended to be left thereon during handling.
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The present invention provides transparent film sheets for use in projection by an OHP which can be used both in dry copying and in the ink-jet printing of characters and/or pictures, can be directly printed with a jet printing ink without the intervention of a layer receptive to the jet printing ink, can be disposed of in a state capable of maintaining secrecy after use without the necessity of being shredded, and can be disposed of as a class of recycling waste like common white paper. Specifically, the present invention provides transparent film sheets formed of a cellulose ether derived from cellulose which is the basic component of common paper.
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This is a continuation of application Ser. No. 597,511, now abandoned filed July 21, 1975.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to means for recovering the waste heat generated in processing plants, and more particularly, to an improved waste heat recovery system for absorbing the waste heat contained in exhaust gases being discharged at one point and transferring it safely, efficiently, and economically to a second (remote) point for beneficial use in the process.
2. Prior Art
A substantial quantity of heat energy is generated as a by-product of many chemical and industrial processes. In many cases, this heat is exhausted into the atmosphere through exhaust stacks and flues because the cost of its recovery is greater than can be economically justified. This heat is known in the field as "waste heat" because it is, in fact, all too often wasted energy. Perhaps, twenty (20) years ago and earlier, an industrial society could afford to waste energy on a massive scale because the cost of one million BTU's of energy was only about 8 cents. Today, however, the cost of one million BTU's of energy is about $2.00. Thus, there exists today a great economic incentive to recover the waste heat of chemical and industrial processes and to use it beneficially in the process; e.g., to preheat inlet combustion air.
Waste heat recovery systems are known to the prior art. However, the systems of the prior art have one or more significant shortcomings and limitations. One waste heat recovery system well known and commonly used in the prior art utilizes the so-called Ljungstrom heat exchanger. The Ljungstrom heat exchanger is a regenerative heat exchanger in that it includes a regenerator drum rotatably mounted in a housing divided into separate compartments through which the hot exhaust gases and the cool gases to be heated flow. The drum, driven by an electric motor, has a capacity for heat absorption and release. As the drum rotates, it absorbs waste heat from the hot exhaust gases in one compartment and gives up the heat to the cooler gases in the other compartment.
The Ljungstrom heat exchanger imposes several severe limitations upon any waste heat recovery systems which utilizes it. In the first place, the regenerator drum must be relatively large in order for sufficient waste heat to be recovered. The large drum, in turn, requires the use of large exhaust and inlet compartments and associated ducts, the latter often 6 feet or larger in diameter. Secondly, by virtue of the use of a drum as the basic heat exchange medium, the two compartments of the housing must be located adjacent to one another. Thus, if the gases heated by the drum are to be used at a location remote from the location of the source of the waste heat gases, ducting must be provided between the exchanger and such remote point. Further, a blower of sufficient capacity must also be provided in order to force the heated gases to flow to the remote point of utilization. Thus, such regenerator drum systems suffer from the disadvantages of higher cost (due to the ducting and blower capacity required) and from the fact that they require relatively large installations which, together with the associated ducting, tie up much valuable property in a non-productive manner. For the foregoing reasons, a waste heat recovery system utilizing a Ljungstrom heat exchanger may prove to be economically unfeasible in some applications. In addition, such systems are typically more difficult to install than systems which use a fluid heat transfer medium, such as the present invention. In the latter case, 4 inch pipes are typically used in lieu of 6 foot or larger ducts. Another disadvantage of waste heat recovery systems which employ a Ljungstrom heat exchanger is that they are limited to transferring waste heat from hot exhaust gases to cooler combustion air.
Heat exchange apparatuses and methods are known in the prior art. Such apparatuses are generally used to transfer "process heat", as distinguished from waste heat, from one point in the process to another. Many such heat exchangers utilize a liquid heat transfer medium. However, the temperatures and other conditions present in a waste heat recovery application are typically far more severe than those encountered in applications wherein process heat is being transferred. Thus, a reliable and economically waste heat recovery system cannot be constructed by simply utilizing the heat exchanger apparatuses and methods of the prior art, suitable for the transfer of process heat, to solve a waste heat recovery problem.
U.S. Pat. No. 3,623,549, issued to Horace L. Smith, is an example of a prior art heat exchanger utilizing a plurality of heat transfer liquids. Smith's invention transfers heat from a gas at one location to a cooler gas at a second location which may be considerably removed from the first location. Smith discloses the use of at least two independent flow circuits through which different heat transfer liquids flow. Each flow circuit comprises a pair of interconnected finned tube type heat exchangers. The first heat exchanger of each circuit is located in a duct through which the hot gas flows, while the second is located in a duct through which the cool gas flows.
While U.S. Pat. No. 3,623,549 teaches the use of a suitable heat transfer liquid in closed flow circuits for the transfer of heat from one point to a second remote point, it applies such teachings to a general and relatively simple application of hot and cool gases flowing in two separate ducts. Smith's invention does not address itself to the particular conditions typically found in waste heat recovery applications where, for example, the temperatures and pressures at various points are critical parameters which must be controlled. To illustrate this point, the following two temperature constraints on waste heat recovery systems are cited: (i) the temperature of the heat transfer liquid must not reach a level which could damage the pumping means typically used in the flow circuit; (ii) the temperature of the exhaust gases must be permitted to drop to a temperature at which some of the gases may begin to condense onto the heat exchanger located in the exhaust stack, because such condensation would cause corrosion of the exchanger. If condensation of the exhaust gases is not prevented or substantially mitigated, the heat exchanger in the stack would have to be replaced periodically, thereby causing expense and down time in the operation of the process. Thus, the teachings of Smith are inadequate for the waste heat recovery applications for which the present invention is advantageously suited.
There have been attempts in the prior art to apply heat exchange apparatuses, utilizing a fluid as a heat transfer medium, for the recovery and transfer of waste heat. U.S. Pat. No. 2,699,758 issued to David Dalin et al., is an example of one such attempt. Dalin et al. disclose an apparatus for improving combustion in the furnaces of steam boilers by preheating the combustion air, in two stages, to a relatively high temperature by using the flue gases as a source of heat for this purpose. They teach the use of water as a first heat transfer medium in a first stage of waste heat recovery and superheated steam as the medium of heat transfer in the second stage thereof.
Unlike Smith, Dalin et al. disclose the use of some temperature and pressure control means; e.g., (i) an economizer 19 to insure a definite temperature differential between the two zones of the flue passage at which the heat exchangers draw their heat; (ii) a thermostatically controlled valve 34 which controls flow through a bypass pipe 33; and (iii) a thermally responsive control element 35 which controls the opening of the valve 34. However, the invention of Dalin et al. suffers from one of the major shortcomings of the prior art at the time of its invention (circa 1950); namely, the unavailability of heat transfer liquids suitable for the high temperatures encountered in waste heat recovery applications. Many of the heat transfer liquids of the prior art flash off at the high temperatures typically encountered in an exhaust stack, thereby creating a fire hazard; others tend to corrode the piping means through which they flow. While water and steam, as heat transfer mediums, do not flash off or cause as much corrosion as other liquids, they have their own disadvantages. Water, since it boils at 100 C, is inherently limited with respect to the amount of heat it can absorb without changing phase. On the other hand, steam, especially superheated steam, introduces the obvious disadvantages of high pressure; for example, severe design requirements with respect to the structural strength of the heat exchange apparatus and associated piping, and (ii) maintenance problems with respect to the detection and repair of leaks.
Still another disadvantage of the Dalin system, attributable to its use of superheated steam as the heat transfer medium, is the limitation that the latter imposes with respect to the distance between the flue passage (or exhaust stack) and the place to which the waste heat is to be delivered. If the distance is great enough, the continuing loss of heat through the conducting pipes may cause the superheated steam to condense to water. As a result of the heat transfer medium being in two phases within the flow circuit (i.e., steam and condensed water), its flow becomes non-uniform difficult to regulate. If the flow of the heat transfer medium cannot be readily regulated, the control of critical temperatures within the system becomes more difficult, if not impossible.
U.S. Pat. Nos. 3,405,509 and 3,405,759 disclose means for recovering waste heat in the exhaust stack of fired oil field equipment. The invention disclosed in U.S. Pat. No. 3,405,509 is limited in that it uses, as the heat transfer medium, the very oil well product fluids, (e.g., a mix of oil and water) which are being processed. U.S. Pat. No. 3,405,759 likewise teaches the use of the process liquid as the heat transfer medium. However, the latter patent also teaches the use of a separate heat transfer fluid contained in a source separate from the the process fluids; in the latter connection, however, the patent teaches the use of water and steam as the separate heat transfer fluid, both of which have the disadvantages and limitations described above with reference to U.S. Pat. No. 2,699,758 (Dalin et al.).
The present invention overcomes the shortcomings and limitations of waste heat recovery systems of the prior art. By utilizing a heat transfer fluid which is superior to water and steam, this invention enables waste heat to be recovered and transferred to remote locations without the need for large ducts and blowers, as is the case with the Ljungstrom exchanger; without the problems of high pressure as is the case with superheated steam; and without the limitation of low heat transfer capacity in the low pressure range, as is the case with water. Thus, the present invention is advantageous with respect to both the cost and case of installation and maintenance. Moreover, its installation does not tie up large areas of property in a non-productive utilization. In addition to being cost effective, this invention includes the critical temperature and pressure control means required for the effective and safe recovery of waste heat.
While the individual elements which comprise the present invention are each known in the prior art, there has heretofore been no waste heat recovery system which combines in one structure all the features and advantages found in this invention.
BRIEF SUMMARY OF THE INVENTION
The present invention comprises a pair of heat exchangers interconnected by suitable conduits, serial pumping means, a reservoir for storing a heat transfer fluid and temperature and pressure control means. The heat exchangers, conduits, pump and reservoir define a closed flow circuit within which the heat transfer fluid circulates. The first heat exchanger is located in an exhaust stack or flue passage of the processing equipment from which waste heat is to be recovered. The second heat exchanger is located at some point remote from the exhaust stack where the recovered heat is to be transferred to combustion air, a process gas or liquid, for some beneficial purpose. The heat transfer liquid is the medium which absorbs waste heat from the exhaust gases and carries it to the remote location for release to the combustion air, process gas or liquid. This invention also includes temperature and pressure control means, as well as certain means to ensure the safety of its operation.
Other objects novel features and advantages of the present invention will become apparent upon making reference to the following detailed description and the accompanying drawing. The description and the drawing will also further disclose the characteristics of this invention, both as to its structure and its mode of operation. Although a preferred embodiment of the invention is described hereinbelow, and shown in the accompanying drawing, it is expressly understood that the description and drawing thereof are for the purpose of illustration only and do not limit the scope of this invention.
BRIEF DESCRIPTION OF THE DRAWING
In the accompanying drawing, in which a preferred embodiment of the present invention is illustrated:
FIG. 1 is a schematic representation of the invented system installed within a processing system.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is installed in, and operates in conjunction with, functionally independent process equipment of one kind or another. In the embodiment of the invention described herein, such process equipment includes a process heater 10, an exhaust stack 12, and an inlet duct 14 for conducting "combustion" air to the process heater 10. A motor 16 is typically used to operate a blower 18 at the front end of inlet duct 14. At the exhaust end, a fan 15 is often utilized to induce an exhaust draft.
The present invention comprises the following basic elements: (i) a first heat exchanger 20, preferably of the conventional finned coil type, installed within the exhaust stack 12 and adapted to recover waste heat from the hot exhaust gases flowing therethrough; (ii) a second heat exchanger 22, also of the conventional, finned coil type, installed within the inlet duct 14 and adapted to release the recovered waste heat to the cooler incoming combustion air flowing therethrough; (iii) conduit 24 which interconnects the outlet side 26 of recovery heat exchanger 20 with the inlet side 28 of air preheat exchanger 22; (iv) serial conduits 30a, 30b, and 30c which interconnect the outlet side 32 of air preheat exchanger 22 with the inlet side 34 of recovery heat exchanger 20; (v) a reservoir 36 for storing a heat transfer liquid 38 which circulates between heat exchangers 20 and 22; (vi) a pumping means 40 for forcing the circulation of heat transfer liquid 38 through the flow circuit defined by the heat exchangers 20 and 22, the reservoir 36 and conduits 24 and 30; and (vii) various temperature and pressure control means described more fully below.
While the present invention is being described with reference to an application for preheating incoming combustion air with recovered waste heat, it should be understood that the invention is not so limited, and that the recovered waste heat may be utilized beneficially in other ways in the process. In addition, while the embodiment being described comprises coil type heat exchangers, other suitable heat exchangers through which a heat transfer fluid flows may be utilized. Persons skilled in the art would have the capability of selecting the appropriate type of heat exchanger for any particular application.
In this embodiment the reservoir 36 is a pressure vessel in which approximately 25 pounds per square inch gauge (psig) of nitrogen is maintained. A nitrogen source is connected to reservoir 36 and the pressure is controlled by a valve 42. The purpose of the nitrogen gas is to provide an inert atmosphere within reservoir 36 and throughout the flow circuit generally, in order to prevent undesired oxidation of the heat transfer liquid 38.
In recent years, the chemical industry has developed superior heat transfer liquids capable of operating at extreme temperatures from as low as -80° up to 900° F. Such liquids include o-dichlorobenzene, diphenyl-diphenyloxide eutectic, di-aryl ethers and tri-aryl ethers sold by Dow Chemical Company under the trademark "Dowtherm" and hydrogenated terphenyls, and polychlorinated biphenyl and polyphenyl ether sold by the Monsanto Company under the trademark "Therminol". Other suitable heat transfer liquids are alkyl-aromatic petroleum oil, sold by Socony Mobil Oil Co. under the mark "Mobiltherm"; alaphatic petroleum oil sold by Exxon under the mark "Humbletherm"; and a good grade, pure lubricating oil. Any of these products would be suitable for most applications in which the present invention has utility. These preferred heat transfer liquids do not become too viscous for controllable flow at the low temperatures nor do they tend to flash at the high temperatures. Thus, they enable the invented system to be used in a wide range of applications.
Pumping means 40 may be any conventional pump, such as a centrifical fluid pump, capable of circulating the heat transfer liquid 38 under pressure. Pumping means 40, in this embodiment, is located serially in the flow path defined by conduit 30b and 30c.
In operation, heat transfer fluid 38 circulates in the flow circuit defined by the heat exchangers 20 and 22, the reservoir 36 and conduits 24 and 30. At the same time, the very hot exhaust gases produced by the process heater 10 are being drawn out through the exhaust stack 12 by the draft fan 15 or by natural convection. These hot gases pass through the coils of waste heat recovery exchanger 20, wherein the circulating heat transfer liquid 38 absorbs some of the waste heat energy. In a typical application, the temperature of the exhaust gases is about 550° F and as high as 900° F when leaving the process heater 10. The flow rate of heat transfer liquid 38 is set so as to remove the desired amount of waste heat from the exhaust gases, but not so much heat as to cool the gases below a temperature at which any of them may begin to condense upon the waste heat recovery exchanger 20. Such condensation will generally cause corrosion of the heat exchanger, thereby decreasing its heat transfer coefficient as well as its useful life.
In an appropriately designed embodiment of this invention, sufficient waste heat may be recovered from exhaust gases emanating from the process heater 10 at 550° to 900° so as to reduce their temperature to as low as 350° or lower, when flue gas quality permits, before their discharge into the atmosphere. Generally, 350° F would be the minimum temperature permissible in order to preclude the condensation of most waste gases containing oxides of sulfur.
The temperature and flow rate of the heat transfer liquid 38 which passes through waste heat recovery exchanger 20 varies with the amount of heat energy absorbed. This is a function of two inter-related heat balances, one between the heat transfer liquid and the source of the waste heat, and the second between the heat transfer liquid and the recipient of the waste heat. The inner diameters of conduits 24 and 30, in turn, are determined by the resultant flow rate. The size of the heat exchangers, the capacity of pumping means 40 and the settings of the various pressure and temperature control means described below are determined by the amount of heat recovered, the logarithmic mean temperature and overall heat transfer rate determined by the above heat balances and resultant heat transfer liquid flow rate. In any event, the heated liquid 38 is circulated to air preheat exchanger 22. In the typical application being described herein, the temperature of heat transfer liquid 38 at the inlet 28 of exchanger 22 would be about 450° F. Meanwhile, relatively cold ambient air is drawn into duct 14 by means of motor 16 and blower 18. The temperature of the inlet air is typically in the range from 30° F to 70° F. Within the duct 14, the air flows through the coils of air preheat exchanger 22, where it absorbs recovered waste heat from heat transfer liquid 38. As a result of the transfer of waste heat, the inlet air temperature, in this application, would increase to about 400° F - 410° F. As a result of using preheated air for combustion, the efficiency of combustion in the process heater 10 may be significantly increased.
Various control means are contemplated by the present invention to ensure its safe and efficient operation. These are now described in detail. Firstly, the liquid reservoir 36 utilizes float detection and correction means comprising a conventional gauge glass 50 and a limit switch assembly 52. The gauge glass 50 is vertically disposed and is coupled, via conduits 54 and 56, to the uppermost and lowermost ends of the reservoir 36 respectively. As known to those in the field, the gauge glass enables a visual determination of the level of the liquid 38 with the reservoir 36.
The limit switch assembly 52 is comprised of (i) a vertical tube adapted to receive heat transfer liquid 38 from the reservoir 36 through conduits 54 and 56 and control valves 58 and 60 respectively, and (ii) three electrical float switches 62a, 62b, and 62c located at three different levels therein. The float switches 62 are responsive to the level of the heat transfer liquid 38 in the vertical tube and, therefore, in the reservoir 36. Thus, the uppermost switch 62a is adapted to be activated when and if the level of liquid 38 rises above the level of the switch. The switch 62a is electrically coupled to an electronic control means 64 which is adapted to issue an audio and/or visual alarm, indicating a potential overflow of the liquid 38 within reservoir 36, in response to a signal from the switch 62a. In a similar manner, float switches 62b and 62c are adapted to detect; i.e., became activated, when and if the level of liquid 38 falls to levels corresponding to their positions within the tube of switch assembly 52. By electrically coupling switches 62b and 62c to control means 64, the former may issue audio and/or visual alarms to indicated (i) that the level of liquid 38 has fallen to a dangerously low level inside reservoir 36, and (ii) that reservoir 36 is practically empty. In the latter case, control means 64 may be adapted to automatically shut down the system to prevent damage to the heat exchangers and pumping means.
The present invention also includes temperature and pressure control means comprising (i) temperature control valve 70 serially coupled in conduit 30a (i.e., in line with respect to the main flow circuit); (ii) by-pass conduit 72 coupling the inlet side 28 of air preheat exchanger 22 with reservoir 38; (iii) pressure control valve 74 serially coupled in conduit 72 (i.e., in line with respect to the by-pass flow circuit); (iv) an optional excess heat disposal coil 76 coupled across conduit 72 by means of control valve assembly 78; and (v) temperature sensing means (e.g., thermocouple transducers) 80a, 80b, and 80c located near the outlet side 26 of waste heat recovery exchanger 20, the outlet side 32 of air preheat exchanger 22 and the inlet side of pumping means 40 respectively. Temperature transducers 80 are electrically connected to an electronic temperature controller within control means 64. The temperature controller may be implemented by a bias bridge circuit which is responsive to any out of balance condition due to changes in the signal level from any of the input temperature transducers 80. Such bias bridge circuits are well known in the electronics control art. The temperature controller, in turn, generates a control signal which is electrically connected to a solenoid 71 which controls the position of temperature control valve 70, thereby closing the temperature control loop. In operation, the foregoing temperature and pressure control means maintains a desired equilibrium condition with respect to the temperatures at the three points monitored, the flow rate of the heat transfer liquid 38 and the amount of waste heat recovered, all of which are interdependent parameters. Under the desired equilibrium condition, sufficient waste heat is recovered from the exhaust gases to enhance the efficiency of the process, but not so much as to reduce the temperature of the exhaust gases to a point where condensation begins. Further, the temperature of the heat transfer liquid 38 at the outlet 26 of waste heat recovery exchanger 20 is maintained below a temperature at which flashing and/or evaporation may occur, while the temperature at the outlet 32 of air preheat exchanger 22 is kept above a temperature at which the liquid may freeze or become excessively viscous. Likewise, pumping means 40 is protected from excessively hot liquid 38 entering its inlet side by the temperature and pressure control means.
Primary temperature control is effected by the position of temperature control valve 70. The setting of temperature control valve is a variable factor which, together with the fixed factors of heat exchanger size, conduit size, pumping capacity, etc., determines the rate of flow of heat transfer liquid 38 through the main flow circuit. The rate of flow of liquid 38, in turn, determines the amount of waste heat recovered and the temperatures of the liquid at various points in the flow circuit. As the rate of flow increases, more waste heat is recovered, but the temperature of the liquid 38 decreases. Likewise, the converse is true; i.e., as the rate of flow decreases, the temperature of liquid 38 increases. The desired temperatures at the critical points of the flow circuit are maintained by setting the temperature controller so that the correction signal is nulled; i.e., the bridge is balanced, when the desired temperatures are sensed. This leaves the temperature valve 70 at a position at which the flow rate of heat transfer liquid 38 corresponds to the attainment of the desired temperatures. If the temperature at any of the monitored points shifts one way or the other, the controller senses the imbalance and responds by issuing an appropriate control signal to the solenoid 71 of the temperature control valve 70.
The by-pass flow circuit, comprised of waste heat recovery exchanger 20, conduits 24 and 72, pressure control valve 74, reservoir 36 and conduits 30b and 30c, provides an automatic pressure control means. A pressure sensing transducer 84 is coupled to conduit 72 in the vicinity of pressure control valve 74 and to a conventional control solenoid 85 which controls the position of said valve. When the pressure in the main flow circuit increases, the increase is detected by transducer 84. The latter responds by opening the pressure control valve 74, thereby increasing the rate of flow through the by-pass flow circuit and reducing the pressure in the main circuit. Conversely, pressure control valve 84 is increasingly closed when the pressure sensed decreases. In this manner, a desired pressure equilibrium is maintained. A secondary and optional temperature control means is provided by excess heat disposal coil 76. By the adjustment of valve assembly 78, a portion of the heat transfer liquid 38 flowing through the by-pass circuit may be passed through exchanger 76, thereby dissipating some heat to the atmosphere or some other suitable heat sink.
One additional safety feature is also contemplated by this invention. It comprises the combination of valve 90 and nitrogen gas pressure tank 92, coupled to the inlet side 34 of waste heat recovery exchanger 20 by conduit 94. The manual or automatic operation of valve 92 permits nitrogen gas, under pressure, to be introduced into the main flow circuit in the direction of flow. Thus, in the event of a pump failure or an interruption in the flow of heat transfer liquid 38 for any reason, the nitrogen can be injected to force the liquid 38 to flow out of the waste heat recovery exchanger 20, thereby preventing it from heating up to an excessively high (and potentially dangerous) temperature and/or pressure.
Although this invention has been disclosed and described with reference to a particular embodiment, the principles involved are susceptible of other applications which will be apparent to persons skilled in the art. Thus, it should be understood that various changes in form, detail and application of the present invention may be made without departing from the spirit and scope of the invention.
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A system for recovering the waste heat normally exhausted into the atmosphere by chemical or other processing plants. The invented system comprises a heat exchange apparatus located in the exhaust stack or flue passage, heat transfer means for carrying the waste heat absorbed from the exhaust gases to a location remote therefrom, and a second heat exchange apparatus for releasing the transferred waste heat for beneficial use at said remote location. The present invention also includes temperature and pressure control means which enhance the safety and efficiency of the system's operation. The heat transfer means disclosed in this invention is a high temperature liquid (and associated pumping and piping means) capable of withstanding temperature up to 900 F. without flashing, changing state, or corroding the heat exchange apparatuses.
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CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a divisional of U.S. patent application Ser. No. 09/948,088 filed on Sep. 6, 2001 by Edward A. Rhad et al which application is incorporated by reference herein in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates, in general, to intravenous (IV) catheters and, more particularly, to a safety IV catheter with a needle tip protector that will automatically cover the needle tip upon needle withdrawal.
BACKGROUND OF THE INVENTION
[0003] An intravenous (IV) catheter is an instrument that is used to introduce certain fluids such as saline solution directly into the bloodstream of a patient. Typically, a needle or other stylet is first introduced through the cannula portion of the catheter and into the skin of the patient at the desired location such as the back of the patient's hand or a vessel on the inside of the arm. Once insertion is complete, the needle is removed from the cannula portion of the catheter. After removing the needle, a fluid handling device such as a syringe is attached to the luer fitting located at the proximal end of the catheter hub. Fluid then flows directly from the fluid handling device through the catheter into the bloodstream of the patient.
[0004] When the needle is removed from the cannula, the health care worker must place the exposed needle tip at a nearby location while simultaneously addressing the task required to accomplish the needle removal. It is at this juncture that the exposed needle tip creates a danger of an accidental needle stick occurring which leaves the health care worker vulnerable to the transmission of various, dangerous blood-borne pathogens such as human immune virus (HIV) and hepatitis.
[0005] The risk of a contaminated needle stick is not just isolated to the health care worker inserting the intravenous catheter. Careless disposal of used needles can put other health care workers at risk as well. Even others outside the health care profession, for example those involved in the clean-up and final disposal of medical waste, are at risk of an accidental needle stick from a carelessly discarded needle.
[0006] The danger to health care workers and others outside the health care profession from accidental needle sticks has yielded the development of catheters with safety mechanisms in which the occurrence of such accidental needle sticks is prevented. An example of a catheter having a safety mechanism is disclosed in U.S. Pat. No. Re. 34,416 issued to Lemieux. A safety catheter is described which includes an element that covers the needle tip upon removal of the needle from the catheter. The safety element includes a split flange at its proximal end which is expanded by the needle as the needle is inserted into an undersized hole at the center of this flange. The safety element is thus held secure within the catheter hub by inserting the needle through the undersized hole which forces the outside perimeter of the split flange against the inside wall of the catheter hub. One of the drawbacks to this design is the amount of friction force exerted against the needle by the split flange. A tight fit of the flange against the catheter wall causes great friction against the needle making it difficult to be withdrawn from the catheter by the clinician. A lose fit leaves the flange prone to releasing prematurely from the catheter as the needle is withdrawn, creating the potential that the needle tip will be left exposed.
[0007] Another example of a catheter having a safety mechanism is disclosed in U.S. Pat. No. 6,117,108 issued to Woehr et al. A safety IV catheter is described including a resilient needle guard which protects the needle tip upon removal of the needle from the catheter hub. The needle guard includes an arm that includes an opening through which a needle passes causing axial movement of the arm. This axial movement forces the arm into a groove or behind a rib located on the inside of the catheter hub, capturing the needle guard in the catheter hub. A potential issue with this design develops when the needle guard is not properly seated into the catheter hub. If the distal end of the needle guard arm is not in alignment with the groove in the catheter hub, excessive forces are placed on the needle causing a high drag force as the clinician removes the needle. And, since the needle guard arm is not properly seated in the groove, it may prematurely release from the catheter hub upon the removal of the needle leaving the needle tip exposed.
[0008] The prior art safety catheters all exhibit one or more drawbacks that have thus far limited their usefulness and full acceptance by health-care workers. What is needed therefore is a safety IV catheter that functions reliably, is easy and inexpensive to manufacture, and easy to use.
SUMMARY OF THE INVENTION
[0009] An intravenous catheter introducer assembly having a safety feature to prevent accidental needle sticks. The introducer assembly includes a needle assembly having an elongated hollow tubular needle with a proximal end attached to a catheter hub and a distal end extending therefrom. The needle has a groove disposed on its outer surface. The introducer includes a protector made of a hollow member having an open distal end and a inwardly disposed resilient flange disposed thereon. The protector is coaxially slidably disposed around the needle with the flange abutting the outer surface of the needle. The introducer also includes a catheter assembly having an elongated hollow tubular catheter with a proximal end attached to a catheter hub and a distal end extending therefrom. The catheter is coaxially disposed about the needle. The catheter hub has a retainer for keeping the protector within the catheter hub until the catheter assembly and needle assembly are separated wherein the flange engages the groove and secures the protector to the needle such that the open distal end of the protector is distal to the distal end of the needle.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The novel features of the invention are set forth with particularity in the appended claims. The invention itself, however, both as to organization and methods of operation, together with further objects and advantages thereof, may best be understood by reference to the following description, taken in conjunction with the accompanying drawings in which:
[0011] [0011]FIG. 1 is a perspective view of the catheter and needle assembly of the present invention.
[0012] [0012]FIG. 2 is an exploded perspective view of the catheter assembly and needle assembly including the needle tip protector of the present invention FIG. 3 is a perspective view of the needle tip protector of the present invention;
[0013] [0013]FIG. 4 is a view of FIG. 3 taken along line 4 - 4 illustrating the tab of the present invention.
[0014] [0014]FIG. 5 is a section view of the catheter assembly and needle assembly taken along line 5 - 5 of FIG. 1.
[0015] [0015]FIG. 6 is a perspective view of the needle tip protector with the needle inserted therethrough shown prior to locking the protector over the needle tip.
[0016] [0016]FIG. 7 is a perspective view of the needle tip protector shown as locked onto the needle after removal from the catheter hub and illustrating the needle tip covered by the protector.
[0017] [0017]FIG. 8 is a perspective view of an alternate embodiment of the needle tip protector.
[0018] [0018]FIG. 9 is a side view of another alternate embodiment of the needle tip protector shown as removed from the catheter hub and illustrating the needle tip covered by the protector.
[0019] [0019]FIG. 10 is a cross-sectional view taken along line 10 - 10 of FIG. 9 showing the clip which locks the needle tip protector over the needle tip.
[0020] [0020]FIG. 11 is a perspective view of another alternate embodiment of the needle tip protector shown with the needle inserted therethrough.
[0021] [0021]FIG. 12 is a side view of another alternate embodiment of a non-circular needle tip protector which illustrates the needle tip covered by the protector.
[0022] [0022]FIG. 13 is a cross-sectional view taken along line 13 - 13 of FIG. 12 of the non-circular needle and needle tip protector.
DETAILED DESCRIPTION OF THE INVENTION
[0023] As used herein, the term “proximal” refers to a location on the catheter and needle assembly with needle tip protector closest to the clinician using the device and thus furthest from the patient on which the device is used. Conversely, the term “distal” refers to a location farthest from the clinician and closest to the patient.
[0024] As illustrated in FIGS. 1 and 2, IV catheter assembly 20 comprises catheter assembly 22 and needle assembly 24 . Needle assembly 24 further includes protector 26 . Catheter assembly 22 includes catheter 28 which is a tubular structure having a proximal end 31 and distal end 29 . Proximal end 31 of catheter 28 is fixedly attached to catheter hub 30 . Catheters are well known in the medical art and one of many suitable materials, most of which are flexible thermoplastics, may be selected for use in catheter 28 . Such materials may include, for example, polyurethane or fluorinated ethylene propylene. Catheter hub 30 is a generally tubular structure having an internal cavity in fluid communication with the internal lumen of catheter 28 . Catheter hub 30 may be made from a suitable, rigid medical grade thermoplastic such as, for example, polypropylene or polycarbonate. For illustration purposes catheter hub 30 is shown translucent, though in actual use it may be translucent or opaque. At the proximal end of catheter hub 30 is integrally attached Luer fitting 32 , commonly known in the medical art. Luer fitting 32 provides for secure, leak proof attachment of tubing, syringes, or any of many other medical devices used to infuse or withdraw fluids through catheter assembly 22 . As shown in FIGS. 1, 2, and 5 , retainer 60 , which is located approximately mid way between the proximal end and distal end of sidewall 36 and fixedly attached thereto as at shoulder 134 , includes aperture 62 which is an opening therethrough. Retainer 60 is generally a doughnut shaped washer made of a material such as, for example, silicone or any other flexible material known to those skilled in the art. As will be described in more detail later, retainer 60 plays an important role in securing protector 26 in catheter hub 30 .
[0025] Referring again to FIGS. 1 and 2, needle assembly 24 comprises needle 38 , which is a tubular structure with proximal end 39 and distal end 41 , needle hub 40 , and protector 26 . Protector 26 is assembled slidably on needle 38 . Needle 38 which is preferably made of stainless steel has a lumen therethrough created by its inner diameter. Proximal end 39 of needle 38 is fixedly attached to needle hub 40 . Bevel 42 which is located at distal end 41 of needle 38 creates a sharp piercing tip. Needle groove 44 , which includes proximal wall 43 and distal wall 45 , is located at distal end 41 of needle 38 proximal to bevel 42 and is smaller in diameter than the nominal outer diameter of needle 38 . Needle groove 44 can be created by any number of means known to those skilled in the art. One such method is by machine grinding around the outside diameter of needle 38 resulting in an annular channel between its nominal outer diameter and inner diameter. Machine grinding is a process well known in the metal forming art. The resulting groove 44 is smaller in dimension than the nominal outer diameter of needle 38 but greater in dimension that the lumen in needle 38 and is important in preventing the complete removal of protector 26 from needle 38 , as will be described in more detail later. In the preferred embodiment, the dimension across groove 44 is 0.002-0.003 inches smaller than the dimension of the nominal outer diameter of needle 38 , dependent upon needle “gauge” size.
[0026] Needle hub 40 is generally a tubular structure having an internal cavity in fluid communication with the lumen in needle 38 . It is preferably made of a translucent or transparent generally rigid thermoplastic material such as, for example, polycarbonate. At the most proximal end of the internal cavity in needle hub 40 is fixedly attached porous plug 46 . A flashback chamber 48 is created in the cavity distal to porous plug 46 . Porous plug 46 contains a plurality of microscopic openings which are large enough to permit the passage of air and other gasses but small enough to prevent the passage of blood. Flashback chamber 48 fills with blood upon successful entry of the needle tip into the targeted vein, providing the clinician visual conformation of the correct placement of the needle.
[0027] Referring now to FIGS. 3 and 4, protector 26 has a proximal end 49 and a distal end 50 and is preferably a hollow tubular structure with cavity 72 therethrough formed from a single piece of thin, resilient material such as, for example, stainless steel or a polymer. Located distal to proximal end 49 of protector 26 is resilient flange 70 . Flange 70 includes a proximal wall and a distal wall. The longitudinal width of flange 70 , the distance between the proximal wall and the distal wall, is less than the longitudinal width of needle groove 44 and is important in preventing the complete removal of protector 26 from needle 38 , as will be described in more detail later. As shown in FIG. 4, resilient flange 70 is biased into cavity 72 of protector 26 resulting in dimension “a” which, when the flange 70 is in its relaxed unrestrained condition, is less than the nominal outer diameter of needle 38 , permitting for a very close but slidable fit of protector 26 over needle 38 .
[0028] Referring now to FIGS. 5 - 7 , it can understood how protector 26 is assembled to needle 38 . The proximal end of needle 38 is fixedly attached to the distal end of needle hub 40 , which contains porous plug 46 fixedly attached to its proximal end. The distal end of needle 38 is inserted through proximal end 49 of protector 26 and then advanced through cavity 72 , moving from proximal to distal. Flange 70 is flexed, as a result of its resilient property, so that needle 38 will pass through cavity 72 of protector 26 . Needle groove 44 is located at the distal end of needle 38 just proximal to bevel 42 . Groove 44 decreases the diameter of needle 38 locally to a dimension smaller than the nominal outer diameter of needle 38 . When needle 38 is retracted, flange 70 locks into groove 44 preventing the complete removal of protector 26 from the distal end of needle 38 .
[0029] As shown in FIG. 1, needle assembly 24 , including protector 26 , is assembled into catheter assembly 22 . Distal end 41 of needle 38 extends distally from distal end 29 of catheter 28 . Protector 26 is held distal to retainer 60 inside the cavity in catheter hub 30 by aperture 62 , which has a diameter smaller in dimension than the outer diameter of protector 26 . Protector 26 is also located proximal to catheter 28 , which has an inner diameter smaller than the outer diameter of protector 26 preventing any further distal movement. Needle assembly 22 is secured onto luer fitting 32 of catheter hub 30 .
[0030] Now, it will be described how in actual clinical use, the IV catheter assembly 20 of the present invention functions. The distal end of needle 38 which extends just past the distal end of catheter 28 is inserted into the patient's vein. The clinician observes blood in the flash chamber in needle hub 40 . The clinician grasps needle hub 40 , and catheter assembly 22 alone is moved distally into the vein. The clinician applies slight pressure to the insertion site to hold catheter assembly 22 secure. The clinician grasps needle hub 40 and begins withdrawal of needle assembly 24 from catheter assembly 22 . During this process, protector 26 remains secure inside catheter hub 30 until groove 44 on needle 38 comes into contact with flange 70 . Prior to groove 44 encountering flange 70 , retainer 60 blocks any further proximal movement of protector 26 . During withdrawal, needle 38 is retracted proximally into catheter 28 and catheter hub 30 . When groove 44 of needle 38 comes into contact with flange 70 of protector 26 , the distance between proximal wall 71 and distal wall 73 of flange 70 which is less than the distance between proximal wall 43 and distal wall 45 of groove 44 causes flange 70 which is biased into cavity 72 to engage into groove 44 thus locking protector 26 on needle 38 . After flange 70 locks into groove 44 , continued proximal movement of needle 38 carries protector 26 proximal as well, forcing proximal end 49 of protector 26 against retainer 60 . When enough force is applied by protector 26 , aperture 62 dilates due to the resilient property of retainer 60 , permitting continued movement proximal, past retainer 60 . Needle assembly 24 is now removed entirely from catheter assembly 22 , with the needle tip covered by protector 26 of the present invention.
[0031] A first alternate embodiment of the present invention is shown in FIG. 8. In this embodiment, protector 126 , similar to protector 26 , is generally hollow tubular structure formed from a single piece of thin, resilient material such as, for example, stainless steel or a polymer. This embodiment has a plurality of flanges 170 . Flanges 170 are located distal to proximal end 149 of protector 126 . Flanges 170 create proximal walls 171 and distal walls 173 and are biased into cavity. 172 of protector 126 .
[0032] A second alternate embodiment of the present invention is shown in FIG. 9. In this embodiment, protector 226 , similar to protector 26 , includes clip 270 . Clip 270 , which functions to replace flange 70 in the preferred embodiment, is slidably assembled to protector 226 . Clip 270 is preferably made of a resilient material such as, for example, stainless steel, or any other suitable material known to those skilled in the art. As shown in FIG. 10, clip 270 is generally a U-shaped wireform secured to protector 226 by bridges 264 and 266 .
[0033] [0033]FIG. 11 shows a third alternate embodiment where protector 326 is a hollow tubular structure preferably formed from a single piece of thin, resilient material such as for example, stainless steel or a polymer. In this embodiment, protector 326 has a flat formed on one side along its entire length. Located distal to proximal end 349 of protector 326 is flange 370 , similar to flange 70 . Needle notch 344 , which functions to replace needle groove 44 , is an indentation in needle 338 . In this embodiment, the depth from surface 347 of needle notch 344 to the outer surface of needle 338 is 0.002-0.003 inches, dependent upon needle “gauge” size. However, the depth from surface 347 of needle notch 344 to the outer surface of needle 338 could be larger than 0.003 inches possibly exposing the lumen of needle 338 . Needle notch 344 locks with flange 370 preventing the complete removal of protector 326 from distal end 341 of needle 338 . To ensure the alignment of flange 370 with notch 344 , needle 338 also has a flat along its entire length which takes the shape of protector 326 to prevent any axial movement of needle 338 in protector 326 . Needle notch 344 could be a single indentation in needle 338 or multiple indentations possibly spaced 180° apart. Similarly, protector 326 could contain a single flange or multiple flanges possibly spaced 180° apart.
[0034] [0034]FIGS. 12 and 13 shows a fourth alternate embodiment of the present invention. In this embodiment, protector 426 is a hollow non-circular tubular structure preferably formed from a single piece of thin, resilient material such as, for example, stainless steel or a polymer. Located distal to proximal end 449 of protector 426 is flange 470 , similar to flange 370 . Needle notch 444 , similar to notch 344 , functions to replace needle groove 44 . Needle notch 444 is an indentation in needle 438 which locks with flange 470 preventing the complete removal of protector 426 from distal end 441 of needle 438 . In this embodiment, the depth from surface 447 of needle notch 444 to the outer surface of needle 438 is 0.002-0.003 inches, dependent upon needle “gauge” size. However, the depth from surface 447 of needle notch 444 to the outer surface of needle 438 could be larger than 0.003 inches possibly exposing the lumen of needle 438 . To ensure the alignment of flange 470 with notch 444 , needle 438 is also non-circular taking the shape of protector 426 to prevent any axial movement of needle 438 in protector 426 . Needle notch 444 could be a single indentation in needle 438 or multiple indentations possibly spaced 180° apart. Similarly, protector 426 could contain a single flange or multiple flanges possibly spaced 180° apart.
[0035] While preferred embodiments of the present invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions will now occur to those skilled in the art without departing from the invention. Accordingly, it is intended that the invention be limited only by the spirit and scope of the appended claims. In addition, it should be understood that every structure described above has a function and such structure can be referred to as a means for performing that function.
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An intravenous catheter introducer assembly having a safety feature to prevent accidental needle sticks. The introducer assembly includes a needle assembly having a groove disposed on its outer surface. The introducer includes a protector made of a hollow member having an open distal end and an inwardly disposed resilient flange or a clip disposed thereon. The protector is coaxially slidably disposed around the needle with the flange abutting the outer surface of the needle and adapted to engage the groove when a catheter assembly is removed from the needle.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a road milling machine with a machine frame and a milling mechanism for milling off material.
2. Description of the Prior Art
The known road milling machines have a machine frame, which is supported by a chassis, and a milling mechanism, which comprises a milling drum for milling off material. The milling drum, which is rotatable about an axis transverse to the operating direction, is located in a milling drum housing.
Furthermore, the known road milling machines have a transport arrangement for conveying the milled material. In the known rear loader road milling machines, the transport arrangement is behind the milling drum housing, when seen in the operating direction, to allow it to feed the milled material, as far as possible free from residues, over the rear of the milling machine to the following truck. A rear loader road milling machine is known, for example, from DE 195 47 698 A1.
With the known road milling machines, the road surface can be milled true to contour and evenly. The so-called stabilisers or recyclers should be differentiated from road milling machines; the role of the former is to produce a stable substructure by addition of binding agents to unstable ground, for example loose soil (stabiliser) or a damaged roadway (recycler).
In the operation of the known road milling machines, particular requirements are demanded of the design of the milling drum housing. The milling drum housing should prevent the milled material being ejected. In particular, the risk of ejection of milled material exists in the operating direction of the milling machine if the milling drum is rotated in the direction opposite to the operating direction. The milling drum housing should also ensure that there is a continuous supply of milled material to the transport arrangement.
DE 10 2008 024 651 describes a rear loader road milling machine whose milling drum is positioned in a milling drum housing that surrounds the milling drum. A so-called hold-down device, which is mounted on a circular track concentrically surrounding the axis of rotation of the milling drum and is adjustable in height, serves to seal the milling drum housing from the surface of the material to be milled. In the known road milling machines, an aim is to have a uniform gap width for the gap between the tips of the milling tools of the milling drum and the inside of the hold-down device over the periphery of the milling drum. A uniform gap width should be obtained, independent of the set milling depth, where the hold-down device runs on a concentric circular track around the axis of rotation of the milling drum.
The stripping elements, which are located behind the milling drum, when seen in the operating direction, are to be differentiated from the hold-down devices. In the known stabilisers or recyclers, the mixed material should be uniformly removed with the stripping elements to a specified depth and evenly distributed.
SUMMARY OF THE INVENTION
The object of the invention is therefore to create a road milling machine with improved material transport of the milled material within the milling drum housing.
This object is achieved, according to the present invention, with the features of the independent patent claims. The dependent claims relate to advantageous embodiments of the invention.
The milling drum housing of the road milling machine in accordance with the invention is a fixed housing, which partially surrounds the milling drum. The opening between the milling drum housing and the surface of the material to be milled off, the depth of which varies with the set milling depth, can be closed with a hold-down device.
In the road milling machine in accordance with the invention, the hold-down device is configured so that the distance between the hold-down device and the milling drum housing increases in the specified direction of rotation of the milling drum, at least over a section of the gap between the milling drum and the hold-down device. Preferably, the distance between the axis of rotation of the hold-down device increases over the whole periphery of the hold-down device, so that the gap width increases over the whole length of the gap between milling drum and hold-down device. However, it is basically sufficient for the gap width to increase over only a section of the periphery of the hold-down device. In this connection, gap width should be understood as the distance between the inside of the hold-down device and a cylinder which encloses the tips of the milling tools of the milling drum.
The milling drum housing and the hold-down device preferably extend in the axial direction over the width of the milling drum. Preferably, the milling drum housing is closed at the sides by side plates.
In a preferred embodiment, both the distance between the axis of rotation and the milling drum housing, i.e. the gap width between milling drum and milling drum housing, and the distance between the axis of rotation and the hold-down device, i.e. the gap width between milling drum and hold-down device, increase upwards in the direction of rotation of the milling drum, i.e. from the surface of the material being milled. As a result, the hold-down device continues the contour of the milling drum housing.
The configuration of the hold-down device with increasing gap width leads to an improvement in transport of the milled material to the transport arrangement. It has been shown that the distance between the milling drum and hold-down device is particularly important for material flow, since the material is picked up in the region of the hold-down device. A uniform distance between milling drum and hold-down device leads to an undesired compaction of the milled-off material. This material compaction impedes transport of material over the milling drum to the rear. Furthermore, the material compaction requires higher power for the drum and leads to increased wear. It has also been shown that an excessively large gap, which requires less power for the drum and leads to reduced wear, also makes transport of material more difficult. The gap width increasing in the direction of rotation of the milling drum, in particular in the region of the hold-down device, improves material flow with a relatively small power requirement and relatively low wear.
While the milled material is conveyed through the gap in the direction of rotation of the milling drum, the packing density of the material can reduce without there being a risk that the material remains compacted or is compacted. As the packing density decreases, the milled material is first conveyed with increasing speed through the gap in the region of the hold-down device and later is ejected to the rear, so that the material can be picked up by the transport arrangement. The relatively small gap width at ground level results in lumps of material accumulating during milling being immediately broken up to the desired particle size.
A preferred embodiment provides that the hold-down device is guided displaceably on a guide track surrounding the milling drum between a first position, in which the hold-down device is lowered, and a second position, in which the hold-down device is raised. When the milling drum having a horizontal axis of rotation penetrates in the vertical direction into the material to be milled, the hold-down device is adjusted in height.
A particularly preferred embodiment provides that the lower edge of the hold-down device and the lower edge of the milling drum housing are essentially at the same level when the hold-down device is in the second position. The maximum milling depth is obtained in this position. However, it is also possible for the milling drum housing and the hold-down device partially to overlap at the maximum milling depth.
For the basic principle of the invention, it is not basically significant how the guide or mounting of the hold-down device is provided, as long as it has sufficient rigidity. In a preferred embodiment, adequate rigidity of the guide is obtained by extending guide elements around the periphery of the hold-down device, which are displaceably guided in the mounting elements surrounding the periphery of the hold-down device. However, as an alternative, it is also possible for the hold-down device to have mounting elements that are displaceably guided in guide elements.
The guide elements of the hold-down device preferably extend beyond the hold-down device, so that the guide elements enclose part of the periphery of the milling drum housing. As a result, the hold-down device can be supported on the milling drum housing via the guide elements when the hold-down device is in the lowered position. Thus the rigidity of the guide is further improved.
Preferably, two guide or mounting elements are provided and are positioned on either side of the milling drum housing or hold-down device. In principle, it is also possible for only one guide element or only one mounting element to be provided.
It has proved to be advantageous if a breaker element, extending in the direction of the axis of rotation of the milling drum, is positioned in the gap between milling drum and milling drum housing. Lumps of material accumulating during milling can be broken down to the desired particle size on the breaker element. However, the breaker element, extending in the direction of the axis of rotation of the milling drum, only comes into use when the lumps have not already been broken during transport through the gap.
While the road milling machine is moved in the operating direction, the opening between the lower edge of the milling drum housing and the surface of the material to be milled should always be tightly closed, regardless of the milling depth.
Tilting of the hold-down device can be avoided by positioning a skid on the lower edge of the hold-down device, with which the hold-down device rests on the material to be milled as the machine advances. With the skid, the hold-down device can move upwards in the guide against its contact force on impact with an obstacle.
In a further preferred embodiment, a mechanism is provided or lifting and lowering the hold-down device, so that the movement of the hold-down device is supported, in particular from the lowered to the raised position.
The mechanism for raising and lowering the sealing element preferably has a measurement unit, which is configured so that the measurement unit measures the force acting on the sealing element when the hold-down device encounters an obstacle. Furthermore, the mechanism for raising and lowering has a control unit, which is configured so that the control unit generates a control signal for raising the hold-down device when the force measured by the measuring unit is greater than a predetermined limit value, so that the hold-down device is raised, and a control signal is generated for lowering the hold-down device when the force is smaller than a predetermined limit value, so that the hold-down device is pressed on the ground with the predetermined contact force.
The force measured with the measuring unit is preferably the essentially horizontal force component acting on the hold-down device when it strikes an obstacle. However, it is also possible that the measured force has a vertical component.
The advantage of the sealing element in accordance with the invention is that obstacles in the operating direction of the construction machine are detected when the force acting on the hold-down device exceeds a limit value. When this is the case, the hold-down device is automatically raised. The hold-down device is only raised until the measured force is again below the limit value. In this case, it is assumed that the obstacle has been negotiated. The hold-down device is then lowered until the hold-down device rests on the ground with the predetermined contact force. The limit value for the measured force should be calculated so that the hold-down device is not raised just for very small obstacles.
In a preferred embodiment, the mechanism for raising and lowering the hold-down device comprises one or more piston/cylinder arrangements where their cylinders have an articulated connection to the machine frame and their pistons have an articulated connection to the hold-down device or their cylinders have an articulated connection to the hold-down device and their pistons have an articulated connection to the machine frame. The piston/cylinder arrangement can be operated hydraulically or pneumatically. However, an electric motor can also be used for height adjustment. The sub-assemblies required for this purpose are state of the art.
BRIEF DESCRIPTION OF THE DRAWINGS
In the following, an example of an embodiment of the invention is explained in detail with reference to the drawings.
These show:
FIG. 1 a rear loader road milling machine in accordance with the invention in a perspective view,
FIG. 2 a simplified schematic representation of the milling drum housing of the road milling machine in accordance with the invention, together with the milling drum and machine frame in a first operating position of the hold-down device,
FIG. 3 the milling drum housing in accordance with the invention in a second operating position of the hold-down device,
FIG. 4 the milling drum housing in accordance with the invention in a third operating position of the hold-down device,
FIG. 5 a schematic representation of the milling drum housing, together with the milling drum, wherein the hold-down device is in a raised position,
FIG. 6 the milling drum housing of FIG. 5 , wherein the hold-down device is in a lowered position and
FIG. 7 a section through a guide element and a mounting element of the guide of the hold-down device and
FIG. 8 a further embodiment of the milling drum housing in accordance with the invention.
DETAILED DESCRIPTION
FIG. 1 shows in a perspective view a road milling machine, specifically a rear loader road milling machine. The road milling machine comprises a machine frame 1 , which is supported by a chassis 2 . The chassis 2 has a front wheel 2 A and two rear wheels 2 B, when seen in the operating direction. The operator's platform 3 is in the rear part of the machine frame. The milling mechanism 4 of the road milling machine is underneath the operator's platform 3 .
The milling mechanism 4 comprises a milling drum 5 , with cutting tools 5 A spaced around its periphery. The milling drum 5 is positioned in a milling drum housing 7 about an axis of rotation 6 running transverse to the operating direction of the milling machine. The milling drum 5 rotates in the milling drum housing 7 in a predetermined direction of rotation D. In the present example, the milling drum 5 rotates in a counter-clockwise direction. The milling drum housing 7 enclosing the milling drum 5 has a discharge opening at the rear, when seen in the operating direction. The milling drum housing is closed off by side plates 33 on the longitudinal sides. On the milling drum housing 7 is the transport arrangement 9 , with a conveyor belt 10 for conveying the milled material, which can be received by a truck driven behind the milling machine.
In the following, the milling drum housing 7 accommodating the milling drum 5 is described in detail with reference to FIGS. 2 to 8
The milling drum housing 7 is fixedly attached to the machine frame 1 . The fastening members for the milling drum housing 7 are not shown in the Figures. In the Figures, the milling drum 5 is represented schematically by a cylindrical body that encloses the tips of the tools 5 A of the milling drum 5 . The milling drum housing 7 extends beyond the width of the milling drum 5 on both sides. It surrounds the milling drum 5 except for an opening 11 A in front of the milling drum, when seen in the operating direction, and a discharge opening 11 B behind the milling drum, when seen in the operating direction. The opening 11 A at the front, when seen in the operating direction is closed by a hold-down device 8 . The milled material is discharged to the rear and is picked up by the conveyor belt 9 of the transport arrangement 10 . A stripper element in the rear part of the milling drum housing 7 is not shown in the Figures.
The height of the hold-down device 8 can be adjusted according to the milling depth. FIGS. 2 to 4 show how the milling drum penetrates into the material to be milled off in the vertical direction. While the milling drum is penetrating into the material, the hold-down device 8 is moved from a first position, shown in FIG. 2 , in which the hold-down device 8 is fully lowered, into a second position, in which the hold-down device is fully raised ( FIG. 4 ). The maximum milling depth is obtained in this position. FIG. 3 shows a middle position of the hold-down device 8 with a smaller milling depth. In the present embodiment, the closed milling drum housing 7 , closed at the front, along with the hold-down device 8 completely surrounds the milling drum 5 over a circumferential angle of approximately 180°.
FIGS. 5 and 6 show a sectional view, wherein the hold-down device 8 is in the raised position ( FIG. 5 ) and in the lowered position ( FIG. 6 ). The hold-down device 8 closes the opening 11 A pointing in the operating direction between the lower edge 12 of the hold-down device 8 and the surface of the road pavement material 13 to be milled off.
The milling drum housing 7 , surrounding the milling drum 5 over a circumferential angle of more than 90°, preferably has a spiral contour. The cross-section of the milling drum housing 7 describes a curve which, in the running direction, is spaced from the axis of rotation about the axis of rotation 6 of the milling drum 5 , wherein the running direction of the curve corresponds to the turning direction of the milling drum 6 . The milling drum housing 7 is configured so that the distance between the axis of rotation 6 and the inside of the milling drum housing 7 continuously increases from the lower edge 17 up to the upper edge 14 . Consequently, the radius r 1 <r 2 <r 3 . For this reason, the width of the gap between the milling drum body 5 surrounding the tips of the milling tools 5 and the inside of the milling drum housing 7 continuously increases from the bottom to the top. However, the increase need not necessarily be continuous. It is only important that the gap width enlarges.
It is preferred that the hold-down device, in particular, has a spiral contour. The cross-section of the hold-down device describes a curve which, in the running direction, is spaced from the axis of rotation about the axis of rotation 6 of the milling drum 5 , wherein the running direction of the curve corresponds to the turning direction of the milling drum 6 . The hold-down device and the lower section of the milling drum housing 7 can have precisely the same curvature. In this case, milling drum housing and hold-down device can lie with one precisely in top of the other in the raised position. However, it is also possible for the spiral contour of the milling drum housing 7 to be continued in the hold-down device 8 when the hold-down device 8 is in the lowered position. The milling drum housing and hold-down device cannot then lie precisely with one on top of the other in the raised position. In practice, the two embodiments exhibit no significant differences.
The gap width, preferably increasing over the whole periphery of the milling drum housing 7 and the hold-down device 8 from bottom to top improves the flow of milled material along the gap 15 , in particular between the milling drum 5 and hold-down device 8 against the operating direction A of the milling machine. The milled material, whose packing density decreases in the direction of rotation D of the milling drum 5 , and whose volume increases, can be conveyed continuously into the gap 15 with increasing gap width. The power required for driving the milling drum and the wear on the milling tools are thereby relatively small.
FIG. 6 shows the hold-down device 8 in the lowered position, wherein the distance between the inside of the hold-down device 8 and the axis of rotation 6 of the milling drum 5 is referenced with r 1 ′, r 2 ′, and r 3 ′ (r 1 ′<r 2 ′<r 3 ′).
In practice, it has been shown that the gap width can vary over the whole periphery of the milling drum between 15 and 80 mm, preferably between 25 and 50 mm. It is not absolutely necessary for the gap width to increase continuously over the whole periphery of the milling drum.
In the present embodiment, the gap width in the region of the hold-down device 8 is larger than that at the lower edge 17 of the milling drum housing 7 . In this embodiment, lumps of removed material can still reach the milling drum housing, which forms a gap with increasing gap width with the milling drum. Therefore, in the present embodiment, a breaker element may be positioned within the gap 15 , extending in the direction of the axis of rotation 6 . Coarser material remaining in the gap 15 can be broken up with the breaker element.
FIG. 8 shows a schematic representation of the guide of the hold-down device 8 . On the outside, the hold-down device has a guide rail 15 A, 15 B on either side extending upwards over the periphery. The guide rails 15 A and 15 B are guided in mounting elements 16 A and 16 B, which are fastened on the machine frame 1 . The fastening of the mounting elements is not shown in FIG. 7 .
FIG. 7 shows a section through the guide rails 15 A, 15 B and mounting elements 16 A, 16 B. The mounting elements 16 A, 16 B have a U-shaped cross-section, in which the guide rails 15 A, 15 B are longitudinally displaceable. Since the mounting elements 16 A, 16 B encompass the guide rails 15 A, 15 B, the guide rails are secured in axial and radial directions. When the hold-down device 8 is in the lowered position, the sections of the guide rails 15 A, 15 B extending upwards are supported on the milling drum housing 7 . Because of this, even greater forces can be absorbed.
At the lower edge 27 , the hold-down device 8 has a sliding element 18 extending along the lower edge, which can be a sliding bar. The hold-down device 8 slides with the sliding element 18 on the surface of the road pavement 13 . In doing so, the hold-down device 8 is supported on the road pavement solely due to its weight. When the milling drum 5 penetrates into the road surface in the vertical direction, the hold-down device 8 moves upwards in the guide.
In the present embodiment, a mechanism 19 is provided for raising and lowering the hold-down device 8 . In particular, supporting the upward movement of the hold-down device 8 when the milling depth is varied.
The mechanism 19 for raising and lowering the hold-down device 8 comprises a piston/cylinder arrangement 20 . The piston/cylinder arrangement 20 is operated by a hydraulic unit 21 , shown only in outline, which supplies a hydraulic fluid to the cylinder 20 A of the piston/cylinder arrangement 20 .
The cylinder 20 A of the piston/cylinder arrangement 20 has an articulated connection to the machine frame 1 and the piston 20 B has an articulated connection to the upper end of a U-shaped profile element 22 , which is fastened to the hold-down device 8 . The hold-down device 8 can be raised and lowered by admitting hydraulic fluid to the cylinder 20 A.
The mechanism 19 for raising and lowering the hold-down device 8 further has a control unit 23 and a processing unit 24 , which are connected together by means of a data line 25 . The control unit 23 , which is connected to the hydraulic unit 21 by a control line 26 , controls the hydraulic unit 21 , so that the piston/cylinder arrangement 20 keeps the hold-down device 8 in contact with the ground with a predetermined downwards force. For example, the hydraulic unit can release the piston in the cylinder, so that the hold-down device 8 rests on the ground under its weight if the hold-down device 8 is not raised when it strikes an obstacle.
The mechanism 19 for raising and lowering the hold-down device 8 further comprises a measuring unit 26 for measuring the force exerted on the hold-down device 8 on impact with an obstacle. Preferably, only the horizontal force component acting on the sealing element is measured by the measuring unit.
The processing unit 24 compares the impact force measured by the measuring unit 26 with a predetermined limit value. When the impact force is greater than the limit value, the control unit 23 generates a first control signal for the hydraulic unit 21 to raise the hold-down device 8 , so that the hydraulic unit 21 actuates the piston 20 B of the piston/cylinder unit 20 . The hold-down device 8 is raised by the piston/cylinder unit 20 until the measured impact force is again less than the predetermined limit value. When the impact force is smaller than the limit value, the control unit 23 generates a control signal for the hydraulic unit 21 , with which the piston/cylinder arrangement 20 is actuated once more to lower the hold-down device 8 again until the lower edge 27 of the hold-down device 8 again rests on the ground with the predetermined downwards force. Alternatively, the piston/cylinder arrangement 20 can also release the hold-down device 8 , so that the hold-down device moves downwards in the guide under its own weight.
The measuring unit 26 has two sensors 26 A, 26 B, for measuring the impact force, positioned between the mounting elements 16 A, 16 B and the guide rails 15 A, 15 B, in the area in which the guide rails extend upwards beyond the hold-down device 8 . When an essentially horizontal force acts on the hold-down device, the ends of the guide rails exert a contact pressure on the ends of the mounting elements, which is measured by the two sensors 26 A, 26 B. The sensors 26 A, 26 B are connected to the processing unit 24 by signal lines 26 A′ and 26 B′. The processing unit 24 processes the measurement signals of the two sensors. Either only one or the other measurement signal can be processed, or both measurement signals together. For example, the two measurement signals can be averaged. Suitable pressure sensors and the processing of the measurement signals are part of the state of the art. A skid 34 can also be provided on the hold-down device, to support the upwards movement and to introduce the force on impact with an obstacle.
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The invention relates to a road milling machine, with a milling drum housing partially surrounding a milling drum, wherein the opening between the milling drum housing and the surface of the material to be milled can be closed off by a hold-down device. The distance between the axis of rotation and the hold-down device increases in the specified direction of rotation of the milling drum at least over a section of the gap between the milling drum and the hold-down device. The particular configuration of the hold-down device leads to an improvement in transport of the milled material to the transport arrangement. The gap width increasing in the direction of rotation of the milling drum improves material flow with a relatively small power requirement and relatively low wear of the milling drum.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of application Ser. No. 09/618,320 filed on Jul. 18, 2000, now U.S. Pat. No. 6,289,145, which is a continuation of application Ser. No. 09/022,591 filed on Feb. 12, 1998, now U.S. Pat. No. 6,097,859, which claims priority from provisional application Ser. No. 60/038,172 filed on Feb. 13, 1997. This application is also related to co-pending application Ser. No. 09/748,025 filed on Dec. 21, 2000, co-pending application Ser. No. 09/766,529 filed on Jan. 19, 2001, co-pending application Ser. No. 09/780,122 filed on Feb. 8, 2001, and co-pending application Ser. No. 09/813,446 filed on Mar. 20, 2001.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not Applicable
REFERENCE TO A MICROFICHE APPENDIX
Not Applicable
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a cross-connect switch for fiber-optic communication networks including wavelength division multiplexed (WDM) networks, and more particularly to such an optical switch using a matrix of individually tiltable micro-mirrors.
2. Description of the Background Art
Multi-port, multi-wavelength cross-connect optical switches with characteristics of large cross-talk rejection and flat passband response have been desired for use in wavelength-division multiplexed (WDM) networks. Four-port multi-wavelength cross-bar switches based on the acousto-optic tunable filter have been described (“Integrated Acoustically-tuned Optical Filters for Filtering and Switching Applications,” D. A. Smith, et al., IEEE Ultrasonics Symposium Proceedings, IEEE, New York, 1991, pp. 547-558), but they presently suffer from certain fundamental limitations including poor cross-talk rejection and an inability to be easily scaled to a larger number of ports. Attempts are being made to address to this problem by dilating the switch fabric, both in wavelength and in switch number, to provide improved cross-talk rejection and to expand the number of switched ports so as to provide an add-drop capability to the 2×2 switch fabric. This strategy, however, adds to switch complexity and cost. Recently, Patel and Silberberg disclosed a device employing compactly packaged, free-space optical paths that admit multiple WDM channels spatially differentiated by gratings and lenses (“Liquid Crystal and Grating-Based Multiple-Wavelength Cross-Connect Switch,” IEEE Photonics Technology Letters, Vol. 7, pp. 514-516, 1995). This device, however, is limited to four (2×2) ports since it relies on the two-state nature of polarized light.
BRIEF SUMMARY OF THE INVENTION
It is therefore an object of this invention to provide an improved multi-wavelength cross-connect optical switch which is scalable in port number beyond 2×2.
Another object of the invention to provide such an optical switch which can be produced by known technology.
Another object of this invention to provide such an optical switch with high performance characteristics such as basic low loss, high cross-talk rejection and flat passband characteristics.
Another object of the invention is to provide a fiber-optic switch using two arrays of actuated mirrors to switch or rearrange signals from N input fibers onto N output fibers, where the number of fibers, N, can be two, or substantially larger than 2.
Another object of the invention is to provide a fiber-optic switch using 1-D arrays of actuated mirrors.
Another object of the invention is to provide a fiber-optic switch using 2-D arrays of actuated mirrors.
Another object of the invention is to provide a fiber-optic switch using mirror arrays (1-D or 2-D) fabricated using micromachining technology.
Another object of the invention is to provide a fiber-optic switch using mirror arrays (1-D or 2-D) fabricated using polysilicon surface micromachining technology.
Another object of the invention is to provide a fiber-optic switch using arrays (1-D or 2-D) of micromirrors suspended by torsion bars and fabricated using polysilicon surface micromachining technology.
Another object of the invention is to provide a fiber-optic switch with no lens or other beam forming or imaging optical device or system between the mirror arrays.
Another object of the invention is to provide a fiber-optic switch using macroscopic optical elements to image or position the optical beams from the input fibers onto the mirror arrays, and likewise using macroscopic optical elements to image or position the optical beams from the mirror arrays onto the output fibers.
Another object of the invention is to provide a fiber-optic switch using microoptics to image or position the optical beams from the input fibers onto the mirror arrays, and likewise using microoptics to image or position the optical beams from the mirror arrays onto the output fibers.
Another object of the invention is to provide a fiber-optic switch using a combination of macrooptics and microoptics to image or position the optical beams from the input fibers onto the mirror arrays, and likewise using combination of macrooptics and microoptics to image or position the optical beams from the mirror arrays onto the output fibers.
Another object of invention is to provide a fiber-optic switch in which the components (fibers, gratings, lenses and mirror arrays) are combined or integrated to a working switch using Silicon-Optical-Bench technology.
Another object of the invention is to provide a fiber-optic switch using 2-D arrays of actuated mirrors and dispersive elements to switch or rearrange signals from N input fibers onto N output fibers in such a fashion that the separate wavelength channels on each input fiber are switched independently.
Another object of the invention is to provide a fiber-optic switch as described above, using diffraction gratings as wavelength dispersive elements.
Another object of the invention is to provide a fiber-optic switch as described above, using micromachined diffraction gratings as wavelength dispersive elements.
Another object of the invention is to provide a fiber-optic switch using fiber Bragg gratings as wavelength dispersive elements.
Another object of the invention is to provide a fiber-optic switch using prisms as wavelength dispersive elements.
Another object of the invention is to provide a fiber-optic based MEMS switched spectrometer that does not require mechanical motion of bulk components nor large diode arrays, with readout capability for WDM network diagnosis.
Another object of the invention is to provide a fiber-optic based MEMS switched spectrometer that does not require mechanical motion of bulk components nor large diode arrays, with readout capability for general purpose spectroscopic applications.
Further objects and advantages of the invention will be brought out in the following portions of the specification, wherein the detailed description is for the purpose of fully disclosing preferred embodiments of the invention without placing limitations thereon.
An optical switch embodying this invention, with which the above and other objects can be accomplished, may be characterized as comprising a wavelength dispersive element, such as a grating, and a stack of regular (non-wavelength selective) cross bar switches using a pair of two-dimensional arrays of micromachined, electrically actuated, controlled deflection micro-mirrors for providing multiport switching capability for a plurality of wavelengths.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be more fully understood by reference to the following drawings which are for illustrative purposes only:
FIG. 1 is a schematic diagram of an optical switch in accordance with the present invention.
FIG. 2 is a schematic plan view of a single layer of the switching matrix portion of the optical switch shown in FIG. 1 .
FIG. 3 is a diagrammatic plan view of a row of individually tiltable micro-mirrors employed in the switch array portion of the optical switch shown in FIG. 1 .
FIG. 4 is a schematic diagram showing switching matrix geometry in accordance with the present invention.
FIG. 5 is a schematic sectional view of a grating made in silicon by anisotropic etching.
FIG. 6 is a schematic diagram of an alternative embodiment of the optical switch shown in FIG. 1 employing a mirror in the symmetry plane.
FIG. 7 is a schematic plan view of a single layer of the switching matrix portion of the optical switch shown in FIG. 6 .
FIG. 8 is a schematic diagram of a WDM spectrometer employing an optical switch in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Referring more specifically to the drawings, for illustrative purposes the present invention is embodied in the apparatus generally shown in FIG. 1 through FIG. 8, where like reference numerals denote like parts. It will be appreciated that the apparatus may vary as to configuration and as to details of the parts without departing from the basic concepts as disclosed herein.
Referring first to FIG. 1, a multi-port (N×N ports), multi-wavelength (M wavelength) WDM cross-connect switch 10 embodying this invention is schematically shown where, in the example shown, N=3. In this switch 10 , the wavelength channels 12 a , 12 b , 12 c of three input fibers 14 a , 14 b , 14 c are collimated and spatially dispersed by a first (or input) diffraction grating-lens system 16 . The grating-lens system 16 separates the wavelength channels in a direction perpendicular to the plane of the paper, and the dispersed wavelength channels are then focused onto a corresponding layer 18 a , 18 b , 18 c of a spatial micromechanical switching matrix 20 . The spatially reorganized wavelength channels are finally collimated and recombined by a second (or output) diffraction grating-lens system 22 onto three output fibers 24 a , 24 b , 24 c . The input and output lens systems are each composed of a lenslet array 26 ( 32 ) and a pair of bulk lenses 28 , 30 ( 34 , 36 ) such that the spot size and the spot separation on the switching matrix 20 can be individually controlled. Two quarter-wave plates 38 , 40 are inserted symmetrically around the micromechanical switching matrix 20 to compensate for the polarization sensitivity of the gratings 42 , 44 , respectively.
Referring now to FIG. 2, a schematic plan view of a single layer 18 a of the switching matrix 20 of FIG. 1 is shown. As can be seen in FIG. 2, six micromirrors 46 a through 46 f are arranged in two arrays 48 a , 48 b that can be individually controlled so as to optically “couple” any of the three input fibers 14 a , 14 b , 14 c to any of the three output fibers 24 a , 24 b , 24 c . Referring also to FIG. 3, an example of the structural configuration of a row of individually tiltable micromirrors on the switch array can be seen. As shown in FIG. 3, each mirror 46 a , 46 b , 46 c is suspended by a pair of torsion bars or flexing beams 50 a , 50 b attached to posts 52 a , 52 b , respectively. Note that each mirror also includes a landing electrode 54 on which the mirrors land when they are deflected all the way down to the substrate.
The advantages of this switching matrix arrangement include low cross talk because cross coupling between channels must go through two mirrors, both of which are set up to reject cross talk, low polarization sensitivity, and scalability to larger numbers of input fibers than two (which is the limit for polarization-based switches). The preferred fabrication technology for the micromirror arrays is surface micromachining as disclosed, for example, in Journal of Vacuum Science and Technology B, Vol. 6, pp. 1809-1813, 1988 because they can be made by this method as small as the optical design will allow, they can be batch-fabricated inexpensively, they can be integrated with on-chip micromachinery from materials such as polysilicon and they can be miniaturized so as to reduce the cost of packaging.
Referring now to FIG. 4, there are several factors to consider for designing the switching matrix 20 . FIG. 4 shows an example of two mirror arrays 56 a , 56 b where each array comprises a plurality of mirrors, Na through Nn. The basic parameters are the Gaussian beam radium (ω 0 ) at the center of the switch, the mirror size in the horizontal direction (s), the distance between the mirror arrays (p), the incident angle on the mirror arrays (β), and the maximum deflection of the micromirrors (t). The maximum angular deflection (α) of the optical beams is dependent on the maximum deflection and the mirror size (in the horizontal direction), or tan α=4t/s (the optical deflection being twice that of the mechanical deflection and the mirrors being tethered at their center points). Conditions that must be satisfied include: (i) the optical beams must be sufficiently separated on the mirrors to keep cross-talk at reasonable levels; (ii) the sizes of the arrays must be small enough such that no shadowing occurs; and (iii) the path length differences through the switch must not introduce significant variations in insertion loss.
If a Gaussian-beam formalism is used, the cross coupling of two parallel beams of radius ω 0 offset by d is given as exp{−(d/ω 0 )2}. If this should be less than 40 dB, for example, the ratio C=d/ω 0 must be larger than 3. This minimum ratio applies to both fiber-channel (horizontal) separation and wavelength channel (vertical) separation. Since the beam radii are larger at the mirrors due to diffraction than at the focus, the above conclusion does not strictly apply, but it may be required that the spacing of the beams must be at least three times larger than the optical beam radius also at the mirrors. This requirement also reduces the losses due to aperture effects to insignificant levels. The minimum mirror spacing (which is larger or equal to the mirror size) is then expressed as:
s=C ω/cos β= C (ω 0 /cos β){1+(λ p /2πω 0 2 ) 2 } 1/2
where C is a factor greater than 3, ω is the beam size at the mirrors, and λ is the wavelength of the light. This requirement, together with the restrictions on angular deflection, puts an upper limit on the number of fiber channels (=N) in the switch. If the maximum deflection angle is assumed small, the maximum number of channels is:
N =1+{4πcos β/ C 2 λ}t
The corresponding array separation and mirror spacing are:
p =2πω 0 2 /λ
and
s =2 1/2 Cω 0 /cos β
If C=3, β=0.3 radian and λ=1.55 micron, N is given by N=1+0.86 t where t is in micron. The conclusion is that the simple geometry of FIG. 4 can be used to design relatively large switches. Using known surface micromachining techniques, switches with three fiber channels can be fabricated with a total sacrificial layer thickness of 2.75 micron. Larger switching matrices will require thicker sacrificial layers, such as 8.1 micron for N=8 and 17.4 micron for N=16.These thicknesses can be obtained by simply using thicker sacrificial layers or by using out-of-plane structures, or through a combination of these.
The minimum beam radium ω 0 is determined from the requirement that the first mirror array should not obstruct the beams after they are reflected from the second mirror, and that the second mirror array should not obstruct the beams before they reach the second mirror. If N is maximized, C=3, β=0.3 radian and λ=1.55 micron, the beam radium in micron must be larger than the number of fiber channels, or ω 0 >N micron. The requirement of maximum path length difference is less restrictive (ω 0 >0.8(N-1) micron). In general, the mirrors should be made as small as possible because miniaturization of the mirrors leads to increased resonance frequencies, lower voltage requirements and better stability. For N=3, ω 0 should preferably be on the order of 3 micron, leading to a mirror spacing of s=13.3 micron. Mirrors of this size, as well as mirrors suitable for larger matrices are easily fabricated by a standard surface micromachining process. This implies that micromachined switching matrices can be scaled to large numbers of fiber channels (e.g., N=16).
The minimum mirror separation in the wavelength-channel dimension may be smaller than the mirror separation s given above by the factor of cos β because the mirrors are not tilted in that direction. The spacing, however, may be larger because there is no switching in the wavelength direction and there is no maximum angle requirement. It may be preferred to add 20 to 30 micron of space between the mirrors for mirror posts (see FIG. 3) and addressing lines. For a switch with N=3 and s=110 micron, for example, a preferred separation in the wavelength dimension may be on the order of 130 micron. If the Littrow configuration is used, the required size of the Gaussian-beam radium on the grating is:
ω g =C w λ 2 /2πΔλ tan θ c
where C w is the ratio of beam separation to beam radium in the wavelength dimension, Δλ is the wavelength separation between channels and θ c is the incident angle (which equals the diffraction angle in the Littrow configuration). With C w =5.2 (25 micron beam radium and 130 micron wavelength-channel separation), λ=1.55 micron, Δλ=1.6 nm (“the MONET standard”) and θ c =45 degrees, ω g is 1.2 mm (the order of diffraction m being 1). This means that the long side of the grating perpendicular to the grooves must be on the order of 5.3 mm and the focal length f 2 of the second lens (the one between the grating and the microswitches) should be about 60.8 mm.
The rotation of the grating about an axis perpendicular to the optical axis and the grating grooves require a corresponding reduction of the grating period by Λ=mλ cos φ/(2 sin θ c ) where φ is the rotation angle of the grating. If m=1, λ=1.55 micron, θ c =45 degrees and φ=30 degrees, the grating period is 0.95 micron.
In a simple system without the microlens arrays shown in FIG. 1, the magnification of the input plane onto the switching matrix is given by the ratio of the focal length f 2 of the second lens to the focal length f 1 of the first lens (e.g., lens 28 between the lenslets 26 and grating 42 ). The role of the lenslet is to allow a different magnification for the mode size and for the mode spacing. In the optimized geometry described above, the ratio of the mode separation to mode radius is 2 1/2 C=4.24. If the fibers are as close together as practically possible (e.g., 125 micron equal to the fiber diameter), the ratio on the input is 125/5=25.The mode radius therefore must be magnified 5.9 times more than the mode spacing. This can be accomplished in several ways.
According to one method, lenslets are used to magnify the fiber modes without changing the mode separation. The lenslets are placed less than one focal length in front of the fibers to form an imaginary magnified image of the fiber mode. Ideally, the lenslet diameters should be comparable to or smaller than the fiber diameter, allowing the minimum fiber separation and a short focal length of the first lens to be maintained. According to another method, the fiber mode is expanded adiabatically over the last part of its length by a heat treatment so as to out-diffuse the core. Mode size increase on the order of 4 times can be accomplished.
According to still another method, the fibers are thinned down or microprisms are used to bring the modes closer together without changing the mode size.
The first two methods require the same magnification or reduction of the input field. The third method has the advantage that less reduction is needed, leading to smaller systems. If N=3, ω 0 =25 micron, s=110 micron and f 2 =60.8 mm, the required magnification is 0.84. If lenslets of 125 micron diameter are used, the required focal length f 1 of the first lens is 72.4 mm. If lenslets of 200 micron diameter are used, the required magnification is 0.525 and the required focal length f 1 of the first lens is 115.8 mm.
Parameters of a switch according to one embodiment of this invention with three input channels and three output channels are summarized in Table 1.
Referring again to FIG. 3, the switching matrix design shown is compatible with the MUMP (the Multiuser Micro Electro-Mechanical System Process at the Microelectronics Center of North Carolina) and its design rules. The full switching matrix includes two arrays each with eight rows of the mirrors shown. The mirrors are actuated by an electrostatic field applied between the mirror and an electrode underneath (not shown). Each of the mirrors in the switching matrix has three states, but the mirrors in the three rows do not operate identically. The central mirror may send the beam to either side, while the outer mirrors only deflect to one side. According to one design, the two on the sides are mirror images of each other, the center mirror being either in the flat state (no voltage applied) or brought down to the point where it touches the substrate on either side. The electrode under the central mirror is split in two to allow it to tilt either way. The side mirrors also have a state that is half way between the flat state and the fully pulled-down state. This may be achieved by having continuous control over the mirror angles. Although this is complicated by the electromechanical instability of parallel plate capacitors because, as the voltage on the plates is increased, the capacitance goes up and this leads to a spontaneous pulling down of the mirror when the voltage is increased past a certain value, this effect can be avoided either by controlling the charge rather than the voltage on the capacitors, or by using an electrode geometry that pushes the instability point past the angle to be accessed. Charge control utilizes the full range of motion of the mirrors but complicates the driver circuitry for the switch. It may be preferable to use electrode geometry to achieve the required number of states.
When the MUMP process is used, the mirror size has a lower limit imposed by the minimum cross section that can be defined in this process. To achieve large tilt angles without too much deflection of the rotation axis of the mirror, the flexing beams must be kept short. The shorter the flexing beam, the larger the mirrors must be for the electrostatic force to be able to pull the mirrors down. Calculations show that the two side mirrors have the required angle when pulled down if use is made of beams that are 15 to 20 micron long, depending on the exact value of the material constants. For the voltage requirement to be acceptable, the mirror size must be on the order of 100×100 micron. The beams of the central mirror may be slightly longer, the maximum angle for the central mirror being half that of the side mirrors. The geometry as shown in FIG. 3 ensures that the side mirrors can be tilted to half their maximum angles before reaching the electrostatic instability. The corresponding resonance frequencies are on the order of 20 to 50 Khz. FIG. 3 shows one of 8 layers of micromirrors in the switching matrix described above; that is, the mirrors are separated by 110 micron in the horizontal (fiber-channel) direction and by 130 micron in the vertical (wavelength-channel) direction. Two such arrays make up a switching matrix as shown in FIG. 2 . The mirrors are shown on landing electrodes, that are shorted to the mirrors, when deflected all the way down to the substrate. Addressing lines and shorts are not shown in FIG. 3 .
The whole switch may be fabricated in so-called silicon-optical bench technology. The lenses, the switching arrays and the in/out modules may be integrated, but commercially available dielectric gratings are too bulky for this technology. Microgratings may be developed, based on anisotropic etching of silicon. Etching of the <100> surface of silicon through rectangular etch masks that are aligned with the [111] directions of the substrate, creates V-shaped grooves defined by the <111 > crystallographic planes of silicon. An array of such V-grooves 56 constitutes a grating that can be used in the Littrow configuration as shown in FIG. 5 . The spacing between grooves can be made arbitrarily small (e.g., 1 micron) by under-etching the mask and subsequently removing this layer. The Littrow angle, which is determined by the crystalline planes of silicon, is equal to 54.7 degrees. By taking advantage of the well-defined shape of a unit cell of the grating, it is possible to obtain high diffraction efficiency in higher order diffraction modes, the V-grooves constituting a blazed grating operated on higher orders. Higher-order operation means that the wavelength dependence of the diffraction efficiency increases. It can be shown that with 8 wavelengths separated by 1.6 nm centered at 1.55 micron and the grating geometry of FIG. 5, the diffraction order can be increased to m=15 with less than 1% variation in the diffraction efficiency between wavelength channels. With m=15, λ=1.55 micron, θ c =54.7 degrees and φ=30 degrees, the grating period is calculated to be Λ=12.3 micron. V-grooves with this spacing can be easily patterned and etched by using standard micromachining technology. V-groove gratings fabricated in this way can be metallized and used as gratings directly, or be used as a mold for polysilicon microgratings that can be rotated out of the plane by using micro-hinges. A potentially very important additional advantage of higher-order gratings, as described here, is the reduced polarization sensitivity as compared to first-order gratings. Since the periodicity is much larger than the wavelength, the diffraction will be close to being independent of polarization. Still, two wave plates may be used to compensate for residual polarization sensitivity due to oblique angle reflections.
Referring now to FIG. 6 and FIG. 7, the fiber-optic switch, being symmetric about its center, can be implemented with a symmetry mirror 58 in the symmetry plane 60 . This essentially cuts the component count in half. The output channels may either be on the input fibers and separable by optical rotators (not shown) or on a separate output fiber array (not shown) that is placed above the input array. In the latter case, the micromirror array 62 and the symmetry mirror 58 are slightly tilted about an axis, such that the light is directed to the output fiber array.
It will be appreciated that the fiber-optic switch of the present invention can serve network functions other than a traditional N×N×M (where M is the number of wavelengths in a WDM system).
It will further be appreciated that the fiber-optic switch of the present invention can be used in connection with diagnostic tools for WDM networks. WDM network management systems and software require knowledge of the state of the entire network. Knowledge of the state of the many distributed optical channels is especially important. The manager requires confirmation of whether or not a channel is active, it power and how much a channel optical frequency has drifted as well as the noise power level. Furthermore, this knowledge permits management software to identify, isolate, and potentially rectify or route around physical layer faults.
Clearly network management requires numerous channel spectrometers that may be deployed in large number at affordable prices. Traditionally, such spectrometers are fabricated from gratings and lenses while an electronically scanned diode array or a mechanically scanned grating provide spectral information. Unfortunately, diode array technology at 1.55 microns, and 1.3 microns, the preferred communications wavelengths, is immature. Such arrays are much more costly and unreliable than those available for the visible spectral region. Moving gratings are bulky and commercial system based on this approach are too costly for wide spread use in production networks.
Accordingly, a variation of the network switch described above can be employed to provide the desired functionality. Referring to FIG. 8, an in-line WDM spectrometer 64 in accordance with the present invention is shown. In the embodiment shown in FIG. 8, WDM optical signals 66 emanating from an input fiber 68 would be collimated and diffracted from the grating 70 forming a high resolution spatially dispersed spectrum at the lens 72 focal plane. A single MEMS switch array 74 would be placed at the lens focal plane, thus permitting the deflection of individual optical channels or portions of a channel by one or more mirrors in the array. A quarter-wave plate 76 is inserted symmetrically around the switching array 74 to compensate for the polarization sensitivity of the gratings 70 . A single infrared diode detector 78 and focusing lens (not shown) would be placed in the return path of the reflected, and suitably displaced, return beam after a second grating diffraction from grating 70 . A full spectrum can then obtained by scanning a deflection across the mirror array. Hence, a synchronized readout of the single photo diode yields the full spectrum to the management software.
The input fiber 68 and output fiber 80 can be arranged in a variety of ways. For example, they can be arranged side by side in the plane as shown in FIG. 8 . An alternative would be to place the output fiber over or under the input fiber. A further alternative would be to use the same fiber for the input and output paths, and separate the signals using an optical circulator or the like.
The micromirror array 74 is preferably a one-dimensional array with one mirror per wavelength. Each mirror would thus operate in one of two states; the mirror either sends its corresponding wavelength to the output fiber 78 or is tilted (actuated) so that its corresponding wavelength is sent to the detector 76 . In normal operation, only one of the mirrors is set up to deflect its wavelength to the detector.
Note also that, if the output fiber if removed and replaced by a beam sink (not shown), the spectrometer will still function although such an embodiment could not be used in an in-line application.
The invention has been described above by way of only a limited number of examples, but the invention is not intended to be limited by these examples. Many modifications and variations, as well as design changes to significantly reduce the overall size, are possible within the scope of this invention. For example, the beam radius in the switching matrix may be reduced. The no-obstruction criterion allows a change to ω 0 =5 micron for a 4-fiber switch, and this allows the focal length of both lenses to be reduced by a factor of 5. As another example, the micromachining technology may be improved to place the mirrors closer. The posts (as shown in FIG. 3) and addressing lines may be moved under the mirrors to reduce the beam radium on the grating by a factor of 1.2. Together with the increased diffraction angle of a micromachine grating (say, to 54.7 degrees from 45 degrees), the focal lengths of the lenses can be reduced by a factor of 1.7. As a third example, the fiber modes may be brought closer together on the in/out modules. If the mode spacing is reduced from 200 micron to 22.2 micron, the first and second lenses may have the same focal length (such that magnification=1). In addition, advanced designs may reduce the number of required components. The switch may be designed so as to be foldable about its symmetry point such that the same lenses and the same grating will be used both on the input and output sides. In summary, it is to be understood that all such modifications and variations that may be apparent to an ordinary person skilled in the art are intended to be within the scope of this invention.
Although the description above contains many specificities, these should not be construed as limiting the scope of the invention but as merely providing illustrations of some of the presently preferred embodiments of this invention. Thus the scope of this invention should be determined by the appended claims and their legal equivalents.
TABLE 1
Components
Parameter Values
Input/output fibers
Fiber channels: 3
Standard single mode fiber
Input-output
MONET standard:
wavelengths
Center wavelength: 1.55 micron
Wavelength channels: 8
Wavelength separation: 1.6 nm
Lenslets
Ball lens, 200-micron-diameter
n < 1.6
First lens
Bulk lens
f 1 = 125.5 mm
Grating
Period: 0.95 micron
Diffraction angle: 45 degrees
Size: >6 mm
Second Lens
Bulk lens
f 2 = 78.5 mm
Switching matrix
N = 3
Mirror spacing:
Fiber dimension: 110 micron
Wavelength dimension: 130 micron
Array spacing: 2.5 mm
Thickness of sacrificial layer: 2.75 micron
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A cross-connect switch for fiber-optic communication networks employing a wavelength dispersive element, such as a grating, and a stack of regular (non-wavelength selective) cross bar switches using two-dimensional arrays of micromachined, electrically actuated, individually-tiltable, controlled deflection micromirrors for providing multiport switching capability for a plurality of wavelengths. Using a one-dimensional micromirror array, a fiber-optic based MEMS switched spectrometer that does not require mechanical motion of bulk components or large diode arrays can be constructed with readout capability for WDM network diagnosis or for general purpose spectroscopic applications.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of U.S. patent application Ser. No. 12/466,128 filed May 14, 2009.
FIELD OF INVENTION
[0002] The invention is related to systems that provide information for detecting and localizing events. In particular the invention relates to optical fences with a distributed fiber interferometer sensor to determine the location of a disturbance event along the object of interest and/or extensive perimeter area under observation.
BACKGROUND OF THE INVENTION
[0003] Fiber optic distributed sensing overcomes the inherent limitations of traditional technologies, such as motion detectors, cameras, thermocouples and strain gauges, enabling monitoring solutions with new advantages for the protection of people and critical assets, especially when monitoring in inaccessible or inhospitable environments.
[0004] In a distributed sensor, the whole optical cable is the sensor itself. Typically, the fiber is integrated around (or into) a valuable asset (building, pipeline, cables, etc.). A single optical fiber can replace thousands of traditional single-point sensors, providing a significant reduction in installation, calibration, and maintenance costs. In addition, assets can now be monitored where previously this was impractical due to their size, complexity, location or environment.
[0005] The monitored structure in the present invention is any object or area under observation. The monitored structure can be the area enclosed into the sensor system completely or partially. The monitored structure can be an object, such as pipe, cable, fence, wall, etc. that is integrated into the system by placing the optical fibers in a proximity to the object or integrated into the object, for example installed into, wrapped by or winded around the object. A single monitored structure can be comprised of different elements that are objects of, generally, different types, for example, monitored areas and monitored objects at the same time.
[0006] The inherent distributed sensing nature of fiber optic sensors can be used to create unique forms of sensors for which, in general, there may be no counterpart based on conventional sensor technologies. Optical fiber is cheap, light, pliable, and immune to electromagnetic interference (EMI), which makes it a cost-effective, flexible and an inert sensor medium.
[0007] Most of the existing distributed sensors are based on Distributed Scattering Sensing (Raman or Brillion), which has a limited sensitivity and immunity to various noises.
[0008] With modern low loss fibers and solid state laser diode sources, it has become possible to develop systems having sensing fibers up to several tens of kilometers in length. In one field of application, these fibers can, for example, be placed under ground, carpets, imbedded in walls, under roads, or under turf. In such installations the sensors can be effective in the detection of personnel, vehicles, animals, etc. into a protected area of interest.
[0009] There is a need in well concealed fiber optic sensing systems to provide economic means for location of events, recognition and identification of disturbance events, and positive means for periodically and remotely proof testing the integrity of the sensing fiber.
[0010] A few distributed optical fiber sensing systems based on a Sagnac interferometer and a Mach-Zehnder interferometers have been previously developed. These systems depend on the interferometric detection of phase differences between two optical signals whose relative phases have been shifted by changes in the optical properties of their respective paths caused by an external factor, such as, for example, acoustical or mechanical perturbation. The change in optical property of the fiber path may be in the form of elongation, change in index of refraction, change in birefringence, or a combination of these or related effects.
[0011] While interferometer-based sensor systems have been developed with a number of refinements, such systems have not been fully optimized for use in applications that require simultaneous monitoring of different types of objects.
[0012] Prior art, for example, U.S. Pat. No. 6,621,947 and U.S. Pat. No. 6,778,717, both by E. E. Tapanes et al., discloses a principle (device and method) behind the counter-propagating signals detection in distributed fiber sensor. Optical signals are launched from a single light source into the waveguide (fence) and simultaneously detected by a two separate photo-detectors. The difference between registered signals allows detecting the place of the optical fence intrusion. Any parameter that alters the fiber will affect both counter-propagating signals in a similar fashion. Thus, the U.S. Pat. No. 7,519,242 by E. E. Tapanes shows the particular buried fiber configuration that is specifically suited for detecting an intruder walking across the ground beneath which fibers are buried.
[0013] However, it is desirable to have a distributed sensing system where the response to the potential perturbation can vary along the cable, being adjusted to either the real system environment or a particular system application. In other words, the real system implementation might require different sensitivity at different areas being monitored, depending on, for example, different structure layouts, various perturbation probabilities within different areas, or the different nature of perturbations within different areas. The prior art does not provide such desirable functionality.
[0014] Polarization phase shift variations are caused by dynamically varying changes in a signals polarization state versus the principal polarization axis of the interferometer. As a result, received counter-propagating signals can potentially interfere constructively or destructively. Thus, it is also desirable, in addition, to have a distributed sensing system where polarization effects are intrinsically managed by the system to dynamically address the variation of polarization states along the fiber sensor. Polarization management techniques for distributed fiber sensing have been disclosed in U.S. Pat. No. 7,499,176 by A. R. Adams and U.S. Pat. No. 7,499,177 by J. Katsifolis, as well as in U.S. Pat. No. 7,142,736 by J. S. Patel et al. Moreover, the U.S. Pat. No. 7,139,476 discloses the method of disturbance event detection/location by using the changes in the states of polarization of counter propagating signals themselves. However, in all these configurations, the external polarization management was applied to the system with uniform perturbation response across the perimeter, as mentioned above.
[0015] There is a need for a distributed fiber sensing link with non-uniform perturbation response across the perimeter, which would drastically expand the applicability of the system.
[0016] Although existing security application of distributed sensor systems are valuable in detecting events over large areas, they are not always sufficiently sensitive, capable of dynamic adjustment/control, convenient in implementation, properly camouflaged or economical for determining the location of events of different nature at different areas. Thus, several systems would be required to distinguish between perturbations, caused, for example, by events of different nature and/or perturbations that correspond to different environments encountered by a system installation.
[0017] Operational pipelines are subject to complex, highly non-linear temporal and spatial processes that usually make it difficult to differentiate between faults and stochastic system behaviors. This makes detecting failures/intrusions a challenging task, leading to integrating different types of data that is remotely captured from several sources, such as proposed fiber-optic system, as well as pressure transient signals and flow (velocity) information. The various types of (high frequency) data can be time synchronized. There is a need for a system capable of detecting small problems that might be precursors of catastrophic bursts, also enabling prompt detection and localization of larger leaks and malfunctioning equipment such as valves.
[0018] There is also a need for a technology to be used in earthquake continuous monitoring/early warning system. For example, when the system has detected a wave (P-wave-representing the warning of a future imminent major earthquake), the visual and acoustic quake alarm can be started.
[0019] There is also a need to adapt existing monitoring system for underwater operating conditions.
SUMMARY OF THE INVENTION
[0020] A system and method for structure monitoring and locating a disturbance event is disclosed. The system includes a compact transceiver chip sending optical signals in three optical fibers that encompass the monitored structure appropriately. The system includes a series of loops, in which the first and the second fiber forming the loop clockwise, while the third fiber is winded along the same loop counterclockwise, wherein the first and the second fibers have the same optical path. The fiber arrangement has different densities in different parts of the monitored structure, such as, for example, critical places in the structure may have a larger number of fiber loops surrounding them. All fibers transmit signals in both directions: from the transceiver to a returning point and back. A set of two detectors registers the returning signals, and the time delay between those signals is calculated using a digital signal processing (DSP) unit, this time delay is indicative of the disturbance event location. Polarization states of the returning signals are controlled by the transceiver's built-in controllers. The event location is determined with different sensitivity in different parts of the monitored structure depending on the density of fibers at different locations.
[0021] The location P of the disturbance event along the first fiber is determined as P=(L−cΔt/n)/2, wherein L is a length of the first and the third fibers, n is a fiber refractive index, c is a velocity of light, and Δt is the difference between the receiving times of the modified signals.
[0022] In one embodiment the first and the second fiber are placed in one cable, which is shaped as a series of loops forming a chain-like structure with each loop characterized by its waveguide length, loop perimeter shape, and number of windings.
[0023] In the preferred embodiment the transceiver formed as an integrated component, including an input waveguide receiving light from the light source, a splitter which splits the input waveguide into a first and a second waveguides, the first waveguide providing input for the first light beam into the first fiber, and the second waveguide providing inputs for the second light beam into the second fiber and the third light beam into the third fiber; a first coupler splitting the second waveguide into a third and fourth waveguides; the third waveguide being connected to the second fiber and the fourth waveguide being connected to the third fiber; a second coupler providing a first detector waveguide being connected to the first waveguide; the first detector waveguide leading the fourth signal to the first photo-detector; and a third coupler providing a second detector waveguide being connected to the second waveguide, the second detector waveguide receiving the fifth and the sixth signals combined and leading it to the second photo-detector.
[0024] Yet another object of the present invention is a method for a structure monitoring and locating a disturbance event. It includes the following steps: sending three optical signals via optical fibers from a transceiver to a returning point and then back; receiving the return signal by a set of photodetectors, measuring a time delay between the signals and locating the disturbance event. The system sensitivity to the disturbance event is different for different parts of the monitored structure. In the preferred embodiment the transceiver formed as an integrated component.
[0025] A shape of the modified signals may be measured, and a type of disturbance is determined using a look-up table. Different kinds of correlation and validation procedures may apply.
[0026] The system may be adapted for operating under water. In particular, it may be used to detect acoustic pressure waves to study environment or to locate and track maneuvering targets.
[0027] Another object of the present invention is a method for an object monitoring and locating a disturbance event. The method includes sending three optical signals via optical fibers from a transceiver to a returning point. The fibers form at least a first loop, wherein the first and the second fiber forming the loop clockwise, while the third fiber is winded along the same loop counterclockwise, wherein the first and the second fibers have the same optical path. After passing the returning point, the signals are received by a detector. The method includes determining a time delay between the signals and locating the disturbance event.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] FIG. 1 shows a conceptual view of the distributed interferometric sensing system with counter-propagating signals.
[0029] FIG. 2 illustrates one possible pattern for cables arrangement in the sensing fiber link.
[0030] FIG. 3 illustrates a loop-based layout for the sensor.
[0031] FIG. 4 shows a system embodiment with multiple loop segments along the sensing fiber link.
[0032] FIG. 5 illustrates a system embodiment with different loops layout along the fiber link. The sensor response to the perturbation at each section of the perimeter is different.
[0033] FIG. 6 shows a schematic example of a single sensing fiber link capable of detecting and locating various perturbations at different sections of the link A system response is customized for each of the section along the perimeter.
[0034] FIG. 7 shows spiral arrangement of fibers around a pipeline with different density of fibers in different elements of the monitored structure (pipe).
[0035] FIG. 8 shows a system embodiment with counter-propagating signals polarization management.
DETAILED DESCRIPTION OF THE INVENTION
[0036] The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which the preferred embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
[0037] The system is designed for structure monitoring and disturbance detection and locating. The sensitivity to the potential perturbation can vary along the fiber cable, depending on the requirements within a particular area. Thus, the sensitivity of the system at particular area can be optimized in terms of local structural layout, depend on how often the perturbation occurs (event probability) or reflect the different types of event within different areas (different types of damage, intrusions, etc.). The optimal sensitivity of the system is based on combination of the foregoing factors that correspond to the each particular monitoring area.
[0038] In the preferred system configuration, the fiber link is integrated into the area with no visible physical barrier present. The system is suitable either for an underground arrangement or integrated into the structure, providing a security (fence) and/or damage monitoring to a required area. The technology is optimized for detection and location of an event, caused by perturbation due to external intrusion or external/internal damage.
[0039] The fence includes the optical fiber cables with the counter-propagating optical signals having certain characteristics that can be modified or affected by an external parameter caused by an event. The applied strain, vibration, acoustic emission, temperature transient, can cause fiber elongation, change in index of refraction, birefringence, or a combination that, in turn, can modify the counter-propagating optical signals and indicate an event.
[0040] Continuous-wave optical signals are launched from a single light source 1 , FIG. 1 , into the waveguide and simultaneously detected by two separate photo-detectors 2 and 3 . (Pulsing of the optical signal may be employed in some arrangements). The receiver detects the affected counter-propagating optical signals and determines the time delay or difference between the modified counter-propagating optical signals in order to determine the location of the event.
[0041] A returning point 4 provides for mixing and reversing the sent signals. It operates in both directions and has three input-outputs 5 , 6 , and 7 connected to the first, second and third fibers respectively.
[0042] Any mentioned sensed parameter that alters the fiber will affect both counter-propagating signals in a similar fashion. However, each affected counter-propagating signals continues traveling the respective remaining portion of the waveguide loop to their respective photo-detector. This will produce a resultant time delay or time difference between the detected signals. The time delay is directly proportional to the location of the sensed event along the waveguide length. Therefore, if the time delay or difference is detected and measured, the location of the event can be determined, quantified and identified.
[0043] The receiver detects the interference pattern. Upon the disturbance a parameter of light passing through one of the waveguides is altered with respect to the same parameter of the light passing through the other waveguide, and thereby it changes the interference pattern detected by the detector.
[0044] An indication of the disturbance is provided by detecting the change in the interference pattern due to the change in the waveguide parameter, where the light passing through one of the output waveguide is altered with respect to another.
[0045] In addition, in certain system configurations a non-sensitive fiber optic delay line can be integrated at either or both ends in order to add additional delay between the transmitted counter-propagating signals.
[0046] The system does not require signal averaging, and it determines the location of events via the time delay measurement between counter-propagating optical signals affected by the same disturbance.
[0047] Schematic set-up of the system, utilizing a Mach-Zehnder (MZ) interferometric sensing technique is shown in the FIG. 1 .
[0048] This generalized embodiment illustrates the distributed sensing element, having Cable I and Cable II as the MZ interferometer arms that include some arbitrary lengths of ‘insensitive’ lengths LI 0 and LII 1 . While not playing an active part in perturbation detection, these fiber segments provide an additional optical delay between the transmitted counter-propagating signals. This can substantially facilitate the practical implementation of the system. The ‘active’ part of the fiber sensor consists of segment LI 1 and LI 2 see FIG. 1 . The perturbation can occur at the point D, anywhere along this active part of the sensor, producing two identical perturbation of the signal, propagating in opposite directions: from D to C and from D to E, as shown in FIG. 1 . The total optical fiber link with total distance:
[0000] L=LI 0 +LI 1 +LI 2 +LII (1)
[0049] The goal is to detect and locate a disturbance at point D, anywhere along the sensitive section of the fiber link The measurable parameter is the Δt—the difference in time of arrival of each of these signals at points C and E, measured by (balanced) photodiodes at the transceiver chip, see FIG. 1 .
[0000]
Δ
t
=
N
(
LI
2
+
LII
)
-
(
LI
1
+
LI
0
)
c
=
N
L
-
2
(
LI
0
+
LI
1
)
c
(
2
)
[0000] where c is the speed of light in a vacuum and N is the effective refractive index of the optical fiber (waveguide).
[0050] The perturbation location from one side of the link (point C) is given by:
[0000]
P
C
LI
0
+
LI
1
=
L
2
-
Δ
tc
2
N
(
3
)
[0000] The same perturbation location from the opposite side of the link (point E) is given by:
[0000]
P
E
LII
+
LI
12
=
L
2
+
Δ
tc
2
N
(
3
a
)
[0051] This result illustrates that only knowledge of the total fiber link length L is required, and not the respective lengths of the various sensitive and insensitive fiber segments in the system.
[0052] The total fiber link may include multiple cable segments having various, generally different, patterns of the fiber arrangements along the link. The information about the total length and individual segments can be easily obtained at the design and installation stages of a system as well as by use of an OTDR method after installation.
[0053] Two (balanced) detectors detect the shape of corresponded counter-propagating signals traveling in respective directions. This shape of is characterized by a rise-time and a fall-time of the said signals, providing a means of calculating a time delay Δt between them at the detectors.
[0054] Once the total length is known and the time delay Δt is measured by the system, the location of the sensed event can be readily determined by equation (3). The time difference between the two modified counter-propagating signals will determine the disturbance location.
[0055] Alternatively, a single detector could be utilized to detect both of the counter-propagating signals so that the signal detector has a synchronized reference to determine the time difference and the length along the cables where a disturbance has occurred.
[0056] The event identification and localization can be validated by off-line validation procedure, which may include:
[0057] Pre-testing the sensor installations in their ambient environment. For example, the natural excitation technique (NExT) for the modal analysis of sensor installation structures excited in operating environment can be used. It provides the state of a linear dynamic system from a series of noisy measurements.
[0058] Lookup tables can be used to compare with the input perturbation values, validating the event by matching (correlating) it against a library of valid (or invalid) events. In particular, the correlation may be estimated using minimum mean square error (MMSE) technique, or other statistical approaches may apply.
[0059] The first embodiment of the proposed system is shown in FIG. 2 . The first and second waveguides can share the same cable while a separate second cable utilizes only one (third) waveguide. The two cables have preferably symmetrical pattern.
[0060] These separate cables can be placed under the surface (e.g. carpet and such) or buried underground. Cable I and Cable II are arranged in a proposed configuration (pattern) with respect to one another, defining a perimeter region having a custom width that is optimized upon application. The width can be defined by particular structural element under observation (e.g. pipeline), or can be defined by a distance which is traversed by a person intruding into the area. For example, the sufficient width can be such that an intruder traveling in a walking or running motion would not step over the fence area. In this case, for maximum effect the cables should be laid in a shallow trench for the entire length of the sensitive zone.
[0061] The system can also be used for monitoring and detecting various soil displacements, for example the ones associated with the underground tunneling activity. In preferred configuration, the buried sensing cables are laid along the bottom of the trench, in a closely spaced proposed loop-based pattern that runs across the full width of the trench.
[0062] It is essential that the pattern of one cable is opposite to that of the other cable, in order to be out of phase. The cables may touch as they cross over or being overlapped. The maximum sensitivity can be optimized for the application.
[0063] In the preferred configuration, an integrated transceiver 10 is connected to the light source 1 . The light is split by a splitter 11 into two beams travelling along the first 12 and the second 13 waveguides. A coupler 14 splits the second beam and directs it to the second and the third fiber. Couplers 15 and 16 (optionally tunable) are integrated in a single LN (LiNbO 3 ) chip, which also includes pair of balanced diodes 2 and 3 . These couplers lead the returning signals to the photodetectors. The cables are terminated at either each end of the perimeter or at one end only if the perimeter is closed. The returning coupler 4 can also be LN integrated or, alternatively, made of fused silica fibers. The integrated configuration leads to a very compact, reliable and flexible system where the operating point can be easily adjusted by means of electro-optical and/or thermo-optical controls.
[0064] Optionally, the simplified version may be based on the terminating polished mirrors instead of a coupler, providing an intrusion alert without determination the event location in this case.
[0065] The protected area can be completely or partially enclosed by the perimeter to provide complete monitoring of the region of interest. Anybody attempting to gain access into the protected area will walk over the preferably hidden cables, and the weight of the intruder will apply a load to the two cables or, potentially, move the cables as the intruder walks over, under and/or along the cables. This will cause a change in parameter, such as a phase of the signal, which, in turn, changes the interference pattern when the modified signal recombines with the counter-propagating modified signal.
[0066] Similarly, a change in parameter, such as a phase of the signal, can be caused by damage to the structure along the monitored perimeter, such as, for example, pipeline or bridge, where the cables are installed.
[0067] The system can be integrated into a structure, such as fence, pipeline, bridge or building elements. The cables can be installed into existing site/layout, integrated into the monitored structure itself or buried underground by excavating a trench. The removed soil can be used to backfill the trench after laying the cables. Once installed, the cables do not require any particular care, such as maintaining very precise pattern uniformity.
[0068] All configurations have the advantage that the concealed cables are sensitive enough to detect even the slightest foot-fall, continuously and discretely, twenty-four hours a day for a very long period of time. Their performance is unaffected by changes in the local environment (rain, hail, temperature, electrical storms and magnetic loads). Noise and vibration effects from background traffic can be screened out. Washouts do not disable the system and can be repaired.
[0069] The advantage of the proposed system is that the fibers cannot be detected by metal detectors or emission measurements, since cables not require any metal components and do not emit electromagnetic radiation. The sensitivity of the detecting system and corresponded alarm level can be arranged to suit the application/operational requirements. The sensitivity of the system is weakly dependent on the fiber length up to several tens of kilometers without signal amplification. Signal amplification can be used for greater fiber length.
[0070] It is desirable to have a distributed sensing system where the sensitivity to the potential perturbation can vary along the cable, being adjusted to the actual system environment/application. In other words, the real system implementation might require a customized (optimized) system response to events that occur at different areas of the monitored system depending on, for example, different structure layouts, various perturbation probabilities within different areas, or different nature of perturbations within different areas.
Distributed Sensing
[0071] Yet another loop-based layout for the interferometric fence structure that based on the three foregoing fibers is proposed. A single loop-element (period) of such fiber sensor is schematically shown in the FIG. 3 . As it can be seen from the FIG. 3 , each fiber has a defined winding direction with respect to other fibers.
[0072] Here the parameters of the fiber sensor, such as, for example, a loop shape α and β, as well as the number of windings within the loop γ can be adjusted accordingly to a required application and optimal response R to particular perturbation Fp:
[0000] R ( t )= R{Fp ( L,t ),α,β,γ}, (4)
[0000] where t is the time and L is the location along the cable.
[0073] The approach can be further extended by using a ‘chain’ of loops of, generally, different α, β and γ. Thus, FIG. 4 illustrates the trench filled with such multiple loops, each made of the three interferometric fibers, respectively.
[0074] The sensitivity of the fence system will depend on amount of windings in each loop as well as on a number/shape of the loops, and can be improved at the expense of fence complexity and additional fiber cost.
[0075] As mentioned, it is desirable to have a variable detection/location capability along the perimeter area of the system. It can be realized by varying the amount of cable installed at the specific location of the perimeter. Thus, an example of the system, where the different amount of cable associated with different area (sensitivity), is shown in FIG. 5 . Here all parameters of the loops layout can vary along the perimeter L. In this case, optimal response R i , to particular perturbation Fp(L i ,t) will be a function of the particular configuration of the fiber at particular area of the perimeter L i :
[0000] R i ( L i ,t )= R{Fp ( L i ,t ),α i ( L i ), β i ( L i ), γ i ( L i )} (5)
[0076] FIG. 6 schematically illustrates the implementation of the single system for monitoring different types of objects, where different system response at different segments of the perimeter is required (distributed sensitivity).
[0077] Alternatively, different responsivity can be assigned to different parts of the same object, as illustrated in FIG. 7 for a single cable, where the number of fiber loops and its shape is adjusted, accordingly to specific geometry of the monitored element or application requirements.
[0078] The detecting of a modified signal might not be sufficient to distinguish a perturbation of interest from other incidental perturbations. In a preferred embodiment the system involves the electronic analysis to decompose the detected signal and further use the training algorithms based on prerecorded database of various perturbations.
[0079] Prerecorded database of perturbations may include, but not limited to, different known patterns of predictable events such as simulated intrusions and simulated damages associated with different segments of the perimeter.
[0080] It is also often desirable in intrusion detection security systems to know when authorized persons have entered a specific area of the perimeter for legitimate purposes and to record their identity. In systems providing surveillance of spaces on campuses or within buildings, it is regularly necessary for authorized persons to enter monitored areas without setting off an alarm.
[0081] Alternatively, more than one described system can be arranged into a secured perimeter, separated by a certain distance.
[0082] The proposed invention is of special interest for pipeline monitoring. FIG. 7 shows one embodiment of the fiber arrangement in this case. U.S. Pat. No. 6,644,848 by Clayton et al. discloses a sensor winding around the pipe. In our invention two cables are winding around the pipe, in opposite directions. The loop density, shape and size may be different in different elements of the pipeline as shown in FIG. 7 for one cable.
[0083] The proposed technology can be used for the pipe-line monitoring including the distributed damage sensing, security monitoring or combination of both. Such fiber optic pipeline intrusion and leak-detection system can operate over large distances detecting, locating and classifying noises and vibrations in the vicinity of the cable, distinguishing among leaks, tampering, intrusions, digging, machinery and vehicles operating nearby. It can help in preventing illegal tapping, intrusions and leaks that cannot be detected by conventional flow metering.
[0084] The system may be adapted for underwater operation. The ability to install proposed sensor underwater brings new opportunities to for a small-area monitoring, structural monitoring, and industrial applications. While fiber sensor systems are well established on the ground, the underwater applications remain quite limited by comparison. The underwater sensing of acoustic waves can be used in number of applications, including seismic monitoring, equipment monitoring and leak detection.
[0085] Another promising application for underwater distributed-sensitivity sensor is seismic monitoring for oil extraction from underwater fields. This is a better alternative to the underwater monitoring which typically involves a ship with a towed array of hydrophones as sensors involving both large capital and operational costs.
[0086] Another application can of the invention is using a broadband (0.05-60 kHz) distributed-sensitivity-sensor system capable of a long-term measurement and characterization of acoustic noise spectrum in deep sea, which is a powerful tool to study the underwater environment. The system also may serve as underwater sensor arrays to locate and track maneuvering targets and detect perturbations caused by acoustics pressure waves.
Polarization Management
[0087] The remote disturbance might be any of various physical occurrences that affect the waveguide on a scale that is comparable to the wavelength of the light. Slightest instances of changing physical pressure, motion or vibration and the like can change light propagation conditions sufficiently in an optical fiber or similar waveguide, to produce an effect that might be discerned as a disturbance and used as a basis to localize the effect. Theoretically, when a disturbance affects both beams propagating over unequal path lengths to a detector, a phase variation should arise at the detector on one of the two beams first, after a propagation delay from the point of the disturbance. A difference between the two signals may persist between the time of reception of the first signal to arrive along the shorter path, until the time of reception of the second signal to arrive along the longer path. After the second signal arrives, the same phase variation that affected the first signal affects the second one, theoretically equally. An interference summing node is effectively a phase comparator. The time span is a function of the difference in distances from the detector to the disturbance along the two paths. From the time difference and information as to whether the phase difference leads or lags, the disturbance can be located to a point. This point can even be at the middle of the loop, with the zero indicative time-difference in such a case.
[0088] The polarization attributes of the counter-propagating signals have to be taken into account. Birefringence changes polarization alignment by inducing a phase difference between two orthogonal components of a light signal. Polarization phase shift variations arise in part because there are dynamically varying changes to the polarization states of the light signals between the signals as they are launched, versus the principal polarization axis of the interferometer at which the received signals can potentially interfere constructively or destructively. Thus, the difference varies as a function of the birefringent state of the fiber along the two counter-propagation paths and the change in polarization alignment can involve a phase difference of its own. The effect of polarization fading and polarization induced phase shift can be quite detrimental, leading to system failure if precautions are not taken.
[0089] Similarly to interferometric adjustment, the polarization aspect of the signal can be adjusted to provide an accurate location of the event. Ideally, the state of polarization for the two interfering beams should be adjusted to be substantially parallel to each other before the interference, to avoid the polarization-induced signal fading and induced phase shift. Accordingly, the intensity criteria can be used as an input to a feedback control for adjusting one or more polarization controllers to maximize the amplitude of the intensity signal, i.e., to achieve the greatest available span between maximum and minimum levels of constructive and destructive interference. In other words, the feedback controls to the polarization controller can be arranged to make the depth of modulation of the interference signal as large as possible.
[0090] At standby condition is assumed when the system is prepared or primed to detect a disturbance. To obtain a maximum value and maximum swing in intensity, two conditions are addressed, namely:
[0091] (a) the polarization orientations of the two beams are aligned,
[0092] (b) the phase difference between the two beams is set to zero.
[0000] Similarly, in order to obtain a minimum value of intensity:
[0093] (a) the polarization of the two beams are aligned;
[0094] (b) the phase difference between the two beams is π radians.
[0095] At the standby condition, the polarization transformation functions of the two counter-propagating optical channels can be effectively balanced by active management of the polarization conditions. Thus, the polarization mismatch for the counter-propagating optical signals, as well as effective phase, will always be the same at the standby condition. As a result, the location of the disturbance can be localized more accurately since the lead/lag time used to calculate the location can be determined dependably and more accurately.
[0096] The received signals can be combined in a polarization insensitive way, by controlling the polarization state of the input beams. In this way, the time difference of the intensity response for the two counter-propagating optical signals can be correlated at the point of detection. The received signals are matched in a way that eliminates the interference signal intensity variations resulting from polarization conditions and thereby demonstrates the lead/lag time without carry forward errors and complications caused by polarization effects.
[0097] In the absence of a disturbance, the intensity of interfering beams theoretically should be more or less constant due to a stable degree of constructive and destructive phase cancellation, i.e., interference, of the two more or less constant signals.
[0098] In a single LN chip, electro-optically adjusted birefringence is not sufficient to achieve effective polarization transformation since mode-conversion between the orthogonal TE and TM components is also required. Efficient 100% electro-optical conversion can be achieved by utilizing an off-diagonal element of the electro-optical tensor to cause mixing between the orthogonal TE and TM modes (normally uncoupled). However, an electro-optical T TM converter alone is also not capable of providing general polarization transformation.
[0099] We propose to integrate into the system transceiver chip a (variable efficiency) polarization conversion scheme where the two electrical fields are applied alternately along the interaction region. For example, if electrical field applied parallel to the X direction of LN chip, an off-diagonal element in the dielectric permittivity tensor is induced via the electrooptic coefficient r 51 =28×10 12 m/V. In such scheme, short sections of birefringence tuning electrodes are periodically interleaved between short sections of T TM mode converter electrodes, and a large number of sections are used in total. Although this arrangement may result in longer interaction lengths, it clearly permits independent control of T TM mode conversion and birefringence tuning. In such orientation the TE and TM modes have significantly different propagation constants due to the large birefringence of LN. The propagation constant of the TM mode is mainly determined by the ordinary refractive index of LN, whereas the propagation constant of the TE mode is mainly determined by the extraordinary index. As shown in FIG. 8 , the two polarization controllers 20 and 21 , each based on 3-sections (cells), integrated into the LN X-cut, Y-propagation transceiver chip.
[0100] The middle section of converters I 20 and II 21 in the FIG. 9 has a constant electrode period Λ, and electro-optic TE TM mode conversion is obtained when a voltage Vc is applied to the mode converter electrodes. In this case, the conversion is most efficient at a wavelength λ 0 defined by the phase-match condition:
[0000] Λ=λ 0 /|no−ne| (6)
[0101] Here, no and ne denote the effective phase indexes of the TE and TM modes and λ 0 is the vacuum wavelength, where mode converter operates with maximum conversion efficiency under chosen Λ. At other wavelengths, this would not be the case; the contributions of adjacent mode converter fingers add slightly out of phase, resulting in a reduced overall conversion efficiency. The optical bandwidth of mode conversion is determined by the total interaction length L, i.e. the 3 dB bandwidth (FWHM) is given by
[0000] Δλ/λ 0 =Λ/L=1 /N, (7)
[0000] where N is the number of electrode periods.
[0102] Polarization controllers 20 and 21 are used to control polarization effects in the counter-propagating optical signals by establishing and maintaining polarization states of the interfering beams for each of the counter-propagating light signals that are amenable to interference of parallel polarization components of the respective beams. This can be accomplished using feedback control so as to cause a polarization controller to seek maximum peak to peak interference signal amplitude. This and other related polarization management techniques permit a processor coupled to the detector (and optionally coupled to provide the feedback signal to the polarization controller) efficiently, easily and accurately to calculate the location of the disturbance.
[0103] Polarization controllers 20 and 21 are readjusted such that the state of polarization of the light beams travel along cables are parallel to each other before they interfere with each other at the detector, for the clockwise and the counter-clockwise propagating light signals, respectively, see FIG. 9 .
[0104] The proposed fiber sensor is preferably realized using integrated planar-wave technology, such as LiNbO 3 electro-optical circuit and includes built-in polarization control elements to dynamically address the variation of polarization states along the fiber sensor. By these means, the phase difference due to signals polarization misalignment can be managed (minimized), enabling an accurate detection/localizing of the perturbation (event).
[0105] Proposed polarization control elements are built into the same electro-optical chip, making them an inherent part of the compact transceiver chip. Using integrated electro-optical planar-wave technology enables effective adjustment of the counter-propagating signals by tuning coupling ratios of splitters and combiners, optical phase adjustments and polarization management. High integration of electro-optical components within the same chip/package leads to a very noise-proof, compact and cost-effective solution.
[0106] The proposed system can either be placed under the ground surface, making it invisible for a potential intruder, or integrated into the structure itself. The technology can also help in detecting tunnels deep under ground, and monitoring the burred fiber-cable for the telltale soil displacements associated with tunneling activity.
[0107] Another application of the proposed system is to utilize the fiber(s) within an (existing) telecommunication cable as the distributed sensor element to provide information related to a damage or intrusion anywhere along cable length. Such an arrangement would be most valuable for protection of the cable facilities of power or telephone companies against unauthorized intrusion or tampering. When deployed in this manner, the sensor can detect direct contact, mechanical pressure, or acoustic signals.
[0108] Distributed optical fiber sensing links disclosed in invention can be effectively implemented in a wide variety of applications. Without limitation, the field of use can include railroads, roads, walls, gates, and bridges maintenance, as well as pipeline infrastructure, construction, fences of various types, petrochemical/nuclear-power infrastructures; earthquake monitoring. Any application that requires the detection, measurement and locating of a particular disturbance along the particular section of the fiber link can benefit from the invention. The invention would offer lower cost, unprecedented versatility, improved operational and safety-related characteristics over existing technologies.
[0109] The description of a preferred embodiment 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 forms disclosed. Obviously, many modifications and variations will be apparent to practitioners skilled in this art. It is intended that the scope of the invention be defined by the following claims and their equivalents.
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A system and method for a structure monitoring and locating a disturbance event is disclosed. The system includes a compact transceiver chip sending optical signals in three optical fibers that encompass the monitored structure appropriately. The system contains a sequence of loops, wherein the first and the second fiber forming the loop clockwise, while the third fiber is winded along the same loop counterclockwise. A set of two detectors registers the returning signals, and a time delay between those signals is calculated, which is indicative of the disturbance event location. The event location is determined with different sensitivity in different parts of the monitored structure depending on the density of fibers in these parts.
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BACKGROUND
[0001] On-the-fly blending of well treatment fluids is not typically used for corrosive chemicals. Generally, blending corrosive chemicals, otherwise known as acids, or hazardous chemicals, is done at a location other than the well site, using batch mixing. The chemicals are mixed in a tank at a bulk chemical plant and then transported to the well site. The mixing and the transportation are costly. Specialized transports are required to transport the mix. Additionally, specially trained personnel are required. In addition to being costly, this can be undesirably time consuming. Further, any real-time change to the mix presents problems, as an entire new batch must be mixed and transported. While this occurs, the job must wait, which can be extremely costly. Further, batch mixing requires that the tank be emptied prior to changing the mix. It is difficult to anticipate the exact amount of mix that will be required for a given application. This generally leads to excess mix left in the tank at the end of a job, or at a change point. Proper disposal of this mix can be environmentally hazardous, costly, and dangerous.
SUMMARY
[0002] The present invention relates generally to blending fluids and more specifically to an improved method of blending well treatment fluids at the well site.
[0003] In one embodiment of the present invention a method for blending a well treatment fluid at a well site, comprises: providing a first centrifugal pump for pumping a first component of the well treatment fluid into a pipe; providing a first valve for controlling the flow of the first component of the well treatment fluid into the pipe; providing a second centrifugal pump for pumping a second component of the well treatment fluid into the pipe; providing a second valve for controlling the flow of the second component of the well treatment fluid into the pipe; and controlling the pumps and the valves so as to control the ratio of the first component of the well treatment fluid to the second component of the well treatment fluid being delivered to the pipe.
[0004] In another embodiment of the present invention a system for blending a well treatment fluid at a well site, comprises: a first centrifugal pump for pumping a first component of the well treatment fluid into a pipe; a first valve for controlling the flow of the first component of the well treatment fluid into the pipe; a second centrifugal pump for pumping a second component of the well treatment fluid into the pipe; a second valve for controlling the flow of the second component of the well treatment fluid into the pipe; and means for controlling the pumps and the valves so as to control the ratio of the first component of the well treatment fluid to the second component of the well treatment fluid being delivered to the pipe.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1 is a schematic view of a system for blending well treatment fluids at the well site.
DETAILED DESCRIPTION
[0006] Referring now to FIG. 1 , shown therein is an exemplary embodiment of a system for blending well treatment fluids at the well site. The system, designated generally by the numeral 100 , may be mounted on a trailer or skid (not shown). The system 100 blends various components of the well treatment fluid directly into a pipe 110 . This reduces or eliminates the need for standard mixing tanks or tubs. This may be accomplished using at least two centrifugal pumps 120 (shown as 120 a , 120 b , and 120 c ). The centrifugal pumps 120 may each pump a different component of the desired well treatment fluid. For example, in an acid treatment, a first centrifugal pump 120 a may pump a hazardous chemical such as hydrochloric acid (HCl), a second centrifugal pump 120 b may pump water, and a third centrifugal pump 120 c may pump a highly corrosive chemical such as Ammonium Bi-Fluoride (“AF”). While HCl, water, and AF are disclosed, it should be understood that the chemicals may include any acid, hazardous chemical, corrosive, or other fluid.
[0007] The system 100 may also include a number of valves 140 (shown as 140 a , 140 b , and 140 c ) for controlling the flow of the various components from the centrifugal pumps 120 into the pipe 110 . The valves 140 may be butterfly valves, or any other valve suitable for use with well treatment fluids.
[0008] Between the centrifugal pumps 120 and the valves 140 , the system 100 may include pressure transducers 150 (shown as 150 a , 150 b , and 150 c ) that act as a pressure controls on the centrifugal pumps 120 , preventing the centrifugal pumps 120 from pushing one another off line. Feedback from pressure transducers 150 may signal pressure set points in centrifugal pumps 120 , such that the centrifugal pumps 120 maintain a desirable balance.
[0009] Between the valves 140 and the pipe 110 , the system 100 may additionally include flow meters 160 (shown as 160 a , 160 b , and 160 c ) and check valves 162 (shown as 162 a , 162 b , and 162 c ) to monitor and control flow rates from the pumps 140 .
[0010] Liquid additives may also be introduced into the pipe 110 . The additives may be stored in liquid additive storage tanks (not shown), and pumped into the pipe 110 via one or more liquid additive pumps 130 . While the liquid additive pump 130 is shown as a hand pump, the liquid additive pump 130 may be any type of pump, including, but not limited to a positive displacement pump. One or more liquid additive valves (not shown) may be included to control the flow of liquid additives from the liquid additive pumps 130 into the pipe 110 .
[0011] The well treatment fluid may be blended directly in the pipe 110 , without the use of any tank. The flow rate and pressure of any of the components may be controlled by controlling the pumps 120 , 130 and the valves 140 . This allows for the ratio of the various components and additives of the well treatment fluid to be modified as necessary for the specific field conditions at any given time. This modification can take place in real-time, allowing the desired well treatment fluid mix to be pumped into the well as it is needed.
[0012] Additionally, the system 100 may have a number of additional valves (not shown), with locations suitable for controlling flow in various ways as would be readily understood by one of ordinary skill in the art. For example, these additional valves may be butterfly valves, some of which are open and some of which are closed.
[0013] A discharge flow meter 170 may be included in the system 100 . This may allow for adjustments to be made to the pumps 120 and valves 140 , such that the correct mix ratio is maintained without creating undesirable negative pressure in the system 100 . After the mix has passed through the discharge flow meter 170 , it may pass through another pump (not shown), which then pumps the mix downhole.
[0014] Computer software may be used to control the mix ratio. The computer software may include a pressure control system, a rate control system, and/or a concentration control system. The pressure control system may control pressure by controlling the pumps 120 . The rate control system may control flow rate by controlling the valves 140 . The concentration control system may control the concentration by controlling the pumps 120 .
[0015] The pressure control system may include a drive signal to the centrifugal pumps 120 and feedback from pressure transducers 150 . Each of the centrifugal pumps 120 may maintain a separate pressure set point. These pressure set points may be based on expected rate and resultant discharge pressure. The optimal pressure set point may place the valves 140 at a predetermined percentage open for each respective expected rate.
[0016] The rate control system may include a drive signal to each valve 140 and feedback from the respective flow meter 160 . The valve 140 for a first (or master) component (e.g. water) may be set to 100% open and the rate may be set by the discharge rate, as measured by the discharge flow meter 170 . The rate set points for the remaining valves 140 may be set by the concentration control system. Thus as the requirements for concentrations change (even during a job), the operator has the ability to ramp up or down the concentration and/or liquid additives depending on the specific need. This may be a desirable alternative to the standard practice of mixing a new batch at the acid plant and transporting the mixture to the well site.
[0017] The concentration control system may include the rate control system and the rate feedback from the master (e.g. water) rate, which may be measured by the corresponding flow meter 160 . Based on a predetermined well treatment fluid mix, the rate set points for the other components may be calculated from a concentration or parts per thousand of the master rate. As the master rate increases, the rate for the other components may also increase. The increasing rate of other components will slow the increasing master rate until the desired concentration is established.
[0018] The system 100 may optionally include additional components. For example, as shown in FIG. 1 , the system 100 may include a tank 180 . Due to the nature of the types of chemicals used, the tank 180 may be situated on the discharge side of the system 100 . The tank 180 may be used to prevent loss if something goes wrong and the job must be stopped. Additionally, the tank 180 may be useful in situations where the flow rates are very low.
[0019] The system 100 may also optionally include a discharge recirculation pump 198 . The discharge recirculation pump 198 may serve two purposes. The first may be for recirculation. The second may be for discharge at very low flow rates. The recirculation pump 198 may be any type of pump for discharge recirculation (e.g. 120 HP pumps).
[0020] This system 100 may be used for acid blending for acidizing wells, otherwise known as “Acid-On-the-Fly,” which involves blending two or more major hazardous chemical components into a pressurized piping system and injecting one or more liquid additives into that flow stream. This system 100 may alternatively be used for fracturing operations, in which case the treatment fluid would be a fracturing fluid. Additionally, this system 100 may be used for drilling operations, in which case the treatment fluid would be drilling mud.
[0021] The ability to blend “On-the-Fly” may reduce the amount of blended chemicals requiring disposal upon completion of the process. It may also lower exposure of hazardous chemicals to personnel and the environment. Furthermore, it may decrease the number of personnel required for the process and decrease the amount of time hazardous chemicals would be in use. Additionally, by blending the chemicals as they are pumped downhole, there may be a significant reduction of waste that must be disposed of, and cost associated with that disposal process. Further, there may be a reduction in cost for transporting the mixed chemicals, since that would no longer be a requirement. Additionally, there may be a reduction of cost for buying and maintaining the highly regulated cargo tank motor vehicles. Additionally, there may be a reduction and/or elimination of the bulk chemical plants (otherwise known as acid plants) currently being used. By eliminating bulk acid plants, transports, and the physically handling of these types of chemicals the risk of personal and environmental exposure may be significantly reduced.
[0022] Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered or modified and all such variations are considered within the scope and spirit of the present invention. In addition, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee.
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A method for blending a well treatment fluid at a well site, including (1) providing centrifugal pumps for pumping components of the well treatment fluid into a pipe, (2) providing valves for controlling the flow of the components of the well treatment fluid into the pipe, and (3) controlling the pumps and the valves so as to control the ratio of the components of the well treatment fluid being delivered to the pipe.
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