Datasets:

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amylonidis

/

PatClass2011

like 0

WO-1978000001-A1

WO

A1

EN

new

C03B19

C03C3, C03C11

B01D17, B01D39, B01J20, B01J35, B01J37, C02F1, C03B19, C03B37, C03C3, C03C11, C03C13, C03C23, C08J5, C12H1, G21F9

B01D 13/04H, B01D 17/02B, B01D 39/20B, B01J 20/28, B01J 35/06B, B01J 37/02C, C02F 1/68C, C03B 19/12, C03B 37/016, C03C 11/00, C03C 13/04, C03C 23/00S, C03C 3/00, C08J 5/22, C12H 1/04B, G21F 9/12

LOW TEMPERATURE SYNTHESIS OF VITREOUS BODIES AND THEIR INTERMEDIATES

A method of making glass of high purity and in virtually unlimited shapes via solution deposition on a porous self-supporting body by reaction between a first solution and a second solution; an a product made thereby. The rust solution containing at least one basic glass forming solute is confined within a porous container, the walls of which are substantially impermeable to the basic solute. The second solution containing at least one acidic solute is diffused into the porous container through its walls which are substantially permeable to the said acidic solute. The reaction between the rust solution and the second solution takes place within the porous container leading to the deposition of a self-supporting porous body on the inside walls of the container. The porous body which is crystalline, vitreous or intermediate between the two, is purified by leaching and/or washing, dried and thermally consolidated, to a transparent non-porous glass.

LOW TEMPERATURE SYNTHESIS OF VITREOUS BODIES AND THEIR INTERMEDIATESFIELD OF THE INVENTIONThis invention relates to a novel method for making a vitreous body and its intermediates. More particularly, the method relates to a low temperature production of a vitreous body via synthesis of a self-supporting body by solution deposition. DESCRIPTION OF THE PRIOR ARTIn recent years, the most commonly employed commercial process for the manufacture of glass is the direct melting process. This process is somewhat tedious and has not been very successful in the melting of easily devitrifiable and high refrac¬ tory glass. Many of the latest technological advances demand glass to be in a state of high purity which is seldom met in a direct process. Operational cost of the direct process is energy-sensitive and recurring energy crises continue to have significant impact on glass making operations. Consequently, a method for preparing glass at low cost, in a state of high purity and in relatively unlimited composition is needed.A number of indirect processes, namely, anodization, shockwave treatment, and neutron bombardment, have been proposed, but their use has never been realized on a large scale. These processes severely limit the operational flexibility and in most cases, the production cost is higher than for the direct process.In U.S. Patents 2,480,672, 2,106,744 and 3,785,793, for example, a process is disclosed wherein the silica content of an easily meltable alkali-borosilicate glass is enriched by phase separation and leaching. The porous glass which is obtained as an intermediate product is thermally consolidated at elevated tempera¬ ture. Although the process is comparatively inexpensive, it suffers from the limitation with respect to choice and regulation of glass-forming compounds. Choice and regulation of modifying compounds can, however, be achieved via a doping operation in the pores of porous glass. Physical doping operations are dis¬ closed, for example, in U.S. Patents 2,336,227, 3,232,782, 3,938,974 and in the Ph.D. Thesis of M. Samanta, Molecular Engineering of Silica-Rich Glasses Produced by Phase Separation, Catholic University of America, 1975. A chemical doping process is disclosed in a pending U.S. patent application, Serial No. 832,230 filed September 12, 1977 by M. Samanta.High purity glass has been prepared by a vapor deposi- tion process as described, for example, in U.S. Patents 2, 326,059, 3,884,550 and 4,062,665 among many others. In such a process vitreous silica is deposited in the form of a self-supporting porous body singly or in combination with a dopant. This process is expensive and the shape of bodies obtainable from such a process is limited. Polymerization processes have been tried for glass making with limited success. Two distinct lines of approach have been attempted. First is the concentration of a colloidal solu¬ tion under controlled conditions as described, for example in U.S. Patents 2,886,404 and 3,535,890. Second is the interaction in solution between a silicon compound and a polymerizing agent therefor, as described, for example in U.S. Patents 3,678,144, 3,827,893, and 4,059,658. The main difficulty in both lines of approach is the large shrinkage accompanying the process which makes the glass susceptible to breakage and which presents a poten¬ tial problem in the design of molds. SUMMARY OF THE INVENTION In the process of the present invention, first and second solutions separated by a permeable barrier are provided. The first solution contains at least one basic or alkaline glass forming solute and the second solution contains at least one acidic solute with the permeable barrier being substantially permeable to the acidic solute but substantially impermeable to the basic solute. When the first solution and the second solution are originally at suitable concentrations, passage of the second solution through the barrier occurs and a chemical combination takes place resulting in the deposition of a porous self-supporting body on the side of the barrier in contact with the first solution. The porous body can be purified, dried and thermally consolidated to a non-porous glass. DETAILED DESCRIPTION OF THE INVENTIONThe present invention facilitates an economical mass production of vitreous bodies in a state of high purity and in virtually unlimited shapes. According to this invention, a porous self-supporting body deposits on a substrate, when a first solu- tion containing a suitable concentration of at least one basic glass forming solute is allowed to react, on the substrate with a second solution containing a suitable concentration of at least one acidic solute. When the concentration of the acidic solute in the second solution falls outside of the range of suitable concentrations, amorphous or crystalline particles result with no interconnectivity. The broadness of the range of appropriate con¬ centrations depends on the particular type of reaction and can be determined experimentally by trial and error. The first solution and the second solution are separated by a permeable barrier the walls of which act as a substrate for deposition of a porous self-supporting body. The second solution is diffused through the through the barrier which is substantially permeable to the acidic solute but substantially impermeable to the basic glass forming solute. This assures a reaction between the first solution and the second solution on the barrier to deposit a porous self supporting body.The nature and composition of the solutions which are useful for glass formation are shown in Table 1 (first solution) and Table 2 (second solution) . The solutions may be binary (containing one solute) or multicomponent (containing more than one solute) . The solvents useful for the purpose of making a solution may be water, hydrocarbons such as benzene, alcohols such as methanol, ketones such as acetone, ethers such as diethyl ether, carboxylic acids such as acetic acid and mixtures thereof.TABLE 1First SolutionAll solutions contain moderately high to very high concentrations of the basic glass forming solute. The solutions may be true solutions or colloidal solutions. The solutes exemplified in the above table may be simple solutes or complex solutes. Simple solutes are those which are combinations of two different oxides; complex solutes are those which are combinations of more than two oxides. An example of the simple solute is the silicate Na2O,x Si02 where x= 2 to 4 available in commercial water glass solution. An example of the complex solute is the silicate or borate,K2O. 2B2O3. 3SiO2 which can be made synthetically. A convenient method for making an aqueous solution of a simple solute or comp¬ lex solute is to mix suitable raw materials in desired proportion, fuse the mixture at high temperature and finally treat the fused mass with hot water with or without the use of pressure. Other methods include dissolving amorphous oxide in hot aqueous alkali. In many cases the aqueous solutions of the simple solutes or complex solutes are turbid, presumably due to the homogeneous distribution of some undissolved solute in colloidal dimension. In cases where more than one basic glass forming solute is used complications might arise due to the interaction of two solutes leading to the formation of a gel. As an example, the inter¬ action of sodium silicate and sodium aluminate in aqueous solu¬ tion leads to the formation of a gel. The problem can be avoided by using a low concentration of one solute so that gel is formed in small amounts which can be dispersed throughout the solution in colloidal dimension.The prefered concentration range of the basic glass forming solute in the first solution should be such that it will be able to provide from 0.10 mole to 40 moles of glass forming oxide from 1 liter of solution. Stronger or weaker concentra¬ tions may also be used to tailor the process to the product desired. In case more than one basic glass forming solute is present or in case the basic glass forming solute is a complex one, the first solution should be able to provide from 0.10 moles to 40 moles of at least one glass forming oxide.TABLE 2Second SolutionMost solutions should contain very low to moderately high concentrations of the acidic solute; very high concentrations have been found to be useful in special circumstances. The con¬ centration range of the acidic solute in the second solution depends on the concentration of the first solution and can be ascertained by trial and error. The solution must be a true solution. Table 2 continued -is a rapid initial movement of the second solution into the first solution because of large differences in osmotic pressures between the two solutions. With the progress of reaction, this difference decrease because some of the impermeable component deposits out of the solution. The reaction at any stage can be controlled by using external pressure either on the first solution or on the second solution.Various additives may be added to the first solution and/or the second solution to have the desired effects. Suitable additives include peptizing agents, protective colloids, coagulating agents, structure modifiers and composition modifiers. Additives may be present in the first solution as dissolved solute or in homogeneous suspension. They increase the viscosity of the solution and offer resistance to the movement of the basic solute which is desirable for producing a self-supporting structure. The additives may co-deposit in the porous body to increase the porosity and pore-size. Additives for the second solution must be present as dissolved solute. They may increase the pH buffering capacity and/or the osmotic pressure of the second solution which is desirable.The porosity and pore-size of the porous self-supporting body are found to be directly proportional to the concentration of the second solution and inversely proportional to the concentration of. the first solution. Thus, an asymmetric distribution of pore- sizes in the deposited porous body can be achieved merely by pro¬ per manipulation of the concentrations of the solutions at various instants of the process. It has been found that washing the depo¬ sited porous body with water increased the pore diameter and the porosity to a small extent due to the slight dissolution of the porous skeleton by a solution of unreacted basic solute. The thickness of the deposited porous structure is a function of duration of combination. The duration of combination also determines a composition profile within the porous body. A portion of the porous body near the walls of the porous container has more complete deposition than a portion far from the walls. This profile in composition can be destroyed- by leaching with an acid.It has already been pointed out that depending on the concentration of the first solution, a range of concentrations of the second solution can be used to form a self-supporting porous body. When the actual concentration is high in the range of concentrations, the deposited porous body is predominantly crystalline. When the actual concentration of the second solution is low in the range of concentrations the deposited porous body is predominantly vitreous.It is possible to develop in the porous body two or more layers having different compositions merely by replacing the first solution and/or second solution with a different composition. This is an example of discontinuous variation of composition in the porous body. A continuous variation of composition in the porous body can be achieved by varying the composition of the first solution and/or the second solution continuously. In making compositionally inhomogeneous porous body, the importance of both first solution and second solution has to be considered since in the deposition process, the glass forming oxide corresponding to the basic glass forming solute is deposited either singly or in combination with an oxide derived from the acidic solute.The physically bound impurities in the porous self- supporting body can be removed by washing with water at room temperature. The composition profile in the porous body due to non-uniform deposition can be eliminated by leaching. Leaching is done with N/1000 to 3N dilute mineral acid at temperatures varying from 25°C to 100°C.The porous structure can be doped physically or chemically with a modifier. Physical doping processes are described, for example in U.S. Patents 2,336,227, 2,232,782, and 3,938,974 and in the Ph.D. Thesis of M. Samanta, Molecular Engineering of Silica-Rich Glasses Produced by Phase Separation , Catholic University of America, 1975. In this process, the porous body is impregnated with a solution of dopant, dried at room temperature to remove most of the solvent, heated to decompose the dopant into an oxide and finally consolidated at high tempera¬ ture to incorporate the oxide. A chemical doping process is disclosed in pending U.S. patent application, Serial No. 832,230 filed September 12, 1977 by M. Samanta. This chemical doping process involves exchange of protons in the porous body with cations in a weak basic medium.Most of the physically bound water in the undoped or doped porous body can be removed by room temperature drying. Rapid drying introduces tension, particularly at the cut edges of the porous body which then tends to crack. This can be prevented by coating the cut edge with a thin film of polyethylene glycol as described in U.S. Patent 2,861, 351. For a porous structure containing pores of 200 A or lower, controlled drying under a relative humidity of 60-90% is preferable. Capillary forces in this case ar-e very high and too rapid drying causes breakage of the structure.Chemically bound water in the form of surface hydroxyl groups cannot be removed by room temperature drying. These can be removed by vacuum drying at temperatures below the consolidation temperature of the porous body as described in U.S. Patent 2,505,001 or by chemical methods as described inU.S. Patents 2,982,053, 3,459,522 and 3,535,890 wherein replace¬ ment of hydroxyl groups in the porous body is done by halogen. An efficient chemical method ϊs> disclosed in U.S. patent application Serial No. 832,231 filed September 12, 1977 by M. Samanta. In this method, the combination of two non-bridging hydroxyl groups in the porous body to form a single bridging oxide group is sought to be achieved in the presence of an acid anhydride.The doped or undoped porous structure, after removal of most of the physically bound water by room temperature drying for 2 days is heated at the rate of 100°C per hour. It is then kept at about 600° for 2 hours and chemically bound water is removed by appropriate treatment. The temperature is raised again at the rate of 100°C per hour until the porous body is consolidated to a non-porous vitreous body. For a crystalline porous body, the consolidation temperature is close to the liquidus temperature of the consolidated glass (liquidus temperature is the maximum temperature at which glass coexists with crystal) . For a vitreous porous body the consolidation temperature is close to. the glass transition temperature of the consolidated glass (glass transition temperature is the temperature corresponding to the breakpoint of the specific heat versus temperature curve of a glass) . For a mixed phase porous body, the consolidation temperature lies between the glass transition temperature and the liquidus temperature.It is found that glass prepared by the process of this invention is extremely pure. Thus, in the deposition of a germania and silica porous body, impurities like Fe, Co, Ni, Cu, Cr preferentially migrate into solution. Glass made from such a porous body is highly transparent to ultraviolet, visible and infrared radiation.In order to indicate more fully the nature and utility of my invention, the following specific examples are set forth. In all examples, tubular cellulose dialyzer membranes having an average pore diameter of 4.8 nm are used. All concentrations expressed in percentage are gms per 100 ml of solution except where otherwise differently stated. All chemicals are laboratory reagent grade chemicals except for sodium silicate and cesium nitrate.EXAMPLE 1In each of the following experiments, a dialyzer tube 4 in length and 0.5 in diameter is closed at one end and then filled with 40°Be aqueous sodium silicate solution (first solution). 40°Be aqueous sodium silicate solution has a composition of 6.5% Na2O, 25% SiO2 and 68.5% H20, all percentages being expressed in gms per 100 gms of the solution. The tube is then closed at the other end. The closed tube which has a length of 2.5 is almost filled with silicate solution and contains very little space filled with air. The tube is completely immersed in a horizontal position in 3000 ml aqueous ammonium chloride solution (second solution) for 24 hours. .Because of the molecular sizes, only ammonium chloride molecules and no sodium silicate molecules can diffuse through the membrane. The results of various experiments are shown in Table 3. The average room temperature recorded during the experiments is 24°C. TABLE 3 Table 3 continued - Table 3 shows that against a concentration of 40°Be aqueous sodium silicate solution (first solution) concentrations of aqueous ammonium chloride solution (second solution) corres¬ ponding to Experiment Numbers 4, 5, 6, and 7 are suitable for the formation of a porous self-supporting body. Thus, against a concentration of 40°Be aqueous sodium silicate solution (first solution) the range of suitable concentrations is from 0.5% to 5% for aqueous ammonium chloride solution (second solution) . Table 3 also shows that when the actual concen- tration of aqueous ammonium chloride solution is high in the range of concentrations, the deposited porous self-supporting body is predominantly crystalline; when the actual concentra¬ tion of aqueous ammonium chloride solution is low in the range of concentrations, the deposited porous self-supporting body is predominantly vitreous.The concentrations of the reactants useful for deposition of a porous self-supporting body, as demonstrated above, may not be suitable under a set of different conditions. Use of a membrane of different pore size, use of different temperature and use of pressure on either solution can alter the concentration of either solute available for reaction on the membrane substrate. Four deposited porous self-supporting bodies are separated from the membranes and their diameters appear to be larger than the diameter of the original dialyzer tube. This is due to the fact that in the initial stage, there is rapid absorption of ammonium chloride solution within the tube due to the large difference in osmotic pressure between the ammonium chloride solution and the sodium silicate solu- tion. Consequently, within the tube there is a development of pressure which is partially relieved by expansion of the tube both in diameter and length. The porous bodies after washing with water 2 times, are leached with .01N H2SO4 at 21°C for 10 hours to remove sodium ions and then washed with water to remove the acid.. The porous bodies after washing are dried at 21°C for 48 hours to remove most of the physically bound water. They are heated under vacuum at the rate of 100°C per hour. They are then held at 600°C for 2 hours. The temperature is raised again at the rate of 100°C per hour until the porous bodies are consolidated to a non-porous glass. Table 3 shows that consolidation temperature for a crystalline porous body is higher than that for a vitreous porous body. Theoretically, a crystalline porous body should have a consolidation tempera- ture close to the liquidus temperature of the consolidated glass, whereas a vitreous porous body should have a consolidation temperature close to the glass transition tempera¬ ture of the consolidated glass. All four consolidated glasses are analyzed for silica, sodium and iron concentration. The average sodium concentration is 50 ppm, the average iron concentration is 15 ppb, and the average silica concentration is 99.99%. Thus, it is found that very pure silica glass can be prepared by this invention. The concentration of sodium which deteriorates the refractoriness and the concentration of iron which deteriorates the optical quality can be further decreased by using raw materials of high purity and/or using a more severe leaching condition.EXAMPLE 2In each of the following experiments, a dialyzer tube 4 in length arid 0.5 in diameter is closed at one end and then filled with 40°Be aqueous sodium silicate solution. The tube is closed at the other end. The closed tube which has a length of 2.5 is almost filled with silicate solution and contains very little air space. The tube is completely immersed in a horizontal position in 3000 ml 50% aqueous aluminum sulfate solution for the desired time. The deposited porous vitreous body is separated from the dialyzer tube and washed with water. The wall thickness of the washed product is measured. The results of various experiments are shown in Table 4.TABLE 4Average temperature of the experiments = 24°C.This example verifies that wall thickness of the deposited porous body is directly proportional to the duration of combination of the two solutions. In the above experiments, changes in length and in diameter of the dailyzer tubes are practically zero, presumably because the osmotic pressures of the two solutions are very close. It has to be noted that reaction between aqueous aluminum sulfate solution and aqueous sodium silicate solution is very slow. Other reactions like the reaction between aqueous ammonium chloride solution and aqueous sodium silicate solution are very fast and a consider¬ able amount of wall thickness of porous body can be built up in a very short time. EXAMPLE 3In the experiments of Example 1, it is found that the shape and size of the deposited porous body were slightly different from the original shape and size of the membrane. This is due to the rapid osmotic absorption of the second solution within the tube towards the beginning of the experi¬ ment. This leads to a development of pressure and makes the membrane dimensionally unstable. In the following experi¬ ment (Experiment No. 12) the system is buffered with respect to change in pressure. A dialyzer tube 0.5 in diameter and 20 in length is closed at one end and is partially filled with 75 ml 40 Be aqueous sodium silicate solution. The open end of the dialyzer tube is fastened to a support and the tube is suspended vertically in 5000 ml 0.5% aqueous ammonium chlo- ride solution so that 75% of the solution within the dialyzer tube is immersed in ammonium chloride solution. The part of the dialyzer tube which is not filled with silicate solution remains more or less collapsed. The initial rapid diffusion - of the second solution into the tube is thus prevented by a counter acting hydrostatic pressure. Further, solution diffused into the dialyzer tube is accommodated by the inflation of the collapsed portion of the dialyzer tube and this prevents any dimensional instability of the immersed portion of the dialyzer tube. The deposited porous glass tube is found to be perfectly cylindrical conforming to the shape and size of the dialyzer tube. The average room temperature recorded during the experiment is 24°C.It is found that non-uniformity in deposition can be caused by variation in pressure from point to point in a porous container. This gives rise to a problem when the portion of the porous container directly involved in the deposition process had a large vertical length. This problem can be minimized or eliminated by positioning the porous container in the second solution to occupy the shortest vertical distance, and providing the porous container with a flexible non-porous closure which can expend to relieve the pressure developed in course of the process. It is preferable to have the porous container as rigid as possible and to have solutions of very close osmotic pressure. An alternative method for relieving the pressure is to provide the opening of the porous container with a solution-tight piston which can yield to pressure by moving away from the container across a path enclosed by a non-porous structure. In another alternative method a hollow needle may be used to bleed off excess pressure.EXAMPLE 4138 gms potassium carbonate, 248 gms boric acid and 314 gms germania are intimately mixed together and the mixture is vitrified by melting in the ceramic crucible at 1300°C. While hot, the molten mass is poured into 1000 ml of water at room temperature whereby the glass is broken into numerous fragile particles. The mixture is filtered and both the resi- due and filtrate are further treated. The residue is ground to powder which is then added back to the filtrate and the combina¬ tion is heated at 100°C for one hour to dissolve as much solute as possible. The volume of the solution is adjusted to 1000 ml. The potassium borogermanate solution thus obtained contains one mole of K2O, two moles of B2O3 and 3 moles of GeO2. The solu¬ tion appears turbid, presumably due to the homogeneous suspen¬ sion of some undissolved solute in colloidal dimension.15,000 ml of pH 5.00 acetic acid-sodium acetate buffer solurion is prepared as follows. 10,000 ml sodium hydroxide solution and 10,000 ml acetic acid solution, each of approximately 0.5N concentration are made. The actual concentrations of acetic acid solution and sodium hydroxide solution are determined by titration and are found to be 0.500N and 0.426N respectively. Using these values, a 15,000 ml pH 5.00 acetic acid-sodium acetate buffer is prepared by adding 6420 ml of sodium acetate to 8580 ml of acetic acid.In each of the following experiments, a dialyzer tube 0.5 in diameter and 20 in length is closed at one end and is partially filled with 75 ml aqueous potassium borogermanate solution. The open end of the dialyzer tube is fastened to a support and the tube is suspended vertically in 5000 ml acetic acid-sodium acetate buffer solution so that 75% of the solution within the dialyzer tube is immersed in buffer solution and the other 25% of the solution stays above the buffer solution. After the desired length of time, the deposited porous glass body is taken out and is separated from the dialyzer tube.The porous glass tube is washed with water five times and dried at room temperature for two days. The samples from several locations inside glass tubes are analyzed for potassium oxide concentration. The results of various experiments are shown in Table 5. TABLE 5This example demonstrates the use of a complex solute (consisting of more than two oxides) in the first solution and the use of a buffered second solution containing an organic acid. Further, this example demonsrates the existance of a composition profile which is a function of time.EXAMPLE 5To 1000 ml vigorously boiling distilled water is added drop by drop, a freshly prepared solution made by dissolving 5gms of ferric chloride in 5 cc of water. As each drop falls into the boiling water, ferric chloride suffers hydrolysis, forming a beautiful deep red ferric oxide sol. The sol obtained is rapidly dialyzed in a cellphane bag against warm water to free it from the hydrochloric acid and undecomposed ferric chloride. The purified sol is then concentrated to a volume of 10 ml by slow evaporation.In the following experiment (Experiment No. 16) 75 ml red colloidal solution is prepared by uniformly mixing 70 ml of 40°Be aqueous sodium silicate and 5 ml of ferric oxide sol. A dialyzer tube 0.5 in diameter and 20 in length is closed at one end and is partially filled with 75 ml red colloidal solution. The open end of the dialyzer tube is fastened to a support and the tube is suspended vertically in 5000 ml 0.75% aqueous ammonium nitrate solution So that 75% of the solution within the dialyzer tube is immersed in ammonium nitrate solution and the other 25% of the solution stays above the ammonium nitrate solution. After 30 hours, the deposited red porous body is taken out and is separated from the dialyzer tube. The deposited porous body on analysis shows the presence of ferric oxide. The average room temperature recorded during the experiment was 24°C. This example demonstrates the use of an additive in the first solution to incorporate a modifying compound in the deposited porous hody.EXAMPLE 6In the following experiment (Experiment No. 17), a dialyzer tube 0.5 in diameter and 20 in length is closed at one end and partially filled with 75 ml of 40° aqueous sodium silicate solution. The open end of the dialyzer tube is fastened to a support and the tube is suspended vertically in 5000 ml 0.5% aqueous ammonium chloride solution so that 75% of the solution within the dialyzer tube is immersed in ammonium chloride solution and the other 25% of the solution stays above the ammonium chloride solution. After 25 hours of reaction, the solution within the dialyzer tube is replaced by 70 ml of of aqueous potassium borogermante solution as prepared inExample 4; other conditions of the experiment remain unchanged. The reaction is allowed to continue for another 25 hours. The deposited composite porous glass is taken out and is separated from the dialyzer tube. The average temperature recorded during the experiment is 27°C. The porous body, after washing with water two times, is leached with 0.005N H2SO4 at 27°C for 10 hours to remove sodium ions and potassium ions and then washed with water to remove acids. The porous body after washing is dried at 21°C for 48 hours to remove most of the physically bound water. It is heated under vacuum at the rate of 100°C per hour up to 600°C. The vacuum is then taken off and the porous glass is treated with SO3 vapor for 2 hours at 600°C. This process removes the chemically bound water. The porous glass is subjected to vacuum again and the temperature is raised again at the rate of 100°C per hour until the porous body is consolidated at 1450°C to a transparent non-porous glass tube. The tube is a composite with the outer wall substantially made of silica and the inner wall substantially made of germania.EXAMPLE 7In the following experiment (Experiment No. 18) doping with cesium salt is performed using the porous silica glass made in Example 3. For good optical quality, both the cesium salt and the porous glass need to be purified. The purification of porous glass is done by leaching with 0.005N H2SO4 at 27°C for 10 hours. A more severe leaching condition is next adopted by leaching the porous glass with 2N H2SO4 at 95°C for 24 hours. The tube is washed with water to remove acids and is ready for the doping operation.Commercial grade CsNO3 contains 3 - 5 ppm of iron which is detrimental to the optical quality of glass. It is found that a solution of CsNO3 saturated at 100°C has a pH of 6, at which some iron must precipitate in order to maintain the solubility product of Fe(OH), at its extremely low value. 250 ml of solution of CsNO3 saturated at 100°C is vigorously boiled under reflux for 6 hours. The solution turns reddish due to precipitation of Fe(OH)3 and the filtered solution is cooled to crystalization at 23°C. The crystals are separated by filtration and the filtrate which is a saturated solution of CsNO3 in water at 23°C is used in the doping process.To 100 ml of CsNO3 solution is added 200 ml of liquid NH,. The purified porous glass tube is dipped into the above solution. In this process, the protons from the porous glass are replaced by the cesium ions. The ion exchange is complete in three days. The tube which looks white is washed with water to remove CsN03 and NH3. The tube is dried at 23°C for 48 hours to remove most of the physically bound water. It is heated under vacuum at the rate of 100°C per hour up to 600°C. It is held at that temperature for 2 hours. The temperature is raised again at the rate of 100°C per hour until the porous body is consolidated at 1450°C to a trans¬ parent non-porous glass tube.It is found that the first solution and the second solution used in the above examples would form a gel when combined without the use of a porous container. The use of a porous container densifies the gel structure which is intra- connected so as to form a self-supporting porous structure. Thus, although the discussion and the example mainly concern themselves with the formation of certain inorganic oxide porous bodies by acid-base type reactions within a porous container, any reaction in which the reactants fulfill the requirement of gel formation and the requirements of permeability for one and impermeability for the other will be suitable for formation of a porous self-supporting body. Thus manufacture of metallic glasses, organic glasses and other inorganic glasses is possible by the process of this invention. In the method thus generalized for low temperature synthesis of a porous self-supporting body a first solution containing at least one first solute and a second solution containing at least one second solute are provided, wherein the first solution is capable of reacting with the second solution to form a gel. The first solution is confined within a porous container the walls of which are sub¬ stantially impermeable to the first solute and the second solution is diffused into the porous container the walls of which are substantially permeable to the second solute. Within the porous container the reaction between the first solution and the second solution takes place to deposit a porous self-supporting body on the walls. The selection of the concen- tation of the first solution and of the concentration of the second solution are done by trial and error. The first solution and/or the second solution may contain additives to have desired effects. The additives are, for example, peptizing agents, coagulating agents, protective colloids, structure modifiers and composition modifiers as known in the art. Additives offer resistance to the movement of the first solute and this may cause an otherwise permeable (through the walls of the porous container) first solute to become an apparently impermeable one. A weakly gel forming reaction can be converted into a strongly gel forming one by use of certain additives. The porous self-supporting body can be purified, dried and consolidated to a non-porous body. The following table summarizes different types of reactions which can be used to synthesize a porous self-supporting body. TABLE 6 By using the process of this invention vitreous bodies and their intermediates can be made at a much lower cost,with much higher purity, in virtually unlimited compositions and in virtually unlimited shapes. It has a great deal of operational flexibility which is a contrast to the tedious conventional process. The simplicity of the process allows it to be prac¬ ticed in a light chemical facility provided with a minimal number of process accessories. Most of the raw materials useful for the process are cheap, easily available and pose very little danger to the environment. Many of the raw materials can be made indigenously. Atmospheric pollution due to emission of harmful gases is totally absent in many cases and this is a big plus over direct melting processes where pollution is caused by oxides of nitrogen, phosphorus, arsenic, carbon and sulfur.The porous self-supporting body prepared by this invention has many desirable physical and chemical properties. These are high refractoriness, chemical inertness, large surface area, controlled porosity and exceptional purity. The main uses of the porous body are as a filtering medium, as a carrier, as an absorbent and as an ion-exchange medium.Dispersed solids can be separated from liquids and gases by means of the porous body. The separation is based on the molecular size and the porous body can be used for purifi- cation of toxic gases and polluted air and for separation of suspended impurities from waste water.Dissolved solute on the other hand, can be separated from the solvent by hyperfiltration using a membrane made from the porous body of this invention. For this purpose the porous body is considered to be superior to the organic membrane com¬ monly used. Use of an asymmetric membrane will contribute to more efficiency. The separation is based on reverse osmosis and can be used for desalination of saline water, purification of waste water and separation of mixtures of fluids from one another.Dissolved solutes can be separated from one another by ultrafiltration using a membrane made from the porous body of this invention. As in the case of hyperfiltration, an asymmetric membrane will be found more useful in this case. The separation is based on molecular sizes and can be used in laboratory and industrial dialysis. When coated with non- thrombogenic material, the membrane can be used in an artificial kidney.Other potential uses of ultrafiltration or hyper- filtration using a membrane made from a porous body of this invention are in the dairy industry, in food processing, in pulp and paper manufacture and in electroplating waste treatment. The membrane useful for ultrafiltration and hyper- filtration can be in the form of flat membranes, tubes or hollow fibers which are easy to fabricate by following the process of this invention.The porous body can be used for chromatographic applications and as a carrier for biologically active materials such as antigens, antibodies and enzymes. As a catalytic support, the porous body will find applications in chemical process industries like petroleum refineries and in the cata¬ lytic converters of internal combustion engines.The porous body of this invention is a strong absorbent for certain types of molecules which may be solids, liquids or gases. As an absorbent, it can purify liquids and gases like purification of air in an enclosed space and puri¬ fication of beer and wine. It can be used as a drying agent to remove moisture from a system. It can be used to separate a mixture of gases and mixture of liquids which are not readily separable by any other means. An example is the separation of n-hexane and n-octane.The porous body of this invention is a very good medium for ion exchange. The exchange is conveniently done by following the procedure disclosed in U.S. patent application Serial No. 832,230, filed September 12, 1977, by M. Samanta.A prospective use will be purification of nuclear waste liquid containing radiocesium Cs137. When a porous body immersed in waste liquid is treated with NH3, Cs137will be absorbed in the porous body and other radioactive impurities like radio- strontium will be precipitated. The precipitate and porous body will be separated from the liquid which will thus be free from the radioactive material. The precipitate can be properly sealed in a suitable container and the porous body can be consolidated before disposal of the concentrated waste.An alternate procedure will be to exchange the protons in the porous body with Li+, Na+ or K+ and then treat the nuclear waste liquid with the exchanged porous body whereby all the radioactive cations will be absorbed within the porous body.A porous body exchanged with an alkali metal cation can be used for water softening, absorbing Ca++ and Mg++ during the process.The porous body prepared by this invention is hydro- philic and it has a strong affinity for water. A mambrane made from the body is readily wetted by water. The membrane will allow the water to pass through, but no air or gas entrained in the liquid will be able to pass. This property makes the membrane useful for intravenous injection devices where the passage of air into the veins has to be prevented by all means. The porous body prepared by this invention can be made hydrophobic by coating the hydrophilic surface with a hydrophobic material or by deactivating the surface hydroxyl groups. A membrane made from a body so treated will not be wetted by water. The membrane will allow air to pass through, but no water entrained in the air will be able to pass. Typical use of the membrane will be in the design of vents. The hydrophobic porous body has a strong affinity for gasoline and oil. So, it can be used for removal of water from gasoline and for removal of oil slicks from sea water.The porous body can be used as a filler and reinforce¬ ment for polymeric material and as a thermal insulator for home and industry. It can be used as an intermediate in processes for making foam glasses.Other uses of the porous body made by this invention are as an electrolytic separator in an electrochemical cell, as a microorganism-impervious cover for medical containers, as a matrix for a composite super conductive body and as a carrier for dynamically produced reverse osmosis membranes.The consolidated glass having a composition profile will have two basic uses. One will be glass strengthening, wherein glass will have a compressive skin because of the composition profile. Typical uses may be in high strength radar domes, and in chemical strengthening of laboratory and commer- cial glassware. The second basic use will be in fiberoptics. Because of the very high purity and the composition profile, glass will be used in making step-index and graded index optical fibers for optical communication and medical endoscopy. The proposed uses of consolidated glass without any profile potentially are many. This invention permits the making of glass within such wide limits of composition that virtually any desired mechanical, chemical, optical and dielectric property can be obtained by selecting a suitable composition. Important uses of consolidated glass should in¬ clude the uses related to household glassware, general labora¬ tory equipment, packaging for electrical components, mirror blanks for astronomical telescopes, acoustic delay lines, wind¬ shields for supersonic vehicles, accessories for thermonuclear reactors, and nose cones for intercontinental ballistic missiles.Of course, many variations and modifications of the subject invention are possible in the 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.

I CLAIM;1. A method for the synthesis of a porous self-supporting body, comprising the steps of: providing a first solution containing at least one basic glass forming solute; providing a second solution containing at least one acidic solute; providing in contact with and separating said solutions a permeable barrier substantially impermeable to said at least one basic solute and substan¬ tially permeable to said at least one acidic solute; and permitting said second solution to pass through said barrier to react with said first solution to deposit on the side of said barrier in contact with said first solution a porous self-supporting body.2. The method of Claim 1 wherein said permeable barrier is a dialyzer membrane.3. The method of Claim 1 wherein said at least one basic solute is selected from the group consisting of borates, aluminates, silicates, germanates, stannates, plumbates, phosphates, arsenates, antimonates, bismuthates, selenates, tellurates, zirconates, titanates, tungstates, vanadates and molybdates.4. The method of Claim 1 wherein said first solution is a true solution.5. The method of Claim 1 wherein said first solu¬ tion is a colloidal solution. 6. The method of Claim 1 and including the step of varying the time during which said solutions are in contact with said barrier so as to obtain a certain thickness for said deposited self-supporting body.7. The method of Claim 1 wherein said deposited self-supporting body is crystalline.8. The method of Claim 1 wherein said deposited self-supporting body is partially vitreous and partially crystalline.9. The method of Claim 1 wherein said deposited self-supporting body is vitreous.10. The method of Claim 1 and including the step of heating said porous body to consolidate it into a non- porous vitreous body.11. The method of Claim 1 and including the steps of: leaching said porous body with acid: washing said porous body with water: drying, said porous body; and heating said porous body to consolidate it into a non-porous vitreous body.12. The method of Claim 1 and including the step of doping said porous body.13. A product made by the process of Claim 1. 14. A product made by the process of Claim 10.15. The method of Claim 1 wherein said first solution contains an additive.16. The method of Claim 1 wherein said second solution contains an additive.17. The method of Claim 1 wherein said first and second solutions contain additives.18. The method of Claim 1 and including the step of varying the rate of deposition of said self-supporting body.19. The method of Claim 1 and including the step of varying the rate of reaction by varying the concentrations of said solutions.20. The method of Claim 1 and including the step of varying the rate of reaction by varying the temperature of said solutions.21. The method of Claim 1 and including the step of varying the rate of reaction by varying the relative pressures of said solutions.22. The method of Claim 1 and including the step of varying the porosity and pore size of said self-supporting body by varying the concentrations of said first and second solutions. 23. The method of Claim 1 and including the step of varying the porosity and pore size of said self-supporting body by varying the concentration of said first solution.24. The method of Claim 1 and including the step of varying the porosity and pore size of said self-supporting body by varying the concentration of said second solution.25. The method of Claim 1 wherein said at least one acidic solute is seleced from the group consisting of acids and salts of strong acids and weak bases.26. The method of Claim 1 wherein the concentration of said first solution is such that one liter of said first solution contains from 0.10 moles to 40 moles of at least one glass forming oxide.27. The method of Claim 1 wherein the solvents for said- first and second solutions are selected from the group consisting of water, hydrocarbons, alcohols, ketones, ethers, carboxylic acids and mixtures thereof.28. The method of Claim 1 wherein said at least one basic solute is a simple solute consisting of two oxides.29. The method of Claim 1 wherein said at least one basic solute is a complex solute consisting of more than two oxides30. The method of Claim 1 wherein said at least one acidic solute is a salt of a strong acid and a weak base.31. The method of Claim 1 wherein said at least one basic solute is selected from the group consisting of silicates and germanates. 32. The method of Claim 1 wherein said barrier is in the form of a container with said first solution on the inside of said container and said second solution on the outside of said container.33. The method of Claim 1 wherein said barrier is in the form of a shaped article whereby said porous self- supporting body conforms to the shape of said barrier.34. A pro duct made by the process of Claim 33.35. The method of Claim 1 and including the step of changing the compositions of said first solution and said second solution during deposition of said self-supporting body to develop in said body, layers of different composition.36. The method of Claim 1 and including the step of changing the composition .of said first solution during deposition of said self-supporting body to develop in said body, layers of different composition.37. The method of Slaim 1 and including the step of changing the composition of said second solution during deposition of said self-supporting body to develop in said body, layers of different composition.38. The method of Claim 1 and including the step of continuously varying the composition of said first solution and said second solution during deposition of said self- supporting body to develop in said body a continuous variation in composition. 39. The method of Claim 1 and including the step of continuously varying the composition of said first solution during deposition of said self-supporting body to develop in said body a continuous variation in composition.40. The method of Claim 1 and including the step of continouously varying the composition of said second solution during deposition of said self-supporting body to develop in said Body a continuous variation in composition.41. The method of Claim 1 and including the step of varying the time during which said solutions are in contact with said barrier so as to develop a certain composition profile for said porous self-supporting body.42. A method for the synthesis of a porous self- supporting body, comprising the steps of:providing a first solution containing at least one gel forming solute: providing a second solution containing at least one solute which will form a gel with the said first solution: providing in contact with and separating said solutions a permeable barrier substantially impermeable to said at least one first solution solute and substantially permeable to said at least one second solution solute: and permitting said second solution to pass through said barrier to react with the said first solution to deposit on the side of said barrier in contact with said first solution a porous self-supporting body. 43. The method of Claim 30 wherein said salt of a strong acid and a weak base is an ammonium salt,44. A product made by the process of Claim 41.45. A product made by the process of Claim 40.

SAMANTA M

SAMANTA M

WO-1978000004-A1

WO

A1

EN

new

F16L13

F16L23, F16L47, B23P11

B23P11, F16L13, F16L23, F16L47

B23P 11/02B, F16L 13/00C, F16L 23/024, F16L 47/22

PIPES AND COUPLINGS AND METHOD OF COUPLING PIPES

A method of securely joining a pipe (1) to a pipe fitting (3) without the need for rotating either element. The fitting (3) or in some cases the pipe (1), is expanded by heating whereby the other element may be inserted in it and the elements are secured together upon cooling by the interengagement of matching grooves (4) and ribs (14) which are provided on the circumferential surfaces of the elements.

Pipes and couplings and method of coupling pipesField of ApplicationThe invention relates to a method of joining pipes to couplings or other fittings, and pipes and couplings or fittings for joining by the method.Disclosure of inventionVarious methods of joining pipes have been known in the prior art but some of these, including the screwing of one element into the other, whilst producing a secure joint, have been impractical in the assembly of complex pipework systems, and the present invention offers the advantage, among others, of ease of installation without loss of security.According to one aspect of the invention there is provided a method of joining members comprising first and second pipe elements of which one member is of thermally expansible material and has an internal cylindrical surface of diameter generally corresponding to the diameter of the cylindrical external surface of the other member, wherein one of said surfaces has at least one circumferential groove therein and the other of said surfaces at least one matching circumferential rib projecting outwardly therefrom, the method comprising expanding the said one member to an extent dependent on the outward extension of said rib or ribs by heating below its melting point to enable one of said membe to enter the other beyond the rib or ribs, assembling the members one within the other, with the or each rib in regis with a corresponding groove, and allowing the expansible member to contract by cooling on to the other member so that the or each rib engages in a corresponding groove.Preferably the said one member is expanded to such an exten that the other member can enter it only by elastic de- formation of the said rob or ribsPreferably there is a plurality of spaced grooves and matching ribs, and the grooves and ribs are of ratchet-like configuration. A sealing and/or sliding agent may be appl to at least one of said surfaces.According to a further aspect of the invention there is provided a combination of members comprising first and second elements characterized in that one member has an internal cylindrical surface of diameter generally corresponding to the diameter of the cylindrical external surface of the other member when both members are at the same temperature, one of said surfaces has at least one circumferential groove therein and the other of said surfaces has at least one matching circumferential rib projecting outwardly therefrom, and the said one member is made of material having such a co-efficient of thermal expansion that it can be expanded by heating below its melting point to such an extent that the one of said member is to enter the other beyond the rib or ribs so that on contraction of said one member the or each rib can engage in a corresponding groove. Prefereably there is a plurality of spaced grooves and matching ribs, and the grooves and ribs are of ratchet-like configuration.According to yet a further aspect of the invention there is provided a pipe element for combination with a further pipe element as aforesaid.Description of FiguresFigures 1 to 4 show sections through combinations of pipes and fittings according to the invention.Description of InventionEmbodiments of the invention will now be described by way of example and with reference to the drawings.The combination shown in Fig. 1 comprises a pipe 1 having a free end 2 and a flanged coupling 3. The pipe 1 is of polypropylene, but inother embodiments may be of other plastics material such as polyethylene, or of metal or other suitable material. The flanged coupling 3 is also of polypropylene, any substitute for which, in other embodiments, will be expansible by heating below its melting point to an extent indicated below.The pipe 1 has an external diameter <3, and at its free end 2 is machined or otherwise formed with circumferential grooves 4. Each groove is defined by a wall 5 substantially perpendicular to the axis of the pipe and an inwardly inclined wall 6, the perpendicular wall being nearer the open end of the pipe. The length of the grooves in the direction of the axis of the tube is 9.5mm. The coupling comprises a flange portion 7 provided with holes 8 for mounting the coupling. Extending from the flange portion is a tubular portion 9 having an internal annular flange 10 which provides an annular shoulder 11 for abutment with end face 12 of the pipe 1 when assembled as will be described below. Between the flange 10 and the open end 13 of the tubular portion 9 of the coupling 3, the internal surface is formed with what may be regarded as a series of circumferential ribs 14 extending outwardly (that is to say towards the axis of the tube) from a theo- retical cylindrical surface of diameter d_. The ribs 14 have faces which are respectively substantially perpendicula to the axis of the tube and inclined at the same angle as the walls 6 of the grooves 4 of the pipe 1. The length and the outward projection of the ribs 14 also correspond to the length and depth of the grooves 4. Between the innermost rib and the shoulder 11 the internal surface of the tube 9 is tapered at 15 at an angle corresponding to the taper 16 at the end 12 of the pipe 1.Typically, the diameter d_ is 50mm and the depth of the groov 4, equal to the projection of the ribs 14, is 2mm. As shown in the drawings that projection of the ribs 14 prevent the insertion of the end 2 of the pipe 1 into the coupling 3 without the distortion of one or other of the components.However, the material of construction of the coupling 3 is such that on heating to a temperature below its melting point, it expands by an amount at least equal to twice the projection of the ribs 14 in a length d_ of the material. Such an expansion will enable the end 2 of the pipe 1 to be inserted into the couplings; a slightly smaller expansion will permit the insertion only by a slight distortion of one or both of the components such as might be effected in a thermal plastics material under an applied load without exceeding the elastic limit.In practice of the method of the invention the coupling 3 is heated in a uniform manner by means for example of hot air, hot oil or by the fluid bed technique. The temperature rise is controlled so that the component does not reach the softening point of the material but sufficiently to ensure that the internal diameter between the peaks of the ribs 14 is only so slightly less than d_ that the end 2 of the pipe 1 can be inserted in the coupling with a snap action by imparting a sharp tap on the coupling in the direction of the axis of the pipe. The end face 12 of the pipe 1 engages the shoulder 11 and thus ensures that the ribs 14 and grooves 4 are in register with one another and, in the absence of a similar force acting in the opposite direction, the pipe 1 will not snap out again. With the source of heat removed, the coupling 3 will cool and return to its original dimensions; in the fully cooled state the components will fit tightly with one another with each rib engaged in a corresponding groove. A certain amount of tolerence can be provided by adjustment of the diameter of the pipe and coupling and of the dimensions of the ribs relative to the grooves, and improved sealing may be afforded by providing a sealing compound in the grooves or between the ribs before assembly of the components. if polytetrafluoroethylene paste is used as the sealing compound, it will also aid the slipping of one component relative to the other. Because of the ratchet-like shape of the ribs and grooves, couplings so assembled will be substantially permanent unless a means can be found of re-heating the coupling without at the same time expanding the pipe.It is envisaged that a range of fittings, such as the coupling 3, will be provided to correspond with pipes having a range of external diameters, The pipes, when cut to the required length, will be cut with external grooves in a similar manner to that in which pipes are sometimes threaded. However, the provision of grooves will be somewhat simpler than the provision of threads and the assembly of the components will be far simpler than screwing of components.Figs. 2 and 3 of the accompanying drawings show respectively an elbow and a T-joint, whilst Figure 4 shows an alternative form of flange fitting. in the fittings shown in Figures 2 to 4, the pipe elements in the form of components respectively designated 20, 21 and 22, are cut with grooves 4 on the outer cylindrical surfaces similar to the end 2 of pipe 1 in Figure 1. These components are joined to pipes, such as pipe 23, in Figure 4, by means of further pipe elements in the form of coupling sleeves 24. Each of the sleeves 24 has an internal annular shoulder 25, and between the shoulder and each open end has a series of ribs 26 formed similarly to ribs 14 on the internal surface of the tubular portion 9of flanged coupling 3. In order to join the pipe to the component the coupling sleeve, which is of thermally expansible material, is heated and snap-fitted to the other elements. It will be understood that the coupling sleeve may be moved relative to a stationary pipe or component, may be moved relative to a stationary coupling sleeve, or there may be movement of both in the snap-fitting operation depending on the requirements of the installation.Two pipes may similarly be joined by the use of a coupling sleeve as described above. Reverting to Figure 1, it will be clear that if the coupling 3 is not used as described above, the end face 13 is available for butt jointing to a pipe of internal diameter d_, and to this extent a coupling or other fitting according to the invention may be regarded as a dual-purpose article.In an alternative embodiment, which may not be quite so advantageous, the end of a pipe may be formed with circumferential grooves at its internal cylindrical surface and a corresponding coupling or other fitting formed with matching ribs at its outer surface. In these circumstances the end of the pipe will have to be expanded by heat to enable the elements to be inserted one within the other.It will also be understood that each of the pipe elements of a combination may comprise a pipe and thus two pipes may be joined one inside the other by the method without the use of a coupling, provided that the outer pipes is thermally expandable.

Claims1. A method of joining members comprising first and second pipe elements of which one member is of thermally expansible material and has an internal cylindrical surface of diameter generally corresponding to the diameter of the cylindrical external surface of the other member, wherein one of said surfaces has at least one circumferential groove therein and the other of said surfaces at least one matching circumferential rib projecting outwardly therefrom, the method comprising expanding the said one member to an extent dependent on the outward extension of said rib or ribs by heating below its melting point to enable one of said members to enter the other beyond the rib or ribs, assembling the members one within the other, with the or each rib in register with a corresponding groove, and allowing the expansible member to contract by cooling on to the other member so that the or each rib engages in a corresponding groove.2. A method as claimed in Claim 1 wherein there is a plurality of spaced grooves and matching ribs.3. A method as claimed in Claim 1 wherein the grooves and ribs are of ratchet-like configura ion.4. A method as claimed in Claim 1 wherein a sealing and/or sliding agent is applied to at least one of said surfaces 5. A method as claimed in any one of claims 1, 2, 3 or 4 wherein the said one member is expanded to such an extent that the other member can enter it only by elastic deformation of the said rib or ribs.6. A pipe element (9) having an internal cylindrical surface of a predetermined diameter, for combination with a further pipe element (2) having a cylindrical external surface of corresponding diameter which external surface has at least one circumferential groove (4) therein or at least one circumferential rib projecting outwardly therefrom, characterised in that said pipe element is provided εt its internal surface with a circumferential rib (14) or groove matching the or each groove or rib, respectively, of the said further pipe element (2) and that said pipe element (9) is made of material having such a coefficient of thermal expansion that it can be expanded by heating below its melting point to such an extent that said further pipe element (2) is able to enter it beyond the rib or ribs (14) so that on contraction the or each rib (14) can engage in a corresponding groove (4) .7. A pipe element as claimed in Claim 6 having a plurality of spaced grooves or ribs.8. A pipe element as claimed in Claim 6 or Claim 7 wherein the cr each groove or rib is of ratchet-like configuration.9. A combination of members comprising first and second pipe elements characterised in that one member has an internal cylindrical surface of diameter generally corresponding to the diameter of the cylindrical external surface of the other member when both members are at the same temperature, one of said surfaces has at least one circumferential groove therein and the other of said surfaces has at least one matching circumferential rib projecting outwardly there¬ from, and the said one member is made of material having such a co-efficient of thermal expansion that it can be expanded by heating below its melting point to such an extent that the one of said members is able to enter the other beyond the rib or ribs so that on contraction of said one member the or each rib can engage in a corresponding groove.

ADVANCED CHEM EQUIP LTD; ADVANCED CHEMICAL EQUIPMENT LTD

ARMITAGE ARTHUR

WO-1978000007-A1

WO

A1

EN

new

F02D11

F02M47, F02M63

F02M 47/02D, F02M 63/02C, R02B 275/14

DIRECT INJECTION FUEL SYSTEM

Injection pressure generated by a suitable flow source (16) and a pressure-flow regulator (28) is carried by a common rail or manifold (20) to each injector valve of an engine. The valves (22) are of the closed differential needle, hydraulic-operated type, opening and closing for the injection period by virtue of hydraulic pressure imbalance and balance exerted on the effective piston areas of the valve needle. Balance conditions are controlled by fuel flow through ports and orifices (72, 74, 78, 102) of electric solenoid-operated sliding spool valves (52) by an engine-driven timer device (38, 40) which controls the start and end of the injection period. Controlled by-pass flow from the spool valves (52) may be collected by a low pressure manifold for return to the reservoir along with the overflow from a high pressure manifold (20).

DIRECT FUEL INJECTION SYSTEM Technical FieldThis invention relates to control of fuel injection in internal combustion engines, especially diesel. More particularly, it relates to a common-rail, closed dif¬ ferential needle, hydraulically operated injection valve system for fuel flow control.Background Art U.S.- Patent No. 3.537,547, which I will refer to hereinafter as the AMBAC system, employs a common rail for operation of a diesel engine. Two pumps are required, one a high pressure pump for operating a type of hydraul¬ ic ram which acts on fuel supplied by the other, a low- pressure pump. Fluid from the high pressure pump is not injected into the engine. In the AMBAC system, the fuel is delivered to the injection valves at an injection pres¬ sure equal to the pressure in the common rail. The fuel delivery from the low pressure pump to the ram is init¬ ially mechanically timed from the engine, and initially metered by adjustment of the low pressure pump. Final metering of fuel into the engine is determined by con¬ trolling the length of the injection period, this being accomplished by the high pressure as it varies the en¬ gine speed. As speed and pressure increase; injection duration decreases the so-called torque control. These timing and metering adjustments are critical and high¬ ly complicated. They require use of an expensive pump test stand which can be handled only by special tech¬ nicians.The prior art AMBAC solenoid is single wound and acts electrically in only one direction, return action being by spring. It can be used only on signal to be¬ gin an injection period, apparently playing no part in the duration. The single-wound solenoid operates through a diaphragm and push rod to open or unseat a ball-type check valve.The prior art AMBAC system also employs an hydraul¬ ic imbalance-operated valve, the imbalance being created by the solenoid-operated check on the valves. It is used to control high pressure from a high pressure common rail system to operate a hydraulic ram which forces fuel from the fuel source system into the injection valve for injection into the engine. This valve in itself Is non-adjustable, and in itself cannot control final me¬ tering or duration, this function being performed by the pressure variations in the high pressure system.Therefore, in view of the Inadequacies of the prior art AMBAC system as set out in aforesaid U.S. Patent No. 3,587,547, development of a simple, uncomplicated sys¬ tem for injecting diesel fuel to an engine at the right time and In the right quantity to obtain peak power without an undue amount of pollution represents a high¬ ly desirable result. Furthermore, there is a need for such an improved fuel injection system which does not require the expensive percussion-built injection pumps now in use and one which will permit manufacture and use of economic diesel passenger cars at substantial saving of fuel and improved pollution control.Disclosure of the Invention After extended investigation I have developed just such an improved fuel injection system, particular¬ ly useful for diesel engines.In its broader aspects my invention involves a single-pump fuel injection system In which the pump is of the positive displacement type capable of pro¬ viding sufficient cooling flow against the required rel¬ atively high pressure suitable for proper Injection. The pump of my system may be driven by an associated engine or by other means.According to my invention, a common rail manifold connected to the pump discharge is also joined to a plurality of injection valve assemblies and pressur¬ ized to injection pressure by a pressure-regulating relief valve located at the manifold end opposite the inlet. Overflow from this valve may be piped back to a reservoir. Equal pressure is employed at each valve inlet, with minimum injection lag resulting.The injection valves of the system of the invention are of the closed, differential needle, hydraulic-op¬ erated type, modified according to the invention so that they may be both opened and closed by hydraulic pres¬ sure. This modification makes the spring chamber func¬ tion as a pressure chamber. The injection valve spring helps close the valve at the end of injection. Adjust¬ ments may be made to obtain the proper rate of inject¬ ion and valve balance for best efficiency.An important feature of my invention comprises electrically operated sliding spool valves which cause the mechanical motion of the injection valve needle by controlling the hydraulic pressure balance conditions exerted on the valve needle. Each of the spool valves of the invention consists of two sections, the spool having three lands and two undercut sections. One sec¬ tion controls a by-pass flow from the spring chamber of the injection valve by opening or closing a port leading to a by-pass manifold. The other section re¬ ceives injection pressure from the high pressure system and passes it through a combination port-orifice into the injection valve spring chamber. In the non-inject position, the by-pass port of the first section remains open, permitting flow from the spring chamber, and the port-orifice is in the orifice condition by means of the spool land forming a restriction. Flow through this orifice causes a pressure drop in the spring chamber and allows injection pressure on the valve needle to open the valve for injection.One advantage of my invention is the possibility of using a common low pressure by-pass manifold to re¬ ceive fuel by-passed by the spool valve and connect with the overflow return line from the high-pressure mani¬ fold. Double-wound solenoids may be employed to actuate the spool valve spools in both directions. Solenoid plungers may be used as extensions of the valve spools and equipped so as to hold the spools In their shifted positions. Also, by means of a travel adjustment, spool travel may be set, acting as an orifice size adjustment and rate of injection adjustment. The two oppositely wound solenoid coils may be terminated at three exter¬ ior connectors in such a way as to provide positive bi¬ directional valve spool motions as each coil may be commonly connected to one of three terminals, and this terminal connected by wiring to a suitable electric power source through an on-off control switch. The other two ends of the two coils may be separately connected to the other two terminals, and these terminals connect¬ ed by wiring to proper respective terminals on a timer.According to my invention the preferred timer de¬ vice is mechanically driven by and timed to the engine of my injection system and includes two sets of contacts mounted on suitable bases, with one set to control start of injection and the other to control the end of injection. Each set contains a separate contact for each Injection valve of the engine, and these contacts are connected by wiring to corresponding terminals on the aforesaid solenoids. Included may be a rotating con¬ tact or brush for use in energizing the solenoids in se¬ quence.One set of contacts amy be made variable in relation to the other set so that the length of the injection period may be varied, thereby achieving control of me¬ tering and engine speed.Normal shutdown may be accomplished by an on/off switch.Emergency shutdown may be accomplished by a manual control on a pressure relief valve to dump off the in¬ jection pressure in the high pressure manifold.According to my invention I prefer to use a var¬ iable speed type governor to throttle the engine. This governor employs a fulcrum lever to articulate a mov¬ able contact disc in a timer. The governor is thus en¬ abled to read the engine speed and automatically set the fuel delivery for the particular engine speed read. This, especially when combined with my system of meter¬ ing, which is accomplished by electrical control of duration of injection, permits the air-fuel ratio to be strictly and easily adjusted on the engine inframe at any and all engine RPM points by matching the fuel delivery curve to a volumetric efficiency curve, there¬ by insuring peak torque with a minimum of pollutants and substantially no smoke. signal source 118 Includes as basic components there¬ of a rotatable contact plate 120, for injection dura¬ tion control, a grounding bush rotor 122 and a stat¬ ionery contact plate 124 timed to the engine.In the timer-governor of Fig 5 the setting of throttle 108 controls the operation of the governor. The brushes complete the circuit to open the coil in the solenoids such as the one depicted in Figs 2 and 3. One set of double windings (64 of Figs 2 and 3) is to pull the valve into position. The stationary contact plate 124, which is timed to the engine via the cam¬ shaft gives a constant beginning of injection by pull¬ ing the valve to open the port or a constant ending by pushing the valve to close the port. The other plate 120, rotatable, lags behind. When the amount of fuel needed by the engine is injected as dictated by the gov¬ ernor throttle, a second brush contacts the other plate and de-energizes the opposing set of windings, causing the solenoid to go in the other direction. Contact plates 120 and 124 are adjustable at the initial timing.It can be readily seen from the foregoing descrip¬ tion that my fuel injection system, by providing control of pressure by a spool valve-solenoid arrangement, elim¬ inates a leak-off chamber and permits improved fuel in¬ jection or delivery and obtains optimum efficiency by better control of fuel-air ratio. Constant high pressure rail and manifold system such as depicted in Fig 1 which employs a single high pressure pump for both pressure and fuel delivery. The spool valve-solenoid arrangement such as shown in Fig 4 controls the pressure so that the high pressure source is tapped off, with the spool valve, which is electrically controlled by the solenoid, going down as pressure comes in via lower lines 98 and 78 and then back through by-pass inlet port 76 and line 96 into chamber 86 as by-pass outlet port 74 connected to by¬ pass manifold 32 of Fig 1 is closed. By-pass outlet port 74 is opened when the orifice formed near 80 becomes o- pen as the spool valves turn and go up, thus providing an exit for pressure in the injection valve, as In Fig 4, thereby dropping the pressure therein so that the constant high pressure opens the valve and injects fuel to the engine exactly as needed in a controlled manner as the needle valve 94 moves.Following are several features or advantages of the fuel injection system of the invention.1. A single high pressure pump or fuel to be in¬ jected and an injection pressure which is set and con¬ trolled by a compound pressure-regulating valve where¬ by excess may be spilled back to a tank. No adjustment of the pump is necessary, the injection pressure being adjustable by the regulatory valves.2. An impulse source to begin and end injections, the duration being variable by a movable set of contacts. Beginning and ending of injection may be either constant- variable or vice-versa.3. Hail pressure is dictated by setting a compound pressure relief valve. 4. A double wound solenoid enables positive elec¬ trical action in either of both directions upon sig¬ nals for a definite beginning and ending of the injec¬ tion period. It is mechanically connected to and op¬ erates an associated spool valve.5. An electrically operated solenoid valve with two sections or chambers. One section starts or stops fuel flow into a by-pass manifold, and the second sec¬ tion restricts or opens an orifice, creating a pressure drop or pressure balance on an Injection valve needle, thereby opening and closing it for injection. Because the valve spool travel is adjustable, it regulates the size of the orifice, the rate of pressure drop, the valve opening and the rate of injection.6. Capability of obtaining an optimum fuel air ratio (20:1 running) for a maximum 90% volume efficiency. Since conventional intake manifolds have no butterfly controls, the amount of air in the engine cuts back as the RPM increases. Since the fuel curve increases as the air curve increases, on accelerating, the engine fuel delivery must be cut back to between the torque peak and the hp peak. This can be done according to my invention by use of the nozzle valve being operated di¬ rectly hydraulically.While the invention has been described in terms of preferred embodiments, the claims appended hereto are intended to encompass all embodiments which fall with¬ in the spirit of the invention.

Having thus described my invention and certain pre¬ ferred embodiments thereof, I claim:1. In a fuel injection system an electrically operated spool valve device comprising in cooperative association a spool valve, a double-wound solenoid adapted to oper¬ ate said valve, an orifice adapted to be opened when the spool valve turns and moves upward, a by-pass port a- dapted to be opened when the spool valve turns and moves up, and entering and exiting channels adapted to be con¬ nected to an injection valve.2. The spool valve device of Claim 1 in cooperative as¬ sociation with at least one additional spool valve de¬ vice of the same structure in common manifold alignment.3. The spool valve device of Claim 2 in cooperative as¬ sociation with a governor, timer, pressure pump and in¬ jection valve.4. In a fuel injection system an Injection valve com¬ prising a high pressure inlet, a high-low pressure cham¬ ber, a nozzle body, a wall, an injection pressure cham¬ ber, a needle valve positioned at the end of said in¬ jection valve opposite said high pressure inlet, and lines adapted for releasing pressure from said inject¬ ion valve and returning pressure thereto.5. The injection valve of Claim 4 in cooperative as¬ sociation with a solenoid-operated spool valve where¬ by the pressure In said injection valve may be controlled. 6. The injection valve of Claim 5 wherein the solenoid- operated spool valve comprises the spool valve device of Claim 1.7. The injection valve of Claim 4 in cooperative assoc¬ iation with a governor, timer, pressure pump, common rail manifold and solenoid-operated spool valves and fuel source.8. A direct injection fuel system comprising in cooper¬ ative association a governor-timer, a single high pres¬ sure pump adapted to supply and distribute fuel at a controlled pressure and amount to an engine, and a com¬ mon rail manifold in association with a plurality of injection valves connected to corresponding solenoid- operated spool valves adapted to regulate the pressure in said injection valves.9. The system of Claim 8 wherein the governor-timer comprises a governor comprising a throttle, fulcrum lever, peak fuel adjuster, air-fuel ratio adjuster, an RPM reader, and, in association with said governor, a timer comprising a rotatable contact plate for injection duration control, a grounding brush rotor and a sta¬ tionary contact plate adapted to be timed to an engine.10. A process for controlling fuel-air ratio and pressure injection of fuel into an internal combustion engine which comprises generating injection pressure by a high pressure pump and a pressure-flow regulator valve, carry¬ ing same along with fuel by a common rail manifold to a plurality of needle valves in hydraulically operated in¬ jection valves, controlling fuel flow in said valves through pressure ports and orifices to and from a corres¬ ponding plurality of solenoid-operated sliding spool valves and employing a governor-timer to control, a- long with said spool valves, the starting and ending of the injection of fuel into said internal combustion en¬ gine. Having thus described my invention and certain preferred embodiments thereof, I claim:1. In a fuel injection system an electrically operated spool valve device comprising in cooperative association a reciprocating action spool valve operated by a double-wound solenoid and an Injection valve having two matching passages therebetween, apressure differential orifice created when, in operation, the spool moves from a non-inject to an inject position, said orifice adapted to be created when the spool valve moves upward, a by-pass port adapted to be opened when the spool valve moves upward, and entering and exiting channels.2. The spool valve device of Claim 1 in cooperative as¬ sociation with at least one additional spool valve device of the same structure in common manifold alignment.3. The spool valve device of Claim 2 in in cooperative as¬ sociation with a governor, timer, pressure pump and injection valve.4. In a fuel injection system an injection valve com¬ prising a high pressure inlet, a high-low pressure chamber, a nozzle body, a wall, an injection pressure chamber, a needle valve positioned at the end of said injection valve opposite said high pressure inlet, and interconnecting passages be¬ tween said injection valve and a reciprocating action spool valve operated by a double-wound solenoid, said passages adapted for releasing pressure from said injection valve and returning pressure thereto.5. The injection valve of Clain 4 in cooperative as¬ sociation with a solenoid-operated spool valve whereby the pressure in said injection valve may be controlled. 6. The injection valve of Claim 5 wherein the solenoid- operated spool valve comprises the spool valve device of Claim 1.7. The injection valve of Claim 4 in cooperative as¬ sociation with a governor, timer, pressure pump, common rail manifold and solenoid-operated spool valves and fuel .source.8. A direct injection fuel system comprising in cooper¬ ative association a speed governor which comprises a throttle and a fuel adjuster, a timer-made up of a rotatable contact plate for injection duration control, a grounding brush rotor and a stationary contact plate adapted to be timed to an engine, a single high pressure pump, adapted to supply and distribute fuel at a controlled pressure and amount to an engine, and a common rail manifold in association with a plurality of in¬ jection valves connected to corresponding solenoid-operated spool valves adapted to regulate the pressure in said injection valves.10. A process for controlling fuel-air ratio and pres¬ sure injection of fuel into an internal-combustion engine which comprises generating injection pressure by a high pres¬ sure pump and a pressure-flow regulator valve, carrying same along with a fuel by a common rail manifold to a plurality of needle valves in hydraulically operated injection valves, con¬ trolling fuel flow in said valves by means of a plurality of solenoid-operated sliding spool valves having pressure dif¬ ferential orifices created when the spools move from a non- inject to an inject position and employing a governor-timer to control, along with said spool valves, the starting and ending of the injection of fuel into said Internal combustion engine . STATEMENT UNDER ARTICLE 19STATEMENT EXPLAINING THE AMENDMENT AND DRAWING ATTENTION TO THE DIFFERENNCE BETWEEN THE REPLACED SHEETS AND THE REPLACEMENT SHEETSClaim 1 of replacement sheet 12 has been amended to make clear that(1) Applicant's spool valve is a reciprocating-action valve 24 operated by a double-wound solenoid 26, (2) The two principal parts (of which there may be a series) of Applicant's feed value system are the spool valve24 and the injection valve 22, which have two matching pas¬ sages 76, 96 and 78, 98 between them, as depicted in Fig. 4 in detail, and(3) The orifice near 80 Is a pressure-differential ori¬ fice created when the spool moves from a non-inject to an inject position (sheet 10, lines 1-15)In Claim 4 of replacement sheet 12 it is now specified, as with respect to Claim 1, that Applicant's valve 24 is a double-wound solenoid 26 and that there are interconnecting passages 76, 96 and 78,98 between the spool valve 24 and the injection valve 22 (sheet 10, lines 1-15).On replacement sheet 13 Claim 9 has been combined with Claim 8 to specify that Applicant's speed governor 106 (sheet 8, fourth to last line) is made up basically of a throttle 108 and a fuel adjuster 114 and that his timer 118 comprises a rotatable contact plate 120 for injection duration control (line 2, sheet 9), a grounding brush rotor 122 (line 3, sheet 9) and stationary contact plate 124 (line 4, sheet 9) adapted to be timed to an engine.Claim 10 bridging sheets 13 and 14 has been amended on replacements sheets 13 and 14 to specify how Applicant's solenoid-operated sliding spool valves have a pressure dif¬ ferential orifice created, as. explained hereinabove and in Applicant's specification, when the spool moves from a non- inject to an inject position (lines 1-15 - sheet 10). Please note in this respect Applicant's remarks hereinabove in con¬ nection with the changes made in Claim 1 on replacement sheet 12.

PFEIFFER W M

PFEIFFER W M

WO-1978000009-A1

WO

A1

XX

new

E03D9

B01D23, B63B29, E03D11, C02C1

E03D11

E03D 11/11

NON-POLLUTING TOILET SYSTEM

A toilet system capable of rendering the effluent innocuous and reducing the solid matter therein to microparticle size comprising a reversible, motor-driven pump (56) and a two-position valve (58) operable, on the one hand, for taking water into the system for flushing effluent from the bowl (10) into a treating chamber (12) and, on the other hand, to empty the treating chamber and discharge the effluent from the system so that both the pump and the valve are self-purging. There is a two-position switch (S3) for reversing the motor-driven pump and a valve rod (80, 82) for moving the two-position valve from one position to the other. A motor-driven macerator (54) in the treating chamber provides for effecting maceration of the effluent flushed into the treating chamber. A bacteriacide may be employed to render the effluent innocuous. The macerator is operable independently of the motor-driven pump so that the system can be purged without simultaneous operation of the macerator.

Non-Polluting Toilet System There is need for a non-polluting toilet system for marine use, recreational vehicles, mobile homes, vacation homes, construction sites, trains, planes and the like, regardless of whether or not sewer facilities are available. Chemical and incinerator-type toilet systems have been developed to meet the aforesaid means. However, such systems as have been developed have in common been unable to meet the good health and sanitary requirements and/or the federal standards with respect to decontamination and/or reduction in particle size or have not been sufficiently non- polluting as far as disease-causing bacteria are con¬ cerned; and have required extensive plumbing, holding tanks, pumps, valves and the like which are difficult to keep sufficiently clean to eliminate odor and which form a harbor for the development of bacteria. The objective sought herein was to design a system which would reduce the bacteria to zero or virtually zero coliform bacteria count and to reduce the solid content to microparticle size below any presently available system. Also, a system so designed as to simplify the plumbing, provide pump and valve components which are self-purging so as to eliminate the last vestige of odor and bacterial contamination, and the unpleasant duty of having to disassemble pumps, valves and the like in the system for cleaning. SUMMARY OF IN ENTION As herein illustrated, the toilet system comprises a bowl, a reversible motor-driven pump operable in one direction to supply flush water to the bowl to flush the same, a single treating chamber for receiving effluent flushed from the bowl, means for supplying a bacteriacide to the treating chamber and a macerator in the treating chamber for reducing the solid content to microparticle size. The macera- tion is effected in isolation from any other fluid. Valve means operable in one position to cause the' pump to effect flushing of the effluent from the bowl into the treating chamber and in the other position to discharge the treated effluent from the chamber provides for purging the system. There is a control circuit including switch means for reversing the motor-driven pump, switch means for initiating operation of the macerator motor, a timer for terminating operation of the macerator motor and manually or electrically- operable means for shifting the position of the valve. The treating chamber is of a predetermined capacity such as to receive a predetermined volume of effluent for treatment and the pump is designed to discharge the entire amount of the treated effluent from the treating chamber and terminate the macerating cycle.Alternatively, the system may be provided with two motor-driven pumps, one for delivering water to the bowl to effect flushing and the other to withdraw the treated effluent from the treating tank and discharging it, When a two-pump system is employed, a filtering assembly may be included so that the system becomes a closed loop wherein a predetermined quantity of water may be used repeatedly, thus to economize on the use of water. The invention will now be described in greater detail with reference to the accompanying drawings, wherein: FIG. 1 is a plan view of the toilet structure;FIG. 2 is an elevation taken from the left- hand side of FIG. 1;FIG. 3 is an elevation taken at the rear side of FIG. 1;FIG. 4 is a vertical section taken on the line 4-4 of FIG. 1;FIG. 5 is a fragmentary section taken on the line 5-5 of FIG. 4; FIG. 6 is a plan view partly in section of the motor-driven pump and valve assembly;FIG. 7 is a section taken on the line 7-7 of FIG. 6;FIG. 8 is a section of a modified form of the valve assembly;FIG. 9 is a wiring diagram of the control for operating the system; andFIG. 10 is a block diagram of the control for operating the system. FIG. 11 is an elevation of an alternative toilet structure wherein two motor-driven pumps are used;FIG. 12 is a plan view of the two motor- driven pumps; FIG. 13 is a block diagram of the control when using two pumps;FIG. 14 is an elevation of a filtering unit for use in connecting the system to a closed circuit; and FIG. 15 is a view similar to FIG. 6 showing an alternative valve assembly;FIG. 16 is an elevation partly in section of one of the valve components of the valve assembly shown in FIG. 15; andFIG. 17 is a section taken on the line 17-17 of FIG. 16. Referring to FIGS. 2 and 4, the toilet as herein illustrated comprises essentially a bowl 10,. a treating chamber 12 containing a macerator 14 and a combination pump and valve assembly 16, FIGS. 6 and 7, connected by suitable plumbing to the bowl and to the treating chamber in such a way as to enable delivering flush water to the bowl for flushing the effluent therefrom into the treating chamber and, after macera¬ tion has been accomplished, discharging the effluent from the system.The bowl 10 as shown in FIGS. 1 and 4 is of generally oval cross section and is provided at its rear end with an integral extension 18 and an upwardly inclined control panel 20 upon which are mounted switch means and indicators which enable conveniently initia¬ ting the flushing operation and/or the cleaning opera¬ tion and of determining at any time the condition of the apparatus. The upper or rim of the bowl 10 is provided with a downturned skirt 22 which extends all the way around and along the opposite sides of the extension and the panel to afford an attractive appear¬ ance. A seat 24 is mounted atop the bowl in conven¬ tional fashion and is provided for this purpose at its rear end with transversely spaced holes 26-26 for receiving hinge means for pivotally connecting the seat to the bowl. The lower end of the bowl, FIG. 4, has a centrally located opening 25 defined by an annular26.1 flange 2-6 which seats against a cover plate 30 at the top of the treating chamber 12. The plate 30 contains an opening 32 through which the effluent can be flushed into the treating chamber. A combination gasket and splash guard 27 is provided between the bowl and the treating chamber to provide a watertight joint and to prevent splash of the effluent during maceration up¬ wardly into the bowl.The treating chamber.12 is of generally cylindrical cross section at the lower part, having a side wall 34, FIG. 4, which is generally perpendicular to the bottom, except for one side, the forward side, which has an upwardly and forwardly divergent wall 36. The bottom wall 38 is of annular configuration and has at its center a step bearing 40. Near the bottom, at the side substantially opposite the forwardly divergent wall 36, there is a discharge port 42, FIGS. 4 and 5.The annular, hemitoroidal shape at the bottom is likeUnited States that in application/Serial No. 610,097, filed September4, 1975, for HYDRAULIC ATTRITION UNIT FOR MARINE now United States Patent 4,054,519 TOILETS /and provides in conjunction with the macerator blade an especially effective means for beating paper stock into its constituent fibers.The macerator 14 is mounted within the treat- ing chamber 12 in a housing 44, FIG. 4, provided .with a flange 46 at its top by means of which it is attached to the cover plate 30 within an opening 47. The housing 44 is of sufficient size to receive the macerator motor Ml and is provided in its lower part with a horizontal bottom part 48 to which the motor housing can be bolted. The lower part also contains a central bearing 50 for rotatably and sealably receiving the motor shaft 52, to the lower end of which is fixed the macerator blade 54. Desirably, the shaft 52 extends beyond the blade for en¬ gagement with the step bearing 40. The macerator blade 54 is of the kind disclosedUnited States Patent 4,054,519 in the aforesaid peHding-applieatien and as described herein is designed to effect maceration by causing impact of the particles of the effluent with each other rather than a shearing action such as is commonly used by others for effecting the communition of solid material. The specific reason for using a macerator of this kind rather than a shearing type of cutter is that the effluent con¬ tains a large proportion of paper which a shearing blade will not cut through and which requires repeated pounding and recirculation to break it down into its constituent fibers. A cutting blade merely collects the fibers and becomes choked with the fibers so that its efficiency and effectiveness is reduced to uselessness in a very short period of time. The combination pump and control valve assembly16, FIGS. 6 and 7, comprises, as shown, a motor-driven pump 56 and a selector valve 58. The motor-driven pump is mounted at the rear side of the treating chamber 12 and comprises a pump block 60 bolted to the supporting plate or foot plate of the toilet and a motor M2 superimposed upon the block and bolted thereto with its drive shaft 62 extending perpendicularly downwardly therefrom through suitable bearings into a pump chamber 64 in the block 60. An impeller 66 is keyed to the shaft 62 in the pump chamber 64. The pump chamber 64 contains two ports 68 and 70. The motor M2 is reversible so that by effecting rota¬ tion of the pump in one direction, the port 68 will be an intake port and the port 70 will be a discharge port and by effecting rotation of the pump in the opposite direc¬ tion, the port 68 will be a discharge port and the port 70 an intake port.The selector valve 58, FIG. 7, comprises a valve housing 72 containing a vertically arranged valve chamber 74 in which there is slidably mounted a valve spool 76, the upper end of which is connected to the lower end of a spindle 77 which extends through suitable packing 78. The protruding end of the spindle 77 is connected to the lower end of a plunger rod 80 which extends upwardly from the18 valve assembly through the horizontal extension 17 of the bowl so as to be located forwardly of the panel 20. A82 knob'2-Θ at the upper end of the rod provides means which may be grasped to move it upwardly and downwardly. The valve spool contains ports 84 and 96. When the port 84 is brought into alignment with.the port 70 and the pump is rotated in the proper direction, the water will be drawn into the system through the port 68 and delivered through a coupling 88 and conductor 90 into the bowl for flushing the latter. The valve housing 72 is provided with a port 92 which is connected by a pipe 94 to the port 42 in the treating chamber so that when the valve spool is moved to align the port 96 with the port 92 and the pump is reversed the effluent will be withdrawn from the treating chamber and discharged. The selector valve 58 may, as stated above, be manually actuated by lifting and depressing the rod 80. However, as shown in FIG. 8, it may be automatically actuated by means of a solenoid SOL connected to the upper end of the spindle 77.The system is controlled partly through manually operable switches and partly automatically as follows, FIGS. 9 and 10: Referring to FIGS. 1, 9 and 10, there is mounted on the panel 18 a two-position switch S3 which, in one position, effects flushing and, in the other position, discharge. Power is supplied to the system through a cir¬ cuit breaker 102 and when the power is on, this fact is indicated by a white light W adjacent the circuit breaker. It is within the scope of the invention to automate the . entire cycle of operation.It is not only necessary to macerate the effluent, but also to effect decontamination and deodori- zation and, of course, the greater the amount of macera¬ tion and, hence, reduction in particle size, the greater is the effectiveness of the decontaminant and/or deodor¬ izer. A combination decontaminant and/or deodorizer is introduced into the system in suitable form, for example, the form of a tablet directly into the bowl and, for this4 purpose, there is provided, as shown in FIG. 1, at the rear end of the toilet seat, a slot 106 through which the tablet may be dropped. At the underside of the seat adjacent the opening 106, FIG. 4, there is a recess 108 within which there is mounted a switch assembly SI provided at its forward end with an actuator finger 112 which extends into the opening 106 and, when deflected, by dropping the table through the slot 106, will complete a circuit through the switch to start the motor Ml of the macerator. Desirably, the switch-actuating finger 112 is set so that a predetermined force is required to effect its displacement and the tablets are made strong enough to effect such displacement so that a tablet not specifi¬ cally made for this purpose will not actuate the switch and, hence, will not start the macerator. Instead of the switch SI, a sensing device of well-known kind such as a magnetic switch, photocells, proximity switch, microswitch, reed switch or the like may be used operable by, or in response to, the size, shape, hardness, color or embossment of the bacteriacide. The bacteriacide itself may be a tablet, cartridge, capsule, powder or liquid.It is within the scope of the invention to in¬ troduce the bacteriacide into the effluent prior to or after its maceration, for example, it may, as described above, be deposited in the bowl and flushed together with the effluent into the treating chamber, or it may be in¬ jected directly into the treating chamber, for example, by squirting a charge of bacteriacide directly into the treating chamber each time the bowl is flushed or the macerator is started. It is foreseen that a multiplicity of toilet systems such as described may be used in apart¬ ment-type dwelling units, might be connected by suitable plumbing to a common holding tank or discharge tank so that the macerated effluent from the entire building could be temporarily held where, for example, there is not an available sewage system, and where, for example, it is not desirable to have individual holding tanks for each unit. Such a system would eliminate the responsibility of the individual to introduce the bacteriacide into the toilet, shifting the obligation to the building manager or some other responsible person, thus making it a more foolproof system of disposal without accidental contamination through the carelessness of individual users. The effluent so collected may be recoverable as a liquid or solid, for example, by evaporation of the liquid for fertilization purposes.A large proportion, of the effluent, of course, is paper which is not valuable as a fertilizer and, fur- theimore, tends to clog plumbing. Hence, it is desirable to remove this bulk paper fiber from the treated effluent. This can be done by inserting a filter unit between the discharge side of the toilet system and the waste pipe leading to the holding tank or to the sewer system. Desirably, such a unit should be designed to be expendable so that when it becomes filled, it can be removed and replaced by a new filter.The macerator is allowed to run for a predeter¬ mined length of time as determined by a timer T to effect complete decontamination and reduction of the effluent to a particle size which is acceptable and to a bacteria count which is acceptable, whereupon the switch S3 is changed over to the discharge position and, in this posi¬ tion, will start the motor M2 of the pump to rotate the pump in a direction to discharge the macerated effluent from the system. After having run the system through a cycle for the purpose of macerating the effluent and dis¬ charging it, the system can be cleaned of any residual effluent without reintroducing a chemical and without operation of the macerator by simply flipping the switch S3 first to the flush position and then to the discharge position to circulate fresh water through the system. This may be done two or three times so that the entire system is thoroughly cleaned and will contain no residual fluids which could result in a deposit when standing in the system and become a source of bacterial growth or unpleasant odor. Prior to depositing the chemical tablet, it is, of course, necessary to shift the selector valve 58 either mechanically or electronically to a depressed position to provide for taking water into the system and prior to discharge, that is, after the macerator has completed its function, the valve must be shifted by pulling the rod upwardly. At the right-hand side of the20 panel i8, FIG. 1, there is a white light W which in¬ dicates the power is on. At the left-hand side of the20 .panel 18, FIG. 1, there are two lights, an amber light A in the control circuit indicating that the system is in use and a red light R indicating the treating chamber is filled and should be emptied.The selector valve 58 as described above is mechanically or electrically operated. There may be substituted for this selector valve a check valve assembly 150, FIG. 15, containing passages 152 and 154. Passage 152 is connected to the passage 68 of the rever¬ sible motor-driven pump and the passage 154 is connected to the passage 70 of the reversible motor-driven pump. The passage 154 is, in turn, connected by a check valve 156 to the conductor 88 which leads to the bowl and by a check valve 158 to the conductor 94 which leads to the treating tank. The check valves 156 and 158 are so arranged that when the pump is rotating in a direction to draw water into the passage 152 and force it through the passage 154, it will flow through the check valve156 to the bov/l, but will be prevented from entering the conductor 94. When the pump is driven in the opposite direction, the check valve 158 will permit the treated effluent to be withdrawn from the treating tank and dis- charged by way of the passage 154 and the passage 152 while the check valve 156 will prevent entry of the88 effluent into the conductor 188 to the bowl. Since urine is sterile and contains no solid matter, operation of the macerator is not required nor is it necessary to introduce a bacteriacide. The system may be flushed and discharged simply by flipping the switch S3 first to the flush and then to the discharge. If the toggle switch were flipped to the flush position for flushing solid effluent without also starting the macerator motor, the system would instantly become in¬ operative since the conductor pipes and ports of the pump and valve are so small in diameter that they would not pass the effluent, hence, no harm can come of actuating the toggle switch to effect discharge in the event the macerator has not been operated or has become inoperative. The conductor pipes and parts are, for this purpose, approximately 7/16 inches in diameter.The system is made ready for use by closing a master switch S as shown in FIGS. 9 and.10. Closing the switch S energizes the white light W to indicate that the power is on. In order to flush the toilet, the toggle switch S3 is moved to a position to start the pump motor M2 and held in this position until the bowl is completely flushed into the treating chamber, whereupon it is moved back to its neutral, position and-the pump motor M2 stopped. After flushing, a tablet is forced through the slot 106 and, as it passes through, it actuates the switch SI which starts the macerator motor Ml. A timer T in the macerator circuit is adapted, to be set to continue operation of the macerator for a pre¬ determined time and then to stop the macerator motor. When the macerator motor Ml stops, the amber, light A goes on. Following maceration, the toggle switch S3 is moved to a position to start the pump motor. M2 in the opposite direction and held in this position -until the treating chamber is empty, whereupon it is released and the motor M2 will stop. The circuit as thus arranged enables purging the system without operating the macerator by the simple expedient of holding the toggle switch in. the first position to charge flush water into, the treat¬ ing tank and then holding it in said second position to cause the water to be pumped out of the treating chamber. The valve 76 has to be moved in cons.onance with the pump motor to position it in a first position to admit flush water to the bowl for flushing and thereafter to a posi¬ tion to permit the effluent to be pumped out of the treating chamber when the switch is moved to the position to discharge the treating chamber. This may be effected80 by means of the push-pull rod ,82 or by a solenoid 96,FIG. 8. Desirably, both the push-pull rod and solenoid are included in the system, the push-pull rod serving as a backup in the event that, for some reason, the solenoid fails to operate. There is a red light R on the panel which goes on when the treating chamber is filled to indicate to the user that the chamber should be emptied before reuse. A float-operated switch S2 serves to close the circuit to the red light when the effluent in the treating chamber reaches a predetermined level.The system as described above is essentially of great simplicity as compared with most systems designed for the same purpose and is particularly attractive for the reason that its design frees the system from residual accumulations which may become the source of deposits within the system. This is provided by the reversible pump which is thus self-cleaning in operation and by employing a single selector valve through which the flush water reversibly flows. Efficiency in operation is achieved by disabling the macerator during the purging of the system. Further, as previously indicated, the macerator itself is especially effective in breaking up the solid material to a fineness to promote maximum decontamination and deodorization and the fact that the configuration of the macerating chamber and its isola¬ tion from the pump provides both ideal and maximum exposure of the effluent to the macerator. An alternative toilet system is shown in FIGS.11 and 12 wherein two motor-driven pumps 160 and 162 are used provided with motors M3 and M4. The motor-driven pump 160 as shown in FIG. 12 is provided with a fitting 166 for taking water into the system and a fitting 168 for receiving one end of a conductor 170, the other end of which is connected to the bowl 10. The pump 162 is provided with a fitting 172 which is connected by a conductor not shown to the treating tank 12 and a fitting 176 for connection to a discharge line not shown. The control circuit for the two-pump system is illustrated in FIG. 13 wherein there is a combination on/off circuit breaker switch S4 which, when placed in an on position, connects the circuit to a source of power comprising a battery so labeled. When the switch S4 is placed in the on position, a white light W1 is turned on to indicate that the power is on. A switch S5 in the circuit provides for, in one position, starting the motor M3 and its associated pump 160 to take water into the system and deliver it to the bowl for flushing. As in the previously described system, when the effluent has been flushed into the treating tank, the macerator therein is started by forcing a tablet through the slot provided for this purpose, whereupon the macerator runs for a predetermined period so as to effect complete maceration of the solid matter. During operation of the macerator, a red light R1 in the circuit is turned on to show that the macerator is running. When the macerator motor stops, the red light is extinguished, whereupon the switch S5 is moved in the other direction to the discharge position so as to start the motor M4 of the discharge pump 162 and thus discharge the treated effluent from the treating chamber to the discharge line. There are situations where there are restric- tions on the amount of water that is available and restrictions as to discharge and, for this reason, the system may be provided with a filtering unit as shown in FIG. 14 and the system closed. The filtering unit comprises a tank 180 divided by a partition 182 into two chambers 184 and 186. The chambers 184 and 186 are closed at the top by a cover 188 and are interconnected at the top by a conductor 190. The chamber 184 is filled with a plurality of particles . 192 which may be generally spherical in shape and which may be all of the same size or of different sizes. The particles 192 are buoyant and so will float on liquid delivered into the. chamber 184. These particles may be made of plastic and, desirably, have a somewhat roughened surface. A conductor19419-2- is mounted to the cover 188 with a portion extending into the chamber 184 to a position close to the bottom.196 194The upper projecting end/of the conductor 196 is connected to the discharge side of the pump 164 so that the macerated effluent withdrawn from the treating chamber is delivered into the chamber 184 near the bottom. As the effluent rises in the chamber 184, the solid matter is entrained by the particulate material so that the liquid at the top is substantially free of any solid matter. The filtering particles are sufficiently effec- tive so that the water is substantially clear at the top of the chamber 184 and this clear water flows by way of the conductor 190 into the chamber 186. A conductor 198 is mounted to the cover 188 with a portion extending down to near the bottom of the chamber 186 for withdraw- ing the clear water from the filter tank and returning.200 it to the system for flushing. The upper end/of the conductor 198 is connected to the intake side of the pump 160. Thus, there is provided a closed system wherein a predetermined quantity of water is circulated by the pump through the filter tank where the solid matter macerated by the macerator is trapped. The filter tank may be periodally cleaned either by removing the cover 188 and dumping out the filtering particles and replacing them or a drain valve may be provided at the bottom of the chamber 184 so that fresh water may be flushed through the bed of particulate material from the top to the bottom to clean the particulate material.As described hereinbefore, the flush water has been drawn into the system for flushing the bowl by a motor-driven pump and, for marine purposes, where the clean water which is to be used for the system is sea water, a pump is essential. It is very possible and contemplated within the scope of the invention to use the system in areas where the local water pressure is sufficient to supply water to the system without having to pump it and, accordingly, it is contemplated that the motor-driven intake pump may be dispensed with the con¬ ductor 172 connected directly to a domestic water pipe with a suitable valve such as normally used in any flush water and float control for shutting it off when a suffi¬ cient amount of water has been delivered to effect flush¬ ing.It should be understood that the present dis- closure is for the purpose of illustration only and in¬ cludes all modofications or improvements which fall within the scope of the appended claims.

1. A toilet system capable of rendering the effluent innocuous and reducing the solid matter therein to microparticle size comprising a bowl, a reversible, motor-driven pump operable in one direction to supply flush water to the bowl to flush the same, a treating chamber for receiving effluent flushed from the bowl for treatment, a macerator in the treating chamber for macerating the contents thereof in isolation from any other fluid and a two-position valve operable in one position to cause the pump to effect flushing of . the bowl and in the other position to effect dis¬ charge of the treated effluent.2. A toilet system capable of rendering the effluent innocuous and reducing the solidmatter therein to microparticle size comprising a bowl, a reversible, motor-driven pump, a treating chamber, valve means operable when the pump is rotated in one direction to take water into the system through a port and deliver it to the bowl to flush the latter and when the pump is rotated in the opposite direction to withdraw the effluent from the treating chamber and discharge it through the same port, macerator means in the treating chamber for macerating the effluent when flushed into the treating chamber and means for supplying a bacteriacide to the treating chamber. 3. A toilet system capable of rendering the effluent innocuous and reducing the solid matter therein to microparticle size comprising a bowl, a reversible, motor-driven pump, a treating chamber for receiving effluent flushed from the bowl thereinto, a macerator in the treating chamber operable to effect maceration of the effluent therein, means for supplying a bac¬ teriacide to the treating chamber so as to be present therein during the period of operation of the macerator, valve means movable to a position to con¬ nect the pump to the bowl for supplying flush water to the bowl to flush the effluent into the treating chamber and to another position to connect the pump to the treating chamber for discharging the treated effluent from the treating chamber and means for effecting rotation of the motor-driven pump in a direction to take water into the system when the valve is in the one position and in a direction to discharge the treated effluent from the system when the valve is in the other position.4. A toilet system according to claim 3 wherein there is a switch for reversing the motor-driven pump and means for shifting the valve.5. A toilet system according to claim 3 wherein a bac¬ teriacide is used to render the effluent innocuous during the maceration thereof and there is means operable by deposit of the bacteriacide in the bowl to automatically start the macerator. 6. A toilet system according to claim 5 wherein, the treating chamber is of a predetermined capacity such as to receive a predetermined volume of effluent for maceration in isolation and wherein the motor-driven pump is designed to discharge the entire amount of the treated effluent from the treating chamber.7. A toilet system according to claim 6 wherein there is means for terminating the treating cycle within a predetermined time.8. A toilet system according to claim 3 wherein there is a double-acting switch operable in one position to effect rotation of the motor-driven pump in the direction to take in flush water for cleaning the bowl and in the other position to discharge the cleaning water from the treating chamber without concurrent operation of the macerator.'9. A toilet system according to claim 3 wherein there is a slot for receiving and guiding a tablet into the bowl and a switch for initiating operation of the macerator provided with an actuating arm located in a position such that a tablet passing through the slot .will actuate the switch and thus initiate opera¬ tion of the macerator. 10. A toilet system comprising a bowl, a treating chamber to which the bowl is connected for receiving effluent from the bowl, a macerator in the treating chamber, a reversible, motor-driven pump, a two- position selector valve movable to one position to cause the pump in one direction of rotation to take water into the system and deliver it to the bowl to effect flushing and in the other position to cause the pump in the other direction of rotation to empty the treating chamber and discharge the effluent from the system, switch means for controlling the direc¬ tion of rotation of the motor-driven pump and means for changing the position of the two-position valve.11. A toilet system according to* claim 10 wherein the bowl is connected to the top of the treating chamber by way of a splash guard, and the treating chamber is emptied through a port at the bottom thereof.12. A toilet system according to claim 10 wherein the treating chamber is designed to contain the effluent in isolation during maceration and to be completely emptied following maceration.13. A toilet system according to claim 10 wherein the bottom of the treating chamber is toroidal in vertical and diametral section. 14. A toilet system according to claim 10 wherein-the macerator is motor-driven, there is means for receiving a tablet and conducting it into the bowl and a switch operable by receipt of the tablet to start the macerator motor.15. A toilet system comprising a bowl, treating chamber to which the bowl is connected for receiving effluent from the bowl, a motor-driven macerator in the treating chamber, a reversible motor-driven pump, a two-position selector valve movable to one position to cause the pump in one direction of rotation to take water into the system and deliver it to the bowl to effect flushing and in the other* position to cause the motor in the other direction of rotation to empty the treating chamber and discharge the effluent from the system, and a control circuit including a toggle switch operable in one position to actuate the pump motor to rotate in one direction and in the other in the. opposite direction, a solenoid connected to the two position valve operable by actuation of the toggle switch to move it to the - appropriate position for the direction of rotation of the pump motor, a switch actuatable upon entry of a bacteriacide into the treating chamber to start the macerator pump and a timer for. terminating opera¬ tion of the macerator pump following a predetermined interval. 16. A toilet system according to claim 15 wherein there is an ON-OFF switch for supplying power to the control circuit.17. A toilet system according to claim 15 wherein there is an indicator light which becomes illuminated when the ON-OFF switch is on, indicating that the power is on.18. A toilet system according to claim 15 wherein there is an IN-USE light operable when the macerator pump is in operation to indicate that the system is in use.19. A toilet system according to claim 15 wherein there is a FULL light operable when the level of the effluent in the treating chamber reaches a pre¬ determined level.20. A toilet system according to claim 15 wherein the pump is ported with 7/16 inch intake and discharge ports such as to completely block passages of any unmacerated solid matter. 21. A toilet system capable of rendering effluent innocuous and reducing the solid matter therein to a microparticle size comprising a bowl, a treating tank for receiving effluent flushed from the bowl for treatment, a macerator in the treating chamber for macerating the content thereof, means for in¬ troducing water to the bowl to effect flushing and for discharging the treated effluent from the treating chamber and a two-position switch operable in one position to effect initiation of water to the bowl and in the other position to effect dis¬ charge of the treated effluent from the treating chamber.22. A toilet system capable of rendering effluent innocuous and reducing the solid matter to micro¬ particle size comprising a bowl, a treating chamber for receiving the effluent flushed from the bowl for treatment, a macerator in the treating chamber for macerating the content thereof, motor-driven . pump means for supplying fresh water to the bowl to effect flushing and for discharging the treated effluent from the treating chamber following macera- tion and a two-position switch operable in one position to effect flushing and in the other position to effect discharge. 23. A toilet system capable of rendering the effluent innocuous and reducing solid matter therein to microparticle size comprising a bowl, a treating chamber for receiving effluent flushed from the bowl for treatment, a macerator in the treating chamber for macerating the contents thereof, first means for introducing water into the bowl, second means for discharging the treated effluent from the treating tank and filter means interposed between said first and second means such as to provide a closed circuit for repeated circulation of a predetermined quantity of liquid in the system.24. A toilet system.according to claim 23 wherein the filter comprises a tank containing a plurality of buoyant particles which float upon the disseminated effluent and wherein the first means delivers the disseminated effluent to the bottom of the tank and the second means removes the filtered water from the top of the tank.25. A toilet system according to claim 23 wherein the filter means comprises a tank divided into two chambers, one of which contains a mass of buoyant particles, conductor means connected to the first means for delivering the macerated effluent to said one chamber, a conductor connecting the top of the one chamber to the other chamber, and a conductor connecting the bottom of the other chamber to the second means. 26. A toilet system capable of rendering the effluent innocuous and reducing the solid material .therein to microparticle size comprising a bowl, .a treating tank for receiving effluent flushed f om the bowl . for treatment, a macerator in the treating chamber for macerating the contents thereof, a valve and conductor connecting the bowl to a source of water pressure operable to effect flushing of he bowl, a motor connected to the treating chamber for effect- ing discharge thereof and a two-position switch operable in one position to open the valve to effect flushing of the bowl and in the other position to energize the pump to effect discharge of the treating chamber.27. A toilet system capable of rendering the effluent innocuous and reducing the solid matter therein to microparticle size comprising a bowl, a treating chamber for receiving effluent flushed from the bowl for treatment, a macerator in the treating chamber for macerating the contents thereof, a motor-driven pump for supplying flush water to the bowl to effect flushing and for discharging the treated effluent from the treating chamber following maceration and a valve comprising a flow passage and two checks, one of which connects the flow passage to the bowl and the other of which connects the flow passage to the treating tank. 28. A toilet system capable of rendering effluent innocuous and reducing the solid matter therein to microparticle size comprising a bowl, a treating chamber for receiving effluent flushed from the bowl for treatment, a macerator in the treating chamber for macerating the contents thereof, a motor-driven pump for supplying flush water to the bowl to effect flushing and for discharging the treated effluent from the treating chamber following maceration and a valve containing two one-way gates, one of which is opened by operation of the pump in a direction to supply water to the bowl and the other of which is closed and the other of which is opened by operation of the pump in a direction to discharge the effluent from the treating chamber and the one is closed.

INT WATER SAVING SYST INC; INTERNATIONAL WATER SAVING SYSTEMS INC

ALBERTASSI J H; HEINZE W O

WO-1978000014-A1

WO

A1

EN

new

C02B9

E02B15

B63B35, E02B15

E02B 15/04C3

METHOD AND APPARATUS FOR OIL SKIMMING

Method and apparatus for removing oil from water surfaces including a self-propellable vessel having a catamaran type hull (10, 12) defining an oil collection channel (16) therebetween through which is advanced a series of loosely supported, parallel flexible rope belts (38) of floating oil collecting material which are moved countercurrent to the direction of vessel advance at substantially zero differential velocity relative to the water surface to pick up the oil on the surface. The rope belts (38) float freely on the water surface and are free to move vertically and longitudinally under the action of the water. Lateral deflection of the ropes under the action of debris or other obstruction is also possible. The free floating nature of the flexible belts (38) prevents adverse headwaves from being formed at their initial contact with the water surface and allows relatively high vessel speeds.

Method and Apparatus for.Oil Skimming Background of the Invention 1. Field of the InventionThis invention relates to a method and apparatus for remov¬ ing oil from a water surface and particularly to an improved method and apparatus for effecting the continuous removal and recovery of large quantities of oil from extended area water surfaces.2. General Background and Prior Art.Pollution of natural waterways and defining marginal land masses, such as harbors, rivers, lakes and defining shore lines and even open seas by oil floating on the water surface is of primary environmental significance. Recent years have witnessed ever increasing quantities of oil spillage from tanker or barge damage, drilling accidents, tank cleaning or other sources with attendant environmental damage to both land and water. Such has been accompanied by an ever increasing public concern both with the problem and with the apparent inability of current technology to ameliorate, much less to solve, the problem of large volume oil spillage.Although many expedients have been proposed for effecting the removal and collection of oil floating on water prior to adjacent land mass contamination, such as dispersion, skimming, absorbtion, burning and the like, such efforts have been gener¬ ally ineffective, at least insofar as oil spills of any large quantity and consequent areal size are concerned or where water surface turbulence of anything over minimal character is in¬ volved.Prior attempts at the design of skimmers, crafts which move throughout an oil slick and collect the oil therefrom, have pro¬ ved to have very limited effectiveness. An inherent problem with these devices is that they all present a rigid structure, usually in the form of a belt assembly with a rigid support, to the on¬ coming oil. When such a moving rigid structure is presented to an oil slick a headwave is formed in the oil near the structure. At very low relative velocities of the headwave becomes hydro- dynamically unstable. Studies have shown that at relative speeds in excess of approximately 1.25 knots the headwave breaks up, a entrained droplets of oil are swept past the oncoming structureStudies have also shown that this phenomenon occurs even the structure is provided with a continuously moving belt of o collecting material. Thus, a serious limitation of prior skimm designs has been that they can only operate at speeds of t order of 1 knot if they are to have any significant collecti efficiency at all.A further complication that has materially militated again prompt resolution of oil spill problems is the totally unpredic able nature of the causes thereof and the widespread geograph areas within which which such spills may occur. As a practic matter, the necessary time that passes between the initiation- an oil spill and the physical availablity of any collection mea at the locus thereof usually permits the spread of the spill oil over an area that far exceeds the ability of any present d techniques for collecting or otherwise handling the same. As corollary to the above, all problems attendant oil removal a markedly accelerated as the gallonage of the spill increase both with respect to the geograpic ' areas involved and wi respect to disposition of the collected oil itself.Prior patents of possible interest are cited below:PRIOR ART PATENTSU.S. Patent No. Patentee(s) Issue Date3,643,804 D. E. Sharpton 2/22/723,668,118 H. M. Rhodes 6/6/723,670,896 F. E. Hale, Jr. 6/20/723,744,257 W. F. Spanner 7/10/733,968,041 E. A. De Voss 7/6/764,061,569 J.A. Bennett, ETAL 12/6/77 General Discussion of the InventionThis invention may be briefly described as an improved me¬ thod and apparatus for removing oil from a water surface and which, in its preferred embodiment, includes a modularly asse b- lable, self-propellable catamaran type vessel defining a longi¬ tudinal oil collection channel of inverted U-shape. Large surface areas of oil collecting material for example, polypropylene, in the form of elongate endless belts or ropes are freely and loosely supported on the water surface to move therewith and are abvanced through the inverted U-shaped channel countercurrent to the direction of vessel advance and preferrably at a zero differential velocity relative to the water surface to maximixe oil collection. The preferred oil collecting material is polypro¬ pylene, formed in thin strips and radially disposed about a core belt or rope. Although oil collecting material in continuous flat wide belt or sheet form is possible and contemplated in the present invention, a series of independent rope belts is greatly preferred because it allows further freedom of movement in the lateral direction between the individual belts due to the presence of debris or other obstacles.Associated therewith and disposed upon a deck structure bridging the catamaran hulls are means for advancing the oil collecting material concurrently with the movement of the catama¬ ran vessel through the water and for removing the collected oil prior to the reintroduction of the material into the oil collec¬ tion channel. In its narrower aspects, the subject invention includes the conjoint usage of the catamaran hulls or sections thereof to temporarily store the oil removed from the water sur¬ faces.Among other advantages of the subject invention is the pro¬ vision of a self-propellable oil collection vessel that serves to maximize the collection of oil and the separation efficiency of the oil collecting material employed with respect to the quantity of oil exposed to collection and the time of explosable contact therebetween. Further advantages accrue in oil collection and efficiency when the multiple strip poypropylene ropes used. Still further advantages include provision of a collect method and apparatus that is effectively operative independent sea conditions both with respect to surface turbulence and to presence of floating debirs thereon. Still other advanta include the provision of increased oil storage facilities with detrimental diminution of oil collection efficiency and provision of a readilly assemblable modular structure that easily transportable for rapid assembly at the locus of intended use thereof^An object of this invention is the provision of impro method and apparatus for effecting the collection of oil from surface of water in calm waters as well as in relativ turbulent waters when needed and at relattively high speeds.Other objects and advantages of the subject invention w become apparent from the following specification and from appended drawings which illustrate, in accord with the mandate the patent statutes, a certain presently preferred embodiment oil collection apparatus embodying the principles of this inv tion. Brief Description of DrawingsFor a further understanding of the nature and objects of the present invention, reference should be had to the following detailed description, taken in conjunction with the accompanying drawings, in which like parts are given like reference numerals and wherein:Figure 1 is a schematic plan view of an improved oil collec¬ tion apparatus incorporating the principles of this invention.Figure 2 is a schematic side elevation of the apparatus illustrated in Figure 1; andFigure 3 is a vertical section as taken on the line 3-3 of Figure 1. Detailed Description of the Preferred EmbodimentReferring to the drawings there is provided a catamaran t vessel formed of a pair of elongate spaced hull sectio.ns 10, spanned by a deck section 14 suitably constituted, at least part, of metal grating or the like and supported by a plural of cross beams removably securable to the hull sections 10, The transversely spaced hull sections 10 and 12 and the overly deck assembly generally define an inverted generally U-shaped collection channel 16 running the full length of the vessel w the surface of the water disposed intermediate the hull sectio The hull section 10, 12 and overlying decking may be pref ricated in easily assemblable modular sections of, for examp readily transportable 20 foot lengths, and detachably joined at 18 to form an assembled structure. Further, the hull secti 10, 12 are of multi-co partmented construction. Some of th compartments may be filled with buoyant foam material wh others may be utilized for storage of collected oil.As will hereinafter become apparent, and is clear from F ure 2, the oil collecting material herein employed is slack loose when the vessel is at rest and thus floats loosely upon water surface and allows substantial give or movement of t material under water action; hence particular depth of catamar hull section immersion is not a critical or determinati operative parameter and additionally this looseness allows oper tion of the vessel at higher speeds as discussed more ful below.Mounted in the stern portion of each of the catamaran hu sections 10, 12 in an inboard motor 20 controllable both as speed and helm response from an operating console 22 mounted the deck section 14. Although having the vessel being sel propellable is preferred, it is of course possible to utili some of the basic principles of the present invention in a tow type or other type movable vessel. Peripherally disposed abo the deck section 14 is a guard rail assembly 24. The oil collecting material employed in the practice of the herein described invention may be any of a number of types of materials. For example, sponge may be used, in a sheet or other continuous belt configuration, for collection by absorbtion. However, the material preferred for use in the present invention is polypropylene, formed into the structure disclosed in U.S. Patent No. 3,668,118. Such structure is essentially comprised of an elongate core strand having a multiplicity of thin guage narrow polypropylene strips extending generally radially there¬ from and constituting a relatively loose mass of individually discrete strands or strips that compositely provide a markedly extensive or expanded surface area for the oleophilic attraction and adherence of oil. As is apparent from the disclosure of such patent, the composite structure is both easy to handle and effective in removing the olepohilically adherent- oil from the oleophilic material prior to its reexposure to oil . Such material will hereinafter be termed an elongate oleophilic rope element or elongate oleophlic rope material. Mounted on the fore portions of the deck section 14 are a pair of oleophlic rope element driving and oil separation assem¬ blies, generally designated 30 and 32 respectively. As best shown in Figure 2, each of these assemblies includes a pair of compres- sively engaged drive rollers 34, 36, adapted to advance an assem¬ blage of a plurality of elongate oleophilic rope elements, for example, three endless belt type oil ropes 38a, 38b, and 38c in the direction indicated by the directional arrows 40. Associated therewith are a plurality of guide rollers 44 and 46 to direct the path of travel of the elongate oleophlic rope elements from the drive rollers 34, 36 downwardly into loose, floating disposi¬ tion on the water surface intermediate the catamaran hull sections 10 and 12 adjacent to the bow of the vessel. As can be seen in Figure 2, the lowermost bow guide roller 46 is located substantially above the water line W.L. (for example three feet above in an exemplary vessel of forty feet in length) with the ropes having several extra feet of slack which allows the slack oil collecting material 38 to contact and ride onto the init contacted water surface freely or loosely with substantial permitting it (note 38') to be easily moved longitudinal vertically in response to wave or other water action, as we laterally. Additionally preferably no further guide roll other longitudinal or vertical movement restriction mean provided along the length of the oil collection material 38 it is in the water or close thereto. The rope elements 38 float freely on the wate surface without being taut or ri presented or under any substantial tension or restraint ad to the water surface contact and its contemplated movement.Suitable spacing means, such as vertically disposed ba mounted at each end to a housing 54, are desirably includ maintain the elongate oleophilic rope elements,* for example 38b and 38c, in a desired laterally spaced relation .during travel through the drive asemblies 30 and 32.Mounted on the rear of the deck section 14 and prefe well above the water level W.L. is a guide roll assemb adapted to elevate the oil saturated oleophilic rope ele from engagement with the water surface and to direct them an elongate catch pan 52 on which they are supported during advance as effected by the drive rollers 34, 36. Suitable such as radially extending plates or flanges are included i guide rolls assembly 50 to maintain the oil rope belt laterally spaced relation. The catch pan 52 drains towar driving and separation assemblies 30, 32. Each of the oleopo rope element driving and oil separation assemblies 30 includes a housing 54 and an oil sump from which collected o transferred via schematically illustrated conduit 58 and pu are also utilized to transfer collected oil from the compart 62 to other storage vessels.In using the described unit, the separated modular co ents thereof are adapted to be shipped via air or other means of transportation to the locus of their intended us there assembled. By way of example, the main modular compo thereof may comprise the illustrated two catamaran hull sections, the deck gratings, the oleophilic rope clement driving and oil sepoaration assemblies, the control console assemblies and the like, or may include further sub-assemblies thereof. At or near the locus of use, the readily transportable modules are readily assembled to form the structure depicted in the drawings. The assembled structure is then towed to or drive under its own power to the locus of spillage.In operation, the illustrated vessel is adapted to be ad¬ vanced through the oil spill at a predetermined speed. For the purposes of explanation, such rate of advance may be considered as the water moving from the bow to the stern at a rate of Vw knots. Concurrently therewith, the oleophilic rope element driv¬ ing and oil separation assemblies 30 and 32 are adjusted to ef¬ fect a displacement of those portions of the endless belt elong- gate oleophilic rope elements floating upon the water and dis¬ posed within the oil collection channel intermediate the cata¬ maran hull sections 10 and 12 in the bow to stern direction at a predetermined speed, for example, at a rate of V knots. As best shown in Figure 1, each of the oleophilic rope element driving and oil separation assemblies serves a plurality of separate and discrete endless belt type elongate oleophlic rope elements and whose composite transverse extend substantially fills the trans¬ verse space between the hull sections 10 and 12. As will now be apparent, if the speed of displacement V of the elongate oleophilic rope elements is substantially equal to or slightly in excess of that of V of the elongate oleophilic rope elements is substantially equal to or slightly in excess of that of V , optimum conditions will be established with respect to dwell time for oleophlic pick up of the oil on the strands of the oleophlic rope material. Thus, if the transverse extent of the channel formed between the hull sections is substantially filled with the floating oleophilic mop material and the differential speed relation between such material and the water surface is main¬ tained at a minimal or zero value as described above, essentially optimum conditions, effectively, independent of water surface condition or the presence of' floating debris, can be established and maintained for enhanced oil pick up on a quantitative basis. As is also now apparent, each set of the elongate oleophilic rope elements, for example, 3aa, 38b, 28c, will sclective- ely and preferentially entrain oil from the water surface an they pass upwardly and over the guide roll assembly 50 effe vely separate appreciable quantities of the oil from the w surface. The guide roll assembly 50 directs the elongage o philic rope elements 38 on to the surface of the catch pan 5 support the same as it is advanced into the bite of the pressively engaged drive rollers 34 and 36. The drive roller and 36, which preferably have a surface of elastically deform material, serve both to advance the endless belts of elon oleophilic rope material in the manner described and to pressively squeeze or otherwise displace most of the entra oil from the surfaces of the elongate oleophilic rope materia it advances therepast. Such separated oil is collected in sumps from which it is removed and stored in the tank section of the catamaran hull sections 10 and 12. As will no apparent, the depth of immersion of the catamaran hull sect 10 and 12 is not critical since all collection activity t place on the water surface within the channel marginally def by such hull sections. The loose floatation of the oil collec materials, such as the elongate oleophilic rope elements 38, only maintains the same contact with the floating oil but renders the unit effectively impervious to floating debris or in the water, and within limits, to the degree of turbulenc the water surface since the free floating oleophilic mate will travel over and around any debris and will generally con to the water surface contour.The permitted control of the differentiated velocity bet the floating elongate oleophilic rope elements and the ve velocity permits high efficiency utilization of the oleoph capabilities of the rope elements and consequent high volume high efficiency oil separation from the water surface in a mobility vehicle under widely varying conditions of operationExemplary dimensions for a vessel as illustrated and actually buit, tested and successfully used are a forty (12.2m) aluminum catamaran vessel for inland waters use. Such a vessel can be disassembled and the total vessel stored in two eight-foot-by-eight-foot-by-twenty-foot standard containers. The vessel was powered by two diesel engine driven outdrives and was designed for recovery rates of up to one hundred and seventy-five gp (662 1/m) .Each hull had its own plant and oil recovery system and was capable of operating independently of each other. The vessel had an on-board storage capability of two thousand gallons (7,570 1) and its own discharge pumps for unloading purposes. Further specfications and exemplary details are outlined below:-DIMENSION SPECIFICATIONS-LOA 39'- 8 ( 12 .1 m)Beam 13' - 2 ( 4.01 m)Draft (empty) 1' - 0 ( .305m)Endurance Time 16 hoursRadius Operation 125 N.M. (231 km)Engines ( 2) GM 3-53 NFuel 200 gal. (750L)Oil Recovery Rate 175 gpm (662 1/m) --OIL RECOVERY SYSTEM-(2) Oil Mop Mark 11-9 recovery systems(6) Continuous loop Oil Mop 10 (254 mm) ropes 35' (10.7m) long ea.(2) 135 GPM (511 1/m) independent sump/discharge pumps(6) Independent oil tanks (2000 gal. [7,570.1] total)(2) Manifolds for -fill and discharge(6) Manholes (one into each tank).A vessel at least generally identical to the foregoing was successfully tested for effective oil recovery at speeds up to five kts.The foregoing details and examples are merely exemplary, and subject to great variation within the scope of the present invention. Thus the vessel land its oil collecting materials can be of various sizes and configurations from for example a single hull with the oil collecting materials hung off its side to the preferred multi-hull configurations with centrally defined chan¬ nels. Thus, while the fundamental novel features of -invention been shown and described, it should be undrstood that var substitutions, modifications and variations may be made wit departing from the spirit or scope of the invention. Accordin all such modifications and variations are included in the sop the invention as defined by the following claims.

What is Claimed is:1. A vessel suitable for removing and collecting oil float¬ ing oh the surface of water comprising:(a) an elongate hull defining at least in part an oil coll¬ ection area and having means for advancing the hull through the water; and(b) support means associated with said hull supporting at least one oveable belt or pliant, water floatable oil collecting material to float loosely upon the water surface in the oil collecting area to collect oil floating upon the water surface with the material's initial water surface contact area being free to move vertically and longitudinally under the action of the water.2. The apparatus as set forth in Claim 1 wherein there is further included drive means associated with said hull for moving the oil collecting material longitudinally through the oil collecting area and wherein said drive means includes control means for controlling the speed* of advance of the oil colleting material through the oil collection channel.3. The apparatus as set forth in Claim 2 wherein said drive means also serves as separating means for separating the oil >from the oil collecting material after the oil collecting material is removed from the surface of the water and wherein the drive means and the separating means comprise at least one pair of compress- ively engaged rollers.4. The apparatus as set forth in Claim 1 including stronger means associated with said hull for storing the separated oil on the water.5. The apparatus as set forth in Claim 1 wherein said oil collecting material comprises multiplicities of thin strips of oleophilic material suitably arranged on said belt to present- a fibrous mass to said oil covered water surface. 6. Apparatus as set forth in Claim 1 wherein said belt endless and comprises a continuous rope-like formation of s oil collecting material.7. The appartatus as set forth in Claim 6 wherein s rope-like formation of oil collecting material comprises m plicities of thin strips of oleophilic material generally ra ally disposed about a central rope-like belt.8. The apparatus as set forth in Claims 5 or 7 wherein s oleophilic material comprises polypropylene.9. The apparatus as set forth in Claim 6 wherein said s port means includes means for supporting a series of said be disposed in parallel, side-by-side disposition in the oil co ecting area.10. A vessel for removing and collecting oil floating the surface of water comprising: a. a pair of laterally spaced elongate hull sections fining a longitudinally disposed oil channel therebetween; b. deck means bridging said laterally spaced hull secti and overyling said oil collection channel; c. means for advancing said vessel at a predetermined sp through water having oil on the surface thereof; d. a series of parallel, side-by-side endless belts pliant water floatable oleophilic material each having a port thereof disposed within said oil collection channel substantia parallel to the longitudinal axis thereof, the oleophilic ma rial of each belt being adapted to float loosely and freely u the water surface within the oil collection channel and to c lect oil floating upon said water surface by holding such oil it at adherent interfacial relation therewith; e. a guide roll assembly disposed at the stern.of the v sel; c. controlling said speed of hull section advance and collecting material to render the differential therebetween s stantially zero; 11. 45. The method of Claim 9 further comprising the steps of: a-. introducing said oil collecting material to the water surface at a generally forward location in said collection chan¬ nel; *b. removing said oil collecting material from the water surface at a generally rearward location in said collection chan- ne1; and c. removing the collected oil from said oil collecting ma¬ terial. , ,12. 44. The method of Claim 1-5- wherein said belt is endless and there is further included the steps of:1) advancing said belt as it slackly floats on the water said surface in s-as-i-B water collection section as said vessel moves across the water in a direction countercurrent to the direction of the vessel movement; and ii) controlling the relative longitudinal speeds of said vessel and of the floating belt portion to render the difference therebetween substantially zero.1113. t . The invention claimed in Claims 1, 5, 9 or i5 wherein oil the portion of said belt in said et collection section or channel extends longitudinally along the water surface in contact there¬ with a substantial distance of the order of some feet. AMENDED CLAIMS (received by the International Bureau on 20 November 1978 (20.11.78)What is Claimed is:1. A marine vessel suitable for removing and collec ing oil floating on the surface of water comprising:(a) an elongate hull defining at least in part extended oil collection area and having means associat with the vessel for advancing the hull through the wate and(b) support means associated with said hull for su porting at least one moveable belt of pliant, water floa able oil collecting material to float at least in pa loosely and slackly upon the water surface in the o collecting area to collect oil floating upon the water ^su face with the material's initial water surface contact ar being free to move by itself vertically and longitudinal under the action of the water.2. The apparatus as set forth in Claim 1 wherein the is further included drive means associated with said hu for moving the oil collecting material longitudinal through the oil collecting area and wherein said drive mea includes control means for controlling the speed of advan of the oil collecting material through the oil collecti area.3. The apparatus of Claim 2 including separating mea associated with said hull for separating the oil from t oil collecting material after the oil collecting material removed from the surface of the water by said drive means. 4. The apparatus as set forth in Claim 3 wherein said drive means also serves as said separating means, and wherein the drive means and the separating means comprise at least one pair of compressively engaged rollers.5. The apparatus as set forth in Claim 3 including storage means associated with said hull for storing the separated oil on the vessel.6. The apparatus as set forth in Claim 1 including said belt(s) being freely supported on said support means from the initial contact area and back therefrom a substan¬ tial distance.7. The apparatus as set forth in Claim 6 wherein said belt(s) of oil collecting material comprise(s) multiplici¬ ties of thin strips of oleophilic material suitably arranged on said belt to present a fibrous mass to the water surface.8. Apparatus as set forth in Claim 6 wherein said belt(s) comprise(s) endless belt(s).9. Apparatus as set forth in Claim 8 wherein said belt(s) comprise(s) a continuous, rope-like formation of said oil collecting material.10. The apparatus as set forth in Claim 9 wherein said rope-like formation of oil collecting material com¬ prises mutiplicities of thin strips of oleophilic material at least generally radially disposed about a central rope-like belt. 11. The apparatus as set forth in Claims 7 or 1 wherein said oleophilic material comprises polypropylene.12. The apparatus as set forth in Claim 1 wherein sai support means includes means for supporting a series of sai belts disposed in parallel, side-by-side disposition in th extended oil collecting area.13. A marine vessel for removing and collecting oi floating on the surface of water comprising: a. a pair of laterally spaced elongate hull section defining a longitudinally disposed, extended oil collectio channel therebetween; b. deck means associated with said hull sections an overlying said oil collection channel for bridging an connecting together said laterally spaced hull sections; c. propulsion means associated with said hull section for advancing said hull sections through water having oil o the surface thereof; d. support means associated with said hull sections for supporting movable belts and a set of parallel, side-by-side endless belts of pliant, water floatable oi collecting material mounted on and supported by said suppor means with each belt having a portion thereof dispose within said extended oil collection channel substantiall parallel to the longitudinal axis thereof, the oil col lecting material of each belt being supported by sai support means to float loosely, slackly and freely upon th water surface within said oil collection channel with th material's initial water contact area being free to move b itself vertically and longitudinally under the action of the water and being adapted to collect oil floating upon the water surface by holding the oil on it in adherent inter- facial relation therewith; e. guide assemblies associated with said hull sec¬ tions and disposed aft of the initial water contact area and of said drive means; f. drive means associated with said hull sections for advancing the endless belts of oil collecting material through said oil collection channel in a direction such that the portions of the endless belts of oil collecting material disposed within said oil collection channel are advanced countercurrent to the direction of vessel advance through the water and for further advancing the endless belts of oil collecting material over the guide assemblies elevating the oil collecting material from engagement with the water surface; and g. separating means associated with said hull sections for separating the oil from the oil collecting material prior to the reintroduction of the oil collecting material back into the oil collection channel.14. The apparatus as set forth in Claim. 13 wherein the drive means includes control means for controlling the speed of advance of the oil collecting material through said oil collecting channel. 15. The apparatus as set' forth in Claim 13 wherein th drive means and separating means are at least in par combined and comprise at least one pair of compressivel engaged rollers.16. The apparatus as set forth in Claim 13 furthe comprising catch pan means associated with said deck mean and disposed under said oil collecting material in it return path from said guide assemblies for supporting sai oil collecting material and catching oil falling therefro as it is advanced from said guide assemblies to said driv means.17. The apparatus of Claim 13 wherein said oi collecting material is oleophilic material.18. The apparatus of Claim 17 wherein said oleophli material presents a fibrous mass to the water surface.19. The apparatus of Claim 18 wherein said fibrou mass comprises a rope-like formation having multiplicitie of thin strips of oleophilic material at least generall radially disposed about a central rope-like belt.20. In the emoval of oil from a water surface method comprising the steps of:(a) advancing a marine vessel having a longitudinall disposed, extended oil collection area through the oi covered water;(b) supporting and concurrently advancing at least o elongate, pliant belt of oil collecting material counter current to the direction of vessel advance through the water while slackly and flexibly suspending it on the water -surface in..said oil collection area and while allowing the oil collecting material in at least the initial portion of said area to freely move by itself vertically and longi¬ tudinally under the action of the water; and(c) removing the oil collecting material from the water surface to separate the collected oil from the material.21. The method of Claim 20 further comprising the steps of:(a) introducing said oil collecting material to the water surface at a generally forward location in said collection area and allowing it to remain in contact with the water over an extended distance of some feet;(b) removing said oil collecting material from the water surface at a generally rearward location from said collection area; and(c) removing the collected oil from said oil collec¬ ting material on the vessel and returning the material to the water in said air collection area for further oil collecting.22. The method of removing oil floating on a water surface comprising the steps of:(a) providing a vessel defining at least one side of a longitudinally disposed, extended oil collection area having at least one floatable, pliant belt of pliant, water floatable oil collecting material adapted to float slack and flexibly upon the water in said area;(b) moving the vessel in the longitudinal directi across the water while supporting said material of sa belt(s) in said area to float loosely and slackly upon t water surface with its initial water/oil contact porti being free to move vertically and longitudinally by itse in said oil collection area under the action of the water said oil collection area as the vessel moves across t water; and(c) retrieving said belt(s) from the water at generally rearward location from said collection area.23. The method of Claim 22 wherein said belt(s) endless and there is further included the steps of:(i) advancing said belt(s) as it slackly floats on t water surface in said water collection area .as said vess moves across the water in a direction countercurrent to t direction of vessel movement; and ii) controlling the relative longitudinal speeds said vessel and of the floating belt portion in sa collection area to render the difference therebetween su stantially zero.24. The invention claimed in Claims 1, 13, 20 or wherein the portion of said belt(s) in said oil collecti STATEMENT UNDER ARTICLE 19Enclosed are substitute claim pages (pages 13-20 ) for the originally filed pages 13-15 for the above-identifie patent application. New claims 1-24 are very similar to the originally filed claims 1-17 in substantitve content and scope, but are rewritten versions of the original claims to put them in better form and to more clearly define applicant's inventive concept.The new , substitute claims do not include any new matter not found in the original specification and claims as filed. area or channel extends longitudinally along the wate surface in contact therewith a substantial distance, of th order of-some feet.

MCLELLAN C; OIL MOP INTERNATIONAL INC; OIL MOP INC

MCLELLAN C

WO-1978000019-A1

WO

A1

XX

new

F24J3

F24J2

F24J 2/13, F24J 2/18

ENERGY CONCENTRATOR SYSTEM

"A radiant energy concentrator system (10) for maximizing the amount of radiation flux (18) impingin(...TRUNCATED)

"ENERGY CONCENTRATOR SYSTEM BACKGROUND OP THE INVENTION FIELD OF THE INVENTIONThis invention relates(...TRUNCATED)

"WHAT IS CLAIMED IS:1. A radiant energy concentrator system, comprising: (a) reflector means fixedly(...TRUNCATED)

BUNCH J

BUNCH J

EP-0003016-B1

EP

B1

EN

new

C07D498

A61K31, C07D513

A61K31, C07D241, A61P25, C07D513, C07D498

"M07D241:24B, M07D498:04, M07D513:04, C07D 241/24, M07D513:04+281B+241B, C07D 513/04, M07D498:04+267(...TRUNCATED)

"PYRAZINO-BENZOXAZEPINE AND -BENZTHIAZEPINE DERIVATIVES, PROCESSES FOR THEIR PRODUCTION AND PHARMACE(...TRUNCATED)

"Compounds of formula I, wherein R₁ is hydrogen, alkyl of 1 to 4 carbon atoms, hydroxyalkyl with a(...TRUNCATED)

"PYRAZINOBENZOXAZEPINE DERIVATIVES, PROCESSES FOR THEIR PRODUCTION AND PHARMACEUTICAL COMPOSITIONS C(...TRUNCATED)

"WHAT WE CLAIM IS: 1. A compound of formula I, EMI17.1 wherein R1 is hydrogen, alkyl of 1 to 4 carbo(...TRUNCATED)

SANDOZ AG

LEUTWILER, ALBERT, DR.; SORG, DIETER, DR.

EP-0003024-B1

EP

B1

DE

new

B23Q41

B65G47

B23Q41, B65G47

B65G 47/48B2, B23Q 41/02

FLEXIBLE MANUFACTURING SYSTEM

"1. Flexible manufacturing system for workpieces affixed to pallets, comprising a plurality of proce(...TRUNCATED)

"Flexible 6 Fertigungssystem Die Erfindung betrifft ein flexibles Fertigungssystem für Werkstücke,(...TRUNCATED)

"Patentansprüche 1. Flexibles Fertigungssystem für Werkstücke, bestehend aus einer Anzahl Bearbei(...TRUNCATED)

GEBR. HELLER MASCHINENFABRIK GMBH

HAUSSMANN, HERBERT; MAIER, HEINZ

EP-0003025-B1

EP

B1

DE

new

B66C13

G05D3, B63B27

B66C13, G05D3

B66C 13/48, G05D 3/14, B66C 13/30

ROTATIONAL GEAR OR LIFTING GEAR DRIVE CONTROL ARRANGEMENT FOR A CRANE

"1. Regulation means for slewing or fifting gear drives of a crane, in particular for ships, wherein(...TRUNCATED)

"Regelung für Drehwerks- oder Hubwerksantriebe eines Krans Die Erfindung bezieht sich auf eine Rege(...TRUNCATED)

"Patentansprüche 1. Regelung für Drehwerks- oder Hubwerksantriebe eines Krans, insbesondere für S(...TRUNCATED)

O & K, ORENSTEIN & KOPPEL AKTIENGESELLSCHAFT WERK LUBECK; SIEMENS AKTIENGESELLSCHAFT

BEHRENDT, VOLKMAR, ING.(GRAD); BERTLING, TONI, DIPL.-PHYS. DR.-ING.

EP-0003036-B1

EP

B1

DE

new

E04C1

B28B11

B28B11, E04B2

E04B 2/14, B28B 11/00E2

"METHOD OF MANUFACTURING CERAMIC BRICKS, ESPECIALLY BRICKS WITH GRID-LIKE CAVITIES AND APPARATUS FOR(...TRUNCATED)

"1. A method of manufacturing ceramic building blocks with intersecting webs, more particularly perf(...TRUNCATED)

"Keramischer Baustein sowie Verfahren und Einrichtung zu dessen Herstellung Die Erfindung bezieht si(...TRUNCATED)

"Patent ansprüche : 1. Keramischer Baustein, insbesondere Gitterziegel stein mit stirnseitigen Öff(...TRUNCATED)

PETER VAN EYK GMBH & CO. KOMMANDITGESELLSCHAFT

SMEETS, HEINRICH