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United States Patent Office Patented Dec 3,551,226 United States Patent Office Patented Dec. 29, 1970 1. 2 zines) such as diamide, symmetrical (1,2-) or unsym 3,551,226 GELLED MONOPROPELLANT CONTAINING HY metrical (1,1-) dimethylhydrazine, and monomethylhy DRAZINE AND ANONHYPERGOLIC ACD GAS drazine can be gelled using non-hypergolic acid gases such GELLENGAGENT aS CO2. Barry D. Allan and Walter W. Wharton, Huntsville, and The term hydrazines, as used herein, is intended to in Theodore N. Hubbuch, Florence, Ala., assignors to the clude hydrazines and their derivatives. In particular, it in United States of America as represented by the Secre cludes diamide and its derivatives such as monomethyl tary of the Army hydrazine, symmetrical dimethylhydrazine and unsun No Drawing. Filed Oct. 16, 1968, Ser. No. 768,559 metrical dimethylhydrazine. The term hydrazines is also Int, C. CO6c 17/00 intended to include hydrazines and their derivatives modi U.S. C. 149-36 4 Claims O fied by non-hypergolic oxidizers such as those mentioned hereinafter. The term is also intended to include higher hydrazines. ABSTRACT OF THE DISCLOSURE The liquid amines which can be gelled in accordance The gelling of various amines (including hydrazines) 5 with this invention include primary (e.g., n-propyl or such as unsymmetrical or symmetrical dimethylhydrazine, monoethanol amines or ethylene diamine), Secondary diamide and monoethylhydrazine (alone or in admixture) (e.g., diethyl or dimethyl amines), and tertiary (e.g., tri by interaction of the amine and a non-hypergolic acid gas ethanol or triethylamines). The amine may be an aryl such as CO to form a gelled compound for use as a fuel amine (e.g., benzylamine) as well as an alkylamine. Ad for rocket motors. 20 mixtures of these amines can be employed, if desired. Of the hydrazines which can be gelled in accordance with this invention, the unsymmetrical dimethylhydrazine (previously mentioned), examples of such unsymmetrical BACKGROUND OF THE INVENTION hydrazines are phenylhydrazine, ethylhydrazine, propyl This invention relates to an improved method of gelling 25 hydrazine and hydrazine hydroxide. Unsymmetrical hy amines such as hydrazines, and particularly to such a drazines may be considered as amines in which one of the method yielding exhaust products (upon combustion of hydrogens of the NH2 group is replaced by another NH2 the gel) which are beneficial in rocket propulsion systems group. or gas generators. By the term “acid gas' we mean a gas which in water Amines such as hydrazines are useful as liquid fuels 30 solution has an acid reaction, but which is released un for rocket motors. They exhibit favorable combustion changed upon sufficient heating of the water. In addition properties when reacted with an oxidizer such as nitric to carbon dioxide, carbon monoxide, hydrogen sulfide, acid, a relatively high specific impulse being obtained. sulfur dioxide, sulfur trioxide, carbon disulfide, and ethyl Serious safety hazards are presented in the use of these ene oxide are gases of this type. Admixtures of these acid fuels in liquid form. These materials are highly toxic, and 35 gases can be employed, if desired. when handled as a liquid, extreme precautions must be The method of this invention can be carried out in vari taken to avoid leakage or escape of fumes. In addition, ous types of apparatus, either intermittently or continu these fuels react hypergolically with many common ma ously. terials so that a leak could cause a disastrous fire. These As a specific example, about 25% by weight of CO2 problems can be alleviated by converting these fuels to a 40 (based on the weight of gel) in diamide will produce a thixotropic gel, which behaves as a stable solid until dis gel with about 1 centipoise viscosity (at room tempera turbed but flows as a liquid when force is applied. ture). The gas is mixed with the diamide in a conventional Prior methods of gelling hydrazine or similar fuels yield manner such as by bubbling or sparging. The optimum gels having burning characteristics generally poorer than absorption and/or reaction occurs at higher pressures than or, at best, about equal to untreated or ungelled hydra 45 atmospheric and/or lower temperatures than room tem ZS perature. It is therefore an object of this invention to provide Generally speaking, up to about 40% by weight of acid hydrazines or similar fuels in the form of a thixotropic gas may be incorporated in the gelled diamide. gel. Generally speaking, for primary propulsion systems, it Another object of this invention is to provide an im 50 is desirable to incorporate as small a percentage of acid proved method of converting hydrazines or similar fuels gas as possible, but yet enough to produce a gel of the to a thixotropic gel. required viscosity. For secondary propulsion systems, or Still another object of this invention is to provide such gas generators it is desirable to incorporate the maximum a fuel in a propellant which has a relatively high specific amount of acid gas that can be absorbed. impulse and a relatively low flame temperature. 55 It will be understood by those skilled in the art that Yet another object of this invention is to provide such a hydrazines are customarily used with oxidizers. Thus, it propellant which has a higher specific impulse at a given should be apparent that the gelled hydrazine compositions flame temperature than solid propellants or conventionally of this invention may be modified by an oxidizer, addi gelled liquid propellants. tive, preferably an unreactive particulate oxidizer solid in A particular object of this invention is to provide a 60 minor proportion, such as, for example, ammonium ni method of gelling hydrazines or similar fuels which pro trate or perchlorate, potassium nitrate or oxygen. Some duces exhaust products (upon combustion of the gel) fuel and oxidizer combinations are known to be hyper which are beneficial in propulsion systems, gas generators. golic, and the two must, of necessity, be maintained out of contact with each other until it is desired to initiate the SUMMARY OF THE INVENTION 65 combustion. However, in fuel-and-oxidizer combinations It has been discovered that various amines such as hy which are not hypergolic, the oxidizer may be blended di drazines can be gelled using a non-hypergolic acid gas Such rectly with the constituents for forming the gelled hy aS CO2. drazine compositions. The use of an oxidizer additive is desirable because it DESCRIPTION OF THE PREFERRED 70 increases the energy content and permits the incorporation EMBODIMENT of higher concentrations of gelling agent to get stiffer or Various liquid amines (defined herein to include hydra more solid gels without reduction in energy content. 3,551,226 3 4. The non-hypergolic acid gas (such as CO) used to The gelling method of this invention may also be used gel the compound (such as diamide) produces exhaust in conjunction with conventional gelling methods (em products (upon decomposition) which are beneficial in ploying solid or liquid gelling agents) such as those em propulsion systems. This is in contrast to the same com ploying celluloses as the gelling agent. pound gelled with SiO2. In the later instance, the SiO2 We claim: does not react with the compound to produce gaseous 1. A gelled monopropellant composition comprising a products. hydrazine monopropellant that has been gelled with a non Some applications of the method of this invention are: hypergolic acid gas gelling agent to thereby effectively in crease the viscosity of said monopropellant composition (1) gel formation for use in propulsion systems. over that of said monopropellant, said acid gas gelling (2) the suspension of particles (e.g., metals) in fuels for 10 agent being selected from the gases of the group consist use in propulsion systems. ing of carbon dioxide, carbon disulfide, sulfur dioxide, (3) the formation of gels by either of the above methods sulfur trioxide and ethylene oxide. for use in secondary gas generators (propulsion or gas 2. The composition of claim 1 wherein said hydrazine generation systems other than those for primary pro monopropellant is an unsymmetrical hydrazine. pulsion). 5 3. The composition of claim 1 wherein said hydrazine (4) the reduction of the flame (reaction) temperature of monopropellant is diamide, monomethylhydrazine, sym the propellant. metrical dimethyl hydrazine or unsymmetrical dimethyl (5) changing the ignition delay of the propellant so that hydrazine. detonation is not achieved. The reaction is thereby 20 4. The composition of claim 3 wherein said acid gas tailored to useable rates. is carbon dioxide. One basic advantage of this invention is that it may be used to tailor the flame temperature of the gel to that References Cited desired by simply varying the amount of acid gas used. UNITED STATES PATENTS Also, the gaseous decomposition products achieved in 25 accordance with this invention are of a lower flame tem 2,521,026 9/1950 Solomon ------------- 149-36 perature (for a given impulse) than that of conventionally 2,934,417 4/1960 Schulze ------------- 149-36 gelled hydrazines. Also, the reaction of rapidly mixed 2,982,637 5/1961 Kruze -------------- 149-36 samples of gels of this invention with oxidizer is frequent 3,088,272 5/1963 Stengel et al. -------- 149-36 ly non-detonable. 30 It will be apparent that the monopropellant charge may CARL D. QUARFORTH, Primary Examiner be gelled outside of the propellant charge chamber and S. J. LECHERT, JR., Assistant Examiner then poured in or that the charge may be poured into the chamber before gelling takes place, with the closure U.S. C. X.R. removed, and then applying the closure. 35 149-20, 46, 61, 76 .
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