Abstract: Polycyclic spiroorthoester which undergo expansion on polymerization to f resins, rather than shrinkage on polymerization, are employed in fabrication of composite, filament-reinforced, interceptor motor cases. The advantages which accrue to such use of the specified resins relate to the imparting of unique characteristics to the interceptor motor case such as increased structural strength, a reduction in the number of microcracks and voids, and improved bonding between resin and reinforcement. These unique characteristics impart benefits where needed since composite motor cases are fabricated from high strength filaments or tapes such as fiberglass, graphite, poly-p-phenyleneterephthalamide (Kevlar), in a polymeric matrix, and the primary mode of failure is due either to poor adhesion between the matrix and the filament or tapes or because of the development of microcracks or voids in the matrix.The spiroorthoester, 1,4,6-trioxaspiro [4.

Abstract: Mechanical enhancement of the burning rate of solid propellants is achieved y the incorporation of limited percentages of heat-expandable beads into the solid propellant matrix. When the flame front reaches an individual bead, the bead which contains an expanding or blowing agent (e.g., pentane, 4,4'-oxybis(benzenesulfonyl hydrazide) (Celogen OT), etc., expands to several times its volume and ruptures. Bead expansion or rupture causes a disruption of the propellant's surface, and the flame can penetrate into the propellant. This penetration results in a major increase in burning rate.

Abstract: Disclosed is a liner-barrier system which is impermeable when cured to the igh concentrations of carboranyl burning rate accelerator which are incorporated into ultrahigh-burning rate propellants which are being developed for advanced interceptors. The liner-barrier composition, when uncured, comprises a polyvinyl butyral resin coblended with thermosetting resins, such as, phenolic, epoxy etc., that employs triphenylbismuthine as a quick cure catalyst, 4,5-epoxycyclohexylmethyl 4',5'-epoxycyclohexyl carboxylate and polyisocyanate as curative and crosslinking agents to further modify the liner-barrier formulation by reacting with the secondary hydroxyl groups. Further modification of the liner-barrier formulation is achieved by incorporation of aluminum powder to impart additional properties of impermeability. The uncured liner-barrier composition contains from 8.90 to about 10.21 weight percent solids in a solvent blend of isopropyl acetate and isopropyl alcohol which comprises from about 89.79 to about 91.

Abstract: Solid oxidizer particles of ultrahigh surface area are produced by an etching process which includes employing selective extractants in a process which causes the formation of indentations and/or cavities on the surfaces of the oxidizer particles, and crevasses and tunnels in the oxidizer particles. The method is particularly attractive for manufacturing ultrahigh surface area ammonium perchlorate which has limited solubility in the extractants ethanol, butanol, or a mixture of these extractants.

Abstract: Preformed metal/oxidant agglomerates for enhancement of propellant burning ate are prepared from a finely divided metal (aluminum, boron, titanium, etc.), ammonium perchlorate, and a small quantity of the same binder material that goes into the manufacture of the propellant, such as, hydroxyl-terminated polybutadiene crosslinked with a polyisocyanate. Additional ingredients can be incorporated into the agglomerates to bring about further enhancement of burning rate, such as, an ammonium perchlorate decomposition accelerator triphenylbismuthine, a carboranyl burning rate enhancer, iron oxide, etc. Agglomerates are prepared in a fluorinated and/or chlorinated hydrocarbon solvent in which the agglomerate formulation ingredients are insoluble. Any remaining solvent is then evaporated under reduced pressure and the agglomerates are subsequently cured. Optimum mesh size of the agglomerates is 300-500 micrometers.

Abstract: A single cast solid propellant rocket motor grain having a centrally positioned rod portion integrally connected to an outer cylindrical portion at a base portion and comprised of a unitary solid propellant rocket motor grain wherein the central rod portion is approximately twice the thickness of an outer cylindrical portion and having the geometric dimensions and shape to achieve substantially a simultaneous burnout of the propellant burning surfaces after maintaining a burning neutrality from ignition to completion of propellant burning.

Abstract: A general purpose expandable adhesive comprised of a spiroortho ester synthesized from the lactone, 6-caprolactone, and the diglycidyl ethers of bisphenol A and 1,4-butanediol, Cab-o-Sil thickener/thixotrope, silica (325 mesh), and Unirez 2800, amidoamino curing agent, has superior tensile strength, superior bondability and with less void formation to aluminum, steel, wood, and cured concrete as compared with a general purpose adhesive which does not contain a spiroortho ester.

Abstract: A method of determining tensile bond strength and lap shear strength betw a liner/insulation material and a propellant composition which is cured to portions of the liner/insulation material.The liner/insulation material is bonded to a propellant composition in a dogbone configuration by positioning a predetermined size of the liner/insulation material in a groove that is constructed in a mold in a transverse direction for a tensile bond strength specimen whereby the propellant is bonded to each side of the exposed liner/insulation material. The lap shear specimen is formed in a mold wherein a predetermined size of the liner/insulation material is longitudinally positioned in a groove that is constructed in a mold.

Abstract: Nitrosyl fluoride is prepared by laser-induced method wherein the nitrosyl luoride is produced in situ or in close proximity to where it is used to etch semiconductor surfaces.A reaction mixture of a catalyst compound and a fluoro compound, wherein the catalyst compound is an oxide of nitrogen selected from the group of nitrogen oxide compounds consisting of NO, N.sub.2 O, and NO.sub.2 and wherein the fluoro compound is selected from the group of fluoro compounds consisting of NF.sub.3 and N.sub.2 F.sub.4, is irradiated with CO.sub.2 laser radiation to produce FNO. FNO reacts with an exposed silicon material to produce SiF.sub.4 and nitrogen oxide. Since the oxide is regenerated, it can be regarded as a catalyst which can be recovered and recycled.A production scheme for producing nitrosyl fluoride for etching is disclosed wherein the nitrosyl fluoride is produced directly in the laser reaction chamber by passing a CO.sub.2 laser beam through the reaction mixture.

Abstract: Amine salts which are adducts of an ammonium ion donor selected from ammom perchlorate, ammonium sulfate, ammonium formate, and equal molar mixture of ammonium perchlorate and ammonium formate and cyanoethyl substituted tetraethylene pentamine (TEPAN) or the glycidol reaction product of cyanoethyl substituted tetraethylene pentamine (TEPANOL) are employed as a bonding agent in a solid propellant composition employing a polyester binder of polydiethyleneglycoladipate.Unlike hydroxy-terminated polybutadiene wherein a bonding agent is solubilized and still can function as a bonding agent for inorganic ammonium oxidizer salts in the propellant matrix, polyester binders that solubilize the bonding agent renders the bonding agent ineffectual as a bonding agent. Therefore, with a polyester binder it was found that the bonding agent could not be soluble in the prebinder to be effective in improving mechanical properties.

Abstract: An embedment system with controlled shrinkage for use with a composite-modified double-base propellant composition which is comprised of an embedment granule portion in percent by weight of nitrocellulose of about 23.0, nitroglycerine of about 8.8-13.8, triacetin of about 1.2, bisspiro orthocarbonate from about 2.5-5.0, resorcinol of about 1.5, 2-nitrodiphenylamine of about 1.0, ammonium perchlorate (10 micrometers) of about 48.5 and aluminum powder (20 micrometers) of about 10.0 and an embedment resin portion in percent by weight of bisphenol A-epichlorohydrin of about 50.0, epoxidized dimer acid of about 50.0, and a curative which is comprised of equal parts mixture of methylenedianiline, m-phenylenediamine, and i-propyl-m-phenylenediamine with an added accelerator of 2,4-dinitrophenol. This embedment system employs a specific bisspiro orthocarbonate, 3,9-bis(5'-norbornene-2'-yl)-1,5,7,11-tetraoxaspiro[5.

Abstract: A CW tunable laser is employed in a laser photochemical decomposition met to achieve decomposition of a compound of high toxicity to relatively non-toxic decomposition products.Organophosphorus chemical agents containing a characteristic C--O--P group are irradiated with a predetermined power level from about 10 to about 150 W/cm.sup.2 for a predetermined time period to effect cleavage of the C--O bond. The infrared laser excitation level of radiation in the range of 10.4 .mu.m or 9.4 .mu.m is resonant with the absorption band of the C--O--P group contained in the organophosphorus chemical agent. The absorbed radiation effects cleavage of the C--O bond and thereby achieves decomposition of the organophosphorus chemical agent.The disclosed method is highly selective for cleavage of the C--O bond rather then cleavage of the P--O bond, and in the presence of air, the method requires low power levels of the CO.sub.2 laser for rapid and complete dissociation of the organophosphorus chemical agent.

Abstract: Disclosed is a thixotropic flame inhibitor for a rocket propellant grain luding an organic thixotrope in amounts from about 5 parts to about 30 parts into HTPB liquid polymer in amounts from about 70 parts to about 95 parts by stirring at elevated temperatures. After cooling the mixture to room temperature, appropriate quantities of di- or polyfunctional isocyanates and cure catalysts are added to promote cure at room temperature. Fine particulate matter may also be added to increase viscosity. The resulting formulation is a room-temperature curable, thixotropic mixture which will not flow under its own weight when applied to wettable non-horizontal surfaces in appreciable thicknesses, and which, when cured, is suitable as an inhibitor for composite solid rocket propellants. Thixotropy may be controlled by the level of organic thixotrope in the formulation while viscosity may be adjusted by the level of particulate filler; these parameters determine the allowable thicknesses from one-coat applications.

Abstract: A gas generator for passing pressurized liquid monopropellants therethrough or causing exothermic decomposition of the monopropellants. A porous catalytic metal plate is used as the degeneration bed. The monopropellant decomposes exothermically upon contact with the catalytic plate. The porosity is obtained by making the plate from an alloy of the catalyst metal and one other metal, the other metal is then etched away by an acid that does not attack the catalyst metal. The porosity is controlled by the amount of other metal used. Surface areas of several hundred times the original plate surface area are obtainable. The mechanical characteristics of the metal plate allow for greater design flexibility than was available with decomposition beds made of refractory material.

Abstract: Cure shrink-resistant missile motor cases are disclosed along with their method for construction. These cases comprise a matrix resin composition which includes a bisspiroortho carbonate as a fourth component, a curing agent of o-phenylenediamine boron trifluoride etherate as a third component, butanediol diglycidyl ether as a second component, and equal parts by weight of diglycidyl ether of bisphenol A and epoxidized dimer of oleic acid as a second component and additionally, they comprise, in combination therewith, a high strength fiber reinforcement material selected from the group consisting of fibers of glass, graphite, and poly-p-ethylene terephthalamide (Kevlar). The specific bisspiroortho carbonate which achieves an expansion of the matrix resin on polymerization or curing is 3,9-bis(5'-norbornene-2'-yl)-1,5,7,11-tetraoxaspiro [5.5]undecane.

Abstract: Disclosed is a method of microwave drying of ammonium perchlorate grinding pheres. A preferred embodiment of the method employs a tunnel oven in combination with a microwave generator having an appropriate power supply. The tunnel oven receives microwave energy through transmission ducts in communication with a channeling device to distribute microwave energy over the grinding spheres to be dried. A preheated air supply facilitates moisture removal from the tunnel oven after the moisture adhered or occluded to the grinding spheres' surfaces is evaporated from the grinding spheres as a result of molecular vibrations of the water molecules after they absorb the microwave energy. A predetermined microwave frequency range and a predetermined drying time are employed to more efficiently remove adhered or occluded moisture from carbide grinding spheres as compared to conventional convection drying.

Abstract: Ethanol is recovered from fermentation products by a countercurrent extraction process which employs diethyl ether as the extraction solvent to form a diethyl ether-ethanol mixture. The ethanol is salted out by adding calcium chloride to the mixture, and the diethyl ether layer is separated and recycled. The calcium chloride in ethanol solution is removed by adding sodium carbonate to form the solids calcium carbonate and sodium chloride which are removed by filtration. The ethanol is recovered as the filtrate.

Abstract: The polyamine compound, TEPAN, a partially cyanoethylated tetraethylene pamine, is reacted with a selected ammonium salt to form an adduct of TEPAN and the selected ammonium salt. The ammonium salt is selected from ammonium perchlorate (AP), ammonium nitrate (AN), ammonium sulfate (AS), and ammonium formate (AF). The process for preparation of the adduct comprises reacting a water solution of the selected ammonium salt with TEPAN while stirring at room temperature. A TEPAN-glycidol derivative product is also reacted with the selected oxidizer salt to form an adduct of the TEPAN-glycidol derivative product.The disclosed adducts (having adduct ratios of 1.0 to 1.8 equivalents of ammonium salt per mole of TEPAN or TEPAN-glycidol derivative product, TEPANOL) improve mechanical properties and processiblity of composite propellant composition containing about 88 weight percent solids (ammonium perchlorate, aluminum, and Fe.sub.2 O.sub.

Abstract: A cw CO.sub.2 tunable laser is employed to irradiate an allyl halide selected from allyl chloride, allyl bromide, allyl fluoride, 2-methyl-3-chloropropene, and 2,3-dichloropropene and contained in one or more reaction cells at a predetermined pressure. A predetermined power level from about 25 to 150 watts, an irradiating time from about 0.2 second to about 60 seconds, and a selected radiation line for example P(36), P(32), P(28), P(26), or P(22) (that is resonant with an absorption band of the selected allyl halide) are employed to achieve dissociation of the selected allyl halide and to achieve a laser-induced photochemical synthesis of benzene and substituted benzenes.

Abstract: Solid reactant hydrogen gas generator formulations which yield greater than 5 weight percent hydrogen of greater than 98 mole percent hydrogen purity are formulated of a primary heat and hydrogen source selected from ammonia borane from about 50 to about 70 weight percent and hydrazine bisborane from about 0-30.00 weight percent, a first hydrogen-containing compound that functions as an auxiliary heat and hydrogen source consisting of ammonium nitrate from about 10.20 to about 17.82 weight percent, and a second hydrogen-containing compound that functions as an auxiliary heat and hydrogen source consisting of (NH.sub.4).sub.2 B.sub.10 H.sub.10 from about 9.80 to about 17.18 weight percent.