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April 25, 1961 V M H, BOYER 2,981,616 'Li April 25, 1961 v M_ H, BOYER 2,981,616 GAS GENERATOR GRAIN Filed ÜCÍ'. l, 1956 'li "' 26/ BY M2M AGENT 'lf `tent _ ICC 2,981,616 UnitedI tates ï le'ensserr~ia5» 2 vand x represents the valency 'of M, and (2)V at least Forio oxidizing compound selected from the Aclass consistirfg of metal peroxides, inorganic perchlorates and metal iii 2,981,616 trates; said azides and said oxidizing ‘compounds bein‘g GAs GENERATOR GRAIN present in amounts expressed by the V’equation rdm-'45', wherein n represents the number of azide nitrogen atoms, Myron H. Boyer, Puente, Calif., assignor to m represents the number of equivalents ofoxidizing 'coni North American Aviation, Inc. pounds, and y lhas a numerical value of from about Y2:3 a Filed oct. 1, 1956, ser. No. 613,327 to about 3.6. ` » Y d ` ï 10 An example'of the gas generator grain of this 'inven s Claims. (el. sz­­.5) tion vis a composition comprising ’calcium'azide and pól tassium perchlorate ­in amounts ­such that 'ther-'equatiòh n/m has the value 3,. , ' ' Y " i j The azides, M(N3)x, that can be _used in the >preptufaf This invention relates to a novel composition or" matter 15 tion of ’the compositions of vthis inventionca'n Abe any suitable for generating gases. More particularly, this _azide which has suitable stability to permit grindin'grand invention relates to a composition which upon ignition Vhandling in the preparation of the composition, and alsno generates an inert gas useful for pressurizing rocket pro will burn at a satisfactory ­rate Without exploding. - 'A ¿pellant tanks. v ` class of metal azides which satisfy these 'requirements In a rocket or missile which is operated on liquid fuel, 20 are the alkali and alkaline learth azides.V Nonlimit‘i'n'g itis necessary to provide a means for supplying the fuel examples of these include lithium azide, sodium azide, tothe engine at a predetermined rate. This rate must potassium azide, rubidium azide, and cesium azide which be of a magnitude vsuiiicient to sustain uninterrupted constitute the alkali metal azides having the general-for „combustion from which power is derived to operate the mula M(N3). Since the valence, 'xfof M, the `alkali ­rocket. ' The use of pumps is one method for supplying 25 metal is unity, thesymbol x is omitted vfrom the formula. the fuel to the rocket engine. To obviate the use of The alkaline, earth ‘azides include `the calcium aiide, »weighty pumping equipment, a method ofvfeeding the strontium azide, and barium azide.> A,The metal vM'in 'the fuel to the combustion chamber by the development of formula M(N3)X~in this case is >divalent and, "therefore, gas pressure in the fuel tank has been employed. The the symbol x has a numerical value of 2. VThe alkaline .gas Vdeveloping the pressure may be obtained from the 30 earth metals of which the azides are composed :have combustion product of a composition of matter called a atomic weights varying vfrom 40 to 138ginclus'ive. 'When gas generator grain. The gas generator grain is ignited a hydrazine azide and ammonium azide 'are used, itlis at theftime the motor is put into operation and as com advisable to employ anexplosioninhibitor such >as `di bustiòn consumes the grain, the resulting gaseous prod atomaceous earth in order to ­reduce the 'hazard 'of vspdn‘ yl'lct‘sfe'x’e'rt a pressure inside the fuel compartment causing 35 taneous-decomposition. f. , i . ’ Í Y, Èthe fuel to ñow through feed lines to the rocket motor. _The alkali metal azides are found to be particularly ÍOfnfe. gas generator grain employed in the past _was lcorri suited to the preparation of gas generator 'grains and coní 'posedof amixture of ammonium ­perchlorate and a hydro positions containing them constitute `a preferred embodi 'carbo'n and sulfurl'co'ntainin'g polymer. Among the _com ment of this invention. The `alkali metals of which the bústion products of the gas generatorg rain were, there 40 alkali metal azides are composed have atomic weights of fore, hydrogen, carbon monoxide and hydrocarbon gases. from 6 to 133 inclusive. These are reducing _gases,land, consequently, cannot be The oxidizing compounds of which the composition >of Ítisedl `with certain types of lpropellants such as, forex matter of this invention are prepared includemetal per-oit“ ample, nitric acid, as they would destroy the oxidizing ides,V inorganic ,perchlorates y and vmetal nitrates. Vï'fI‘he •‘clutracteristic lof ­the yfuel prior to its introduction into 45 metal peroxides have thek general formula jXÍO,g wherein :the ycombustion chamber >of the motor. Also, the gases t X is a metal having. an atomic weight of from“ 6 t0 about may form explosive vapor mixtures vwith fuels and/or ,138 inclusive, ris the number of metal atoms in the perox-l oxidizer. Other combustion products of „the sulfur-com ide compound and varies from l to_2_. The valueof s vat'ì taining polymers are 'oxides òffsulfur. These are very ies from l to Zand representsl thenumberv of oxygen atoms 'corrosive and cause damage 'to the motor. This not only 50 in the peroxide molecule. `,Nonlirniting examplesof -met'al reduces the period of serviceability but also impairs the ­peroxides employed in the manufacture »of the composi operation of the motor Vdur-ing ñight. The result is that vtion's of this vinvention include peroxides of group-LA the missile or rocket is more diiiicult to control and metals such assodium peroxide, NazOz, potassium per increases the hazard of loss due to motor failure. A oxide, K2O2, rubidiurn peroxide, RbzOg, and cesium per need, therefore, existed for the development of a gas 55 oxide, Cs202; peroxides of group IIa-A_metals sueltas generator grain which, upon combustion, would give olf calcium peroxide, Ca'OZ; strontium peroxide,` YSrO2; barium inert gases only sowas to`•aiîect lneither the properties of the rocket fuel nor the operability of the motor. peroxide,having >the BaOà.m general Examples formula ofY(C1`O4)„ the,inorganic,perchlor­ wherein Y fisse -It is therefore an object of this invention to provide lected from the class consisting of a metal and tlië ía composition of matter suitable for` use as a gas gen 60 ammonium radical, v represents the valenceïof. Y andv erator grain. It is also Van object of this invention to has a numerical value „of 1 ,to 3 __inclusive,pinclude àrn~ -provide a composition of matter which, upon combustion, . monium perchlorate;_group I-A metal perchloratesvpuc'h -produces only inert gaseous products. Another'object as lithium perchlorate, L_iQlO4, , sodium `>perch_loratfç'a >ofthis invention is to‘provide a method for pressurizing NaClO4, potassium perchlorate, „KClOg and`Vr 'rubidiurn propellant or fuel chambers of rockets and missiles. Other 65 perchlorate, RbClO4; group II-,A metal perchlorates such objects will become apparent from -the' discussion that as magnesium perchlorate,4 Mgt’ClOÀQZ, calciumperchlo'f «follows ’ - „ rate, Ca(ClO4)2, strontiumperchlorate,> Sr(ClO4)2, and The above and other'objects of this invention are ac barium perchlorate, Ba(KClO4)2; group VIIIv perchlorates complished by a composition of matter comprising (1) such as ferrie pt'erchlorate,­ _Fe(ClO4)3,vand cobalt ,peri „an‘azide having the general formula M(N3)¿ wherein 70 chlorate, CO( C104) 2;.and group IKII-A metal perchlora is selected ¿from the vclass rconsisting of a metal, a hy such as I`r1(ClO4)3;Y Non-limiting examples of metal nr-z vrlrazino radical Yand an >ärnmc'ouium radical; AN is nitrogen; trates having the' genera-t fórmula T(NO¿); wherein-T ' _is a `metal and z is the" valence of T having a numerical the equation nlm=y wherein n represents the number yalue of from l to 4 inclusive, include group I-A metal of azide nitrogen atoms, m represents the number of nitrates such as lithium nitrate, LiNO3, sodium nitrate, equivalents of oxidizing compounds, and y has a nu NaNO3, and potassium nitrate KNOS; group I-B metal merical value of from about 2.3 to about 3.6. ,nitrates such( as copperV nitrate, Cu(NO3)2; `and silver In addition, the compositions of this invention may ­nitrate, ~Ag(NO3); group II-A` metal‘nitrates `such as also contain minor amounts of metal and metalloid pow „magnesium nitrate, Mg(NO3)2, and‘ barium nitrate, ders and their oxides as burning catalysts. Powdered ;Ba,(NO3)2; group II-B metal nitrates such as zinc nitrate; or comminuted carbon, phosphorus and sulfur` also serve „group III-A metal nitrates such as aluminum nitrate, as burning catalysts. The amounts can range from less „AI(NO3)3, and thalium nitrate, Tl(NO3); group IV-A l0 than 0.1 weight percent to about 3 weight percent based metal nitrates such as stannic nitrate, Sn(NO3)4; group on the weight of the combined azide `and oxidizing com 'VU-A metal nitrate such as bismuth nitrate, Bi(NO3)3; pound. The particle size of the burning catalyst can group VII-B metal nitrates such as manganese nitrate, vary from about 10 to 100 microns.` Nonlimiting ex Mn(NO3)3; and` group VIII metal nitrates such as ferric amples of metal and metalloid powders and their oxides .nitrate, ferrous nitrate and nickel nitrate. Methods for that can be used as burning catalysts are copper, mag ,the preparation of metal peroxides, metal nitrates yand nesium, boron, aluminum, zirconium, vanadium, anti inorganic perchlorates are given infvolumes I and II of mony, manganese, iron, cobalt, nickel, ferrie oxide, silica, ,the text “Chemical Elements andTheir Compounds” by etc. ~ -N>°` V. Sidgwick; 1950 edition, published by the Clarendon In the preparation of the compositions of this inven Press.
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