US2744816A - Solid gas-generating charges - Google Patents

Solid gas-generating charges Download PDF

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US2744816A
US2744816A US373498A US37349853A US2744816A US 2744816 A US2744816 A US 2744816A US 373498 A US373498 A US 373498A US 37349853 A US37349853 A US 37349853A US 2744816 A US2744816 A US 2744816A
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charge
gas
decomposition
phenol
per cent
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Alexander Cantlay Hutchison
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/04—Compositions containing a nitrated organic compound the nitrated compound being an aromatic
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids

Definitions

  • 'Irhis v.invention relates to improvements in solid gasgeneratng charges. More particularly, it relates to charges of the relatively slow-burning kind capable of propagating through themselves a self-sustaining exothermic non-detonating gas-evolving decomposition when a merely local portion of the charge is heated from room temperature to the temperature at which its active decomposition begins.
  • gas-generating charges have found application heretofore for a variety of purposes including, for instance, the actuation of gas pressure operated mechanical devices, safety (flameless) blasting operations, the dispersion of volatilizable pesticides, in. sect repellants and rodenticides, propulsion of-rockets and the expulsion of liquids from containers such vas fire extinguishers.
  • gas-generating charge compositions of the foregoing general type and scope of utility are provided which, however, are characterized and distinguished essentially by the fact that they consist in major part of guanidine nitrate, together with a polynitro-phenol or a polynitroso-phenol United States atent g Cil 2,744,816 Patented l May 8,
  • the pressure required to render possible the self-sustained decomposition of a, charge based on guanidine nitrate may be progressivelynrfeduced by making up the guanidine nitrate vinto chargesfwith progressively increasing amounts of colloided,nitrocellulosenas a binding agent, by mixing the guanidine nitrate with a solution of nitrocellulose in a vvolatileI solvent, formingthe resulting paste into the required shape and evaporating oft the volatile solvent.
  • the. 'use' of a volatile solvent adds to the expense and necessitates' a drying operation, while the applicability of this method is also somewhat limited. ⁇ l
  • non-explosive gas-generating charges based on guanidine nitrate suitable for' a Vvariety of purposes and free from the disadvantages attendant 'on in proportion which may vary considerably but is always much less than one-half that of the guanidine nitrate'component.
  • the charge compositions of the invention are non-explosive and are not capable of being detonated by a blasting cap or other form of commercial detonator.
  • compositions such, for example, as smokeless powders, and conventional blasting compositions which are essentially detonating explosives having a base of nitrocellulose, of nitrocellulose and nitrol glycerin, or of oxidizing salts, but which may sometimes include guanidine nitrate as an incidental component.
  • guanidine nitrate undergoes an exothermic gas-evolving decomposition when it is strongly heated, but under atmospheric pressure conditions the reaction does not sustain itself if a portion only of a quantityof the compound is heated from atmospheric temperature to the temperature at which decomposition begins, unless external heating is maintained.
  • the decomposition leads Vto the production of steam, nitrogen, ammonia and oxides of carbon, but there is also formed a certain amount of a ditlicultly fusible yellow nitrogenous organic residue.
  • mixtures containing guanidine nitrate charges that are capable of decomposing with a high yield of permanent gases when lockallyj heated by a non-detonating element at a lower pressure than-is required for guanidine nitrate alone, said mixtures comprising guanidine nitrate with a proportion of a metallic hypophosphite or ammonium hypophosphite wherethe use of hypophosphites or gelatinized nitrocellul o se,v andcapable of self-sustained non -detonating decoufllpQ'S'if tion when merely locally heated,"with 'a 'high yield yof hot gases at relatively low pressure,v considerablylower than"l the 70Y atmospheres required for guanidine nitratealone, may be obtained by the use in'admixture with guanidine nitrate of a ⁇ polynitro-phenol or va p olynitroso-phenol," i. ⁇ e.
  • a phenol which contains in addition to at'leas "on i phenol hydroxyl group a plurality ofg'subs'titunt'groups each consisting of a nitrogen atomkattachedexclusivly to 'at least one terminal oxygen atom v'and' to one ofthe" nuclear carbon atoms of the phenol.
  • nitro'- guanidine is an explosive, whereas guanidine nitrate is not.
  • polynitroand polynitrosoderiva# tives of phenol that can be employed as thermal decomposition sensitizers in practicing the present invention, the following may be mentioned by way of example:f2': ⁇ 4 dinitro-resorcinol, 2:4:6 trinitro-resorcinol, 2:4 dinitroso'- resorcinol, 4:6 dinitro-ortho-cresol, 3&5 'dinitro-catechol, 2:6'dinitro-paracresol, and 3:5 dinitro-salicylic acidu'Of these, 2:4 dinitro-resorcinol works particularly-*well and is presently regarded as most desirable. y'
  • the proportion of polynitro-phenol for polynitroso-phenol sensitizer to be employedin the novel charges of the invention may varywidely depending upon such factors as the specic purpose and consequently the specific nature of the charge composition, and the conditions (particularly the pressure) under whichy the relatively slow, gas-generating thermal decomposition' is' intended to take place.
  • the limiting considerations are (1) that enough sensitizer must be employed fto'e'nsure' and y(2) that the proportionmust not be so'y high Vas to render such decomposition explosive or detonating in character.
  • the aliphatic carboxylic #acids provide Y a means for adjusting or controlling-the lgas-generating decomposition of the novel charge compositions .within reasonable limits, as maybe desired.
  • the use of sucha carboxylic 'acid in proportion-substantiallyexceeding about per cent-.of the weight of the guanidine nitratev is not ordinarilyto. be recommended for best results.
  • dilueiit .orlheateabsorbing' material such,.for example, as
  • smolreformingagent a. pesticide orotheriller. which ity maybe desired to. disperse. with minimum decomposition.thereof,..it isffrequently. necessary or desirablek to employ ,alargenproportion of ⁇ the aforesaid vsensitizer cbtuimnenLthanthe above-indicated maximum of 20 per cent, theweight of the guanidne'nitrate, in
  • the ⁇ charges according toy the invention may include ian iraliphaticrcarboxylic vacid. selected from fthe grdupeconsistin'gfoftartaric,A maleic, citricA and fumarie acids.; :jiThe :presence of.: an aliphatic carboxylic acid permits less 'ofthe .polynitrorphenol or Apolynitroso-phenol to be.: present: '"aThis.' is because the aliphatic carboxylic acids are 'factasensitizing agents for the decomposition of ⁇ guanidinenitratet Being cheaper than the polynitroandv polynitros-phmolspthey can therefore. sometimesbe used Generally speaking,
  • the generated gases contain Aappreciable'quantities ofvaporized condensable organic matef rials, the presence of which 'may be ⁇ undesirable initier ⁇ v tain applications' -of the charges e. g. if they are yto'be usedas power gases in driving enginesor operating 4other mechanical devices where these organic vapors Vcan condense and cause fouling of pipes or moving parts.
  • a. small pro- ⁇ portion of a promoter such as vanadium pentoxide, amounting forv example to about 0.2 toll per cent ofthe weight .of the guanidine nitrate, has the veect .Ofcompleting the decomposition of the guanidine nitrate, thus.
  • molybdic Yacid, molybdic oxide, ammonium molybdate may be usedin place cfa vanadium compound as a promoter or catalyst for' the same purpose.
  • These materials, or 'the residual' thermal. decomposition products thereof,'as well as the surface contact materialsv tob'e presently mentioned, may Vbe broadly termednonvolatile heat-resistant' materials vcapable of acting cata lyticall'y to promote maximum production of gases .in the selfsustaining decomposition ⁇ of the charge. ,y
  • heat-resisting cata'- lytic solid surfaces'that'are larnentary in character such as those of iron,;s.t'eel or platinum wire ⁇ gauze,or asbestos,
  • the use of the potassium nitrate is especially desirable if the charge is in an unusually cold condition before it is locally ignited, or in an environment such that the gases and vapors are at a lower temperature than that at which they would normally be generated.
  • Using as much as 5% potassium nitrate is permissable, but is virtually never necessary. Therefore since it would increase the quantity of residual slag and also correspondingly reduce the proportion of guanidine nitrate in the charge, the use of as much as 5% is virtually never resorted to in practice.
  • Charges made in accordance with the invention may be used for instance for actuating gas pressure operated mechanical devices, e. g. for driving engines, or for operating pneumatic tools, for operating re extinguishers, for propulsion of rockets and other gas escape reaction propelled devices, for dispersing insecticidal or the like substances, for making colored smokes, or for safety blasting operations by means of blasting assemblies in which the charge is caused to undergo decomposition in a pressure resisting container adapted to vent the gases once a predetermined pressure has been built up within the container.
  • the charge may be in powder, granular or compact form of any required shape, and may or may not include ingredients for reducing or raising the temperature of the gases it generates.
  • thermally volatilizable fumigating or smoke producing materials are examples of ingredients which reduce the temperature of the said gases and, by way of example, ammonium perchlorate and ammonium nitrate are reagents which raise the temperature of the said gases.
  • charges embodying the invention are not for power-gas production but include insecticidal or other substances to be dispersed, such substances may be thermally volatilizable materials as, for instance, insect repellants, insecticides, fungicides, bactericides andother pesticides; 4as well as smoke-producing compounds, includng colored dyestuis.
  • insecticidal or other substances to be dispersed such substances may be thermally volatilizable materials as, for instance, insect repellants, insecticides, fungicides, bactericides andother pesticides; 4as well as smoke-producing compounds, includng colored dyestuis.
  • the charge will usually be required to decompose under atmospheric pressure conditions.
  • any of the aforesaid materials is an organic compound it will be understood that, if the charge is to include asbestos bre or other material of large-surface characteristics, such surfacecontact'material must be employed in such manner that the l'gases and vapors will not undergo to any extent a4 reaction on its surface so intense as to destroy a large proportion of the volatilizable compound in the gas stream.
  • the volatilization of the organic compound has in, itself a cooling etect so that if suiicient of such compound is used the temperature will be too low for any such undesirably intense surface reaction to take place.
  • 4:6 dinitro-ortho-cresol is a polynitrophenol that has itself marked insecticidalv and arachnicidal properties, a fact which may be taken advantage of toa certain extent if the charge contains an excess of the amount of this polynitro-phenol over that recommended hereinbcfore for a charge to be used solely for power-gas generating purposes.
  • an excess of this material is present, not all of it will be decomposed by the" gas producing reaction and the excess will be volatilized and available for effecting fumigation. Normally, however,
  • a specicreagent such -as DBT or Gammexane as illustrated in certain of the following-examples, for producing a fumigating device of the type proposed.
  • the amount of insecticidal or other volatilizable or dispersible material thus included in the charge should not materially exceed about 20 per cent by weight of the entire charge.
  • Another way of reducing the temperature of the gases generated by the guanidine nitrate decomposition is to include in the charge a small proportion, not exceeding about 10 per cent', of a carbonate, e. g. calcium carbonate, decomposable at the temperatures involved, e. g. on the order of l000 C.
  • the amount of such inclusion should ordinarily not exceed about 10 per cent of the charge as a maximum.
  • the charge may safely include up to 20 per cent ammonium nitrate, or up to l0 per cent ammonium perchlorate, provided that with these maximum proportions the charge does not contain more than about 10 per cent of the polynitroor polynitroso-phenol, and provided the mixture is compressed to a density of not less than 1.4 cc. per gram.
  • an oxidizing salt such as ammonium nitrate or ammonium perchlorate
  • Fig. l is a cross section in elevation of one type of cartridge containing a charge ⁇ embodying the invention.
  • Fig. 2 is a cross section in elevation of another type of cartridge illustrating a typical use of a slightly modied charge.
  • Example 1 the charge composition is intended primarily for production of power-gases, with virtually complete decomposition of the guanidine nitrate base, and substantial absence from the gases of organic material condensable in the apparatus utilizing said gases. v To this end, a mixture of the composition:
  • the tube containing the composition is used to operate amante a motonoi rotary ,blower design at a progressivelyin-l creasing speed at aconstant working pressurea ofi about 120 lbs. per square inch. .
  • Example 2 In this case also, production of power gases substantiallyv freefrom condensable components is the objective.
  • the pellet 20 with its asbestos sheath 21 is ejected from the mould and fitted into a cylindrical container (not shown) of approximately l diameter closed at one end and fitted withy ascrew-on cap at the other end carrying a jet 0.055 inch in diameter.
  • the ignition system, indicated generally at 22, for the pellet at the open .end consists of a sliver of cordite 23 heldfon the surface of the composition by means of a tightly tting circular disk of 60-mesh BSS stainless Ysteel wire cloth 24 with a length of thin black-powder fuse 25 runningy from the cordite to the exterior through the jet in the cap of the container.
  • This miniature jet motor forms thepropulsion unit. of a model racing car.
  • the ignition is brought about byigniting the fuse with a match which ignites the cordite, which in turn locally heats the composition of the 'charge to the tmperature at which the evolutionof the gases becomes active, the decomposition then sustaining, itself through the charge. In this manner a thrust of 3 oz. weight lasting for 20 seconds is exerted on the model racing car.
  • the ash is a coherent skeleton of the pellet and amounts to, about 1% of its weight.
  • Alpha-alpha-bis- (parachloro-phenyl) -beta-beta-betatrichloroethan'e (DDT) 15 is preparedby .grinding the ingredients together until. they are well mixed in the form of a tine powder. 2O grams of the mixturev are consolidated into the form of a pellet 1 inch. indiameter by compression. in a moldand ejected.
  • the resulting insecticidal pellet when strongly-heated ⁇ atA contacted b y it, Ithusrendering themlethal .to houseies (e. g.) for some time.
  • the pellet leaves. anion-volatiley residue amounting tol about 10% of its weight.V
  • poly-Y nitrophenyl- is employed in much larger proportion than in Examplesl ⁇ and2.
  • the quantityl of 4this material employed amounts ⁇ to 26.3% ⁇ by weight of the guanidine nitratewhich latter, however, still remains the greatlypreponderating or major ingredient of said charge.: , The 10% residue left bythe pelletcon ⁇ sistsin-part of the before-mentioned diicultly fusible yellow nitrogeneous.- organic material, due tojomissiontfrom this charge. of vanadium pentoxide .or an equivalent pro-A moter necessary to ensure complete decomposition of the guanidine A.nitrate at atmospheric pressure.
  • the .omis. sion also of asbestos or other large-surface:heat-resistant contactmaterials; from this type of charge has the advantage of permitting a larger proportion. of the organicim secticidal material carried by the generated plino escape destructive ,decomposition and to perform its intended, function.
  • Example 4 A mixtureof'the composition:
  • a gas-generating charge 'em-i bodying the invention consists in major part, ⁇ most desir-l ahly at least 60 per cent, of guanidine nitrate heat-sensitized by avariable but always much smaller quantity of a lphenolof the character specified, never exceeding 35.
  • the novel compositions maybe made by simple admixture of the ingredients, and that when the charge is required to be ofcompact structure'andv predetermined form so that it will react only on its exposed external surface, it may be made by compressing the mixture into a mold of the desired shape. Moreover, ifit is required to protect a portion ofthe surface of the compact charge from the hot -gases evolved by means of an adherent covering of heat-insulating material, this may if desired be done in the course of they pressing operation of applying protective material to the surface of the charge after it has been shaped.
  • the gas-producing mixtures of the present invention undergo decomposition much more slowly than do blackpowder compositions, for example, and henceare safer to handle.
  • the gases can be produced at temperatures on the order of 1000 C., which is relatively low for propellent compositions, rendering them particularlyt well suited for use in driving engines.
  • gases generated from guanidine nitrate sensitized by nitrocellulose are much hotter than this, sometimes too hot to use for driving engines.
  • compositionsof the invention can be pressed into tubes and therebyiobtain layer-by-layer combustion, without any danger 4of the .compressed charges breaking up and exposing uncontrolled burning surfaces.
  • 99% of the charge can be converted into gaseous products, leaving behind only about l per cent residue which, moreover, is not entrained in the gases.
  • the temperature of propellent gases can be higher for rockets than for engines, the invention provides novel charge compositions that can be advantageously employed in rockets because said compositions can be used at relatively low pressures, thus requiring only light casings for such rockets.
  • the novel kcompositions may be employed in loose powder form instead of being compressed into pellets.
  • the ingredients of the novel compositions are all dry materials except that a small amount of liquid, on the order of 1 per cent or thereabouts, may be included, for example mineral oil (see' Example 2 hereinabove), to reduce dusting where some or all of the ingredients are in nely powdered form.
  • the two indispensable components of the novel gas-generating charges namely, guanidine nitrate and the decomposition-assisting phenol
  • the two indispensable components of the novel gas-generating charges together constitute at least 75 to 80 per cent of the whole charge, whether or not the charge includes diluent material of the character hereinabove pointed out. Where such diluent is absent, these two components most desirably constitute at least 90 to 95 per cent or more of the charge.
  • Examples 1 and 2 given hereinabove which represent charge compositions that are highly satisfactory where maximum production of clean power gases is the primary objective, somewhat more than 98 per cent of each of the described charges consists of said two components, the proportion of the phenol approximating l per cent of the charge in both instances.
  • a non-explosive gas-generating charge consisting in major part of guanidine nitrate and comprising admixed therewith, in proportion not exceeding 35 per cent by 2.
  • a non-explosive gas-generating charge capable of self-sustained, exothermic non-detonating, tlameless, decomposition at relatively low pressure upon heating a localized portion thereof to incipient active decomposition temperature which charge consists in major part of guanidine nitrate and further includes an admixed compound selected from the group consisting of 2:4 dinitroresorcinol, 2:4:6 trinitro-resorcinol, 2:4 dinitroso-resorcinol, 4:6 dinitro-orthocresol, 3:5 dinitro-catechol, 2:6 dinitro-paracresol, and 3:5 dinitro-salicylic acid, the proportion of such admixed compound being from about 3 to about 35 per cent by weight of the guanidine nitrate component.
  • a non-explosive gas-generatingfv :.zltargeas@ claimed in claim 1,.-.wherein ⁇ aportiononly ofj-"suehlphenol' is replaced :by an aliygahatic': carboxylic ⁇ acid yin. amount: .not exceeding 1.0.,per-cent1of ⁇ the chargezfby. weight, said ⁇ car-- boitylic acidlbeingselected;from the gronpfconsistingrot'y tartaric,.maleic, .citric-and v.fumarie acids. .v
  • material is selectedy from the group consistingoffironfsteel,

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  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
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US3027284A (en) * 1962-03-27 Composite propellants containing a
US3027282A (en) * 1958-12-29 1962-03-27 Phillips Petroleum Co Composite propellants containing modifying agents
US3035950A (en) * 1959-02-27 1962-05-22 Phillips Petroleum Co Reinforced gelled propellants
US3049452A (en) * 1957-08-16 1962-08-14 Phillips Petroleum Co Rubber and propellant composition containing the same
US3145192A (en) * 1957-07-01 1964-08-18 Thiokol Chemical Corp Acetylenic polyurethanes useful as propellants
US3148620A (en) * 1959-08-14 1964-09-15 Wegematic Corp Wear reduction additives
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US3242139A (en) * 1960-01-25 1966-03-22 Phillips Petroleum Co Polyurethane compositions based on 3, 11-dioxa-5, 7, 9-trinitraza-1, 13-tridecanediol
US3311054A (en) * 1965-06-21 1967-03-28 John E Foster Smoke marker arrangement
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US3422169A (en) * 1959-04-01 1969-01-14 Hercules Inc Nitrocellulose product and method of manufacture of propellant grains employing same
US3426684A (en) * 1968-01-18 1969-02-11 Wegematic Corp Wear reduction additives
US4328736A (en) * 1980-06-02 1982-05-11 The United States Of America As Represented By The Secretary Of The Navy Fuseless explosive propellant cartridge
EP1151976A1 (de) * 2000-05-02 2001-11-07 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Verfahren zum Aufblasen eines Gegenstandes
EP1151978A1 (de) * 2000-05-02 2001-11-07 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Verfahren zur Erzeugung von Gas
EP1151977A1 (de) * 2000-05-02 2001-11-07 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Verfahren zur Erzeugung von Gas zur Bereitstellung von Energie
EP1153903A1 (de) * 2000-05-08 2001-11-14 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Verfahren zur Erzeugung von Gas
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US20050115722A1 (en) * 2003-12-02 2005-06-02 Lund Gary K. Method and apparatus for suppression of fires
US20080149232A1 (en) * 2006-12-15 2008-06-26 Jason Newell Gas generant compositions
US20100307775A1 (en) * 2009-06-04 2010-12-09 Alliant Techsystems Inc. Gas-generating devices with grain-retention structures and related methods and systems
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US20130153098A1 (en) * 2010-03-26 2013-06-20 Sudhakar R. Ganta Gas Generant Compositions
US8616128B2 (en) 2011-10-06 2013-12-31 Alliant Techsystems Inc. Gas generator
US8939225B2 (en) 2010-10-07 2015-01-27 Alliant Techsystems Inc. Inflator-based fire suppression
US8967284B2 (en) 2011-10-06 2015-03-03 Alliant Techsystems Inc. Liquid-augmented, generated-gas fire suppression systems and related methods
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JPH08231291A (ja) * 1994-12-27 1996-09-10 Daicel Chem Ind Ltd ガス発生剤組成物
US5641938A (en) * 1995-03-03 1997-06-24 Primex Technologies, Inc. Thermally stable gas generating composition
US5866842A (en) * 1996-07-18 1999-02-02 Primex Technologies, Inc. Low temperature autoigniting propellant composition
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US2195965A (en) * 1936-10-22 1940-04-02 Ici Ltd Gas producing cartridge
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US3049452A (en) * 1957-08-16 1962-08-14 Phillips Petroleum Co Rubber and propellant composition containing the same
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US3422169A (en) * 1959-04-01 1969-01-14 Hercules Inc Nitrocellulose product and method of manufacture of propellant grains employing same
US3382806A (en) * 1959-05-01 1968-05-14 Exxon Research Engineering Co Tubular packet
US3204558A (en) * 1959-08-14 1965-09-07 Wegematic Corp Wear reduction additives
US3148620A (en) * 1959-08-14 1964-09-15 Wegematic Corp Wear reduction additives
US3242139A (en) * 1960-01-25 1966-03-22 Phillips Petroleum Co Polyurethane compositions based on 3, 11-dioxa-5, 7, 9-trinitraza-1, 13-tridecanediol
US3151164A (en) * 1960-01-25 1964-09-29 Phillips Petroleum Co Nitraza thia polymer compositions
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US3397636A (en) * 1967-03-22 1968-08-20 Wegematic Corp Wear reduction additives
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US4328736A (en) * 1980-06-02 1982-05-11 The United States Of America As Represented By The Secretary Of The Navy Fuseless explosive propellant cartridge
WO2001083402A1 (en) * 2000-05-02 2001-11-08 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Process for generating a gas
EP1151978A1 (de) * 2000-05-02 2001-11-07 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Verfahren zur Erzeugung von Gas
EP1151977A1 (de) * 2000-05-02 2001-11-07 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Verfahren zur Erzeugung von Gas zur Bereitstellung von Energie
EP1151976A1 (de) * 2000-05-02 2001-11-07 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Verfahren zum Aufblasen eines Gegenstandes
WO2001083404A1 (en) * 2000-05-02 2001-11-08 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Process for inflating an object
WO2001083403A1 (en) * 2000-05-02 2001-11-08 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Process for generating a gas for providing energy
EP1153903A1 (de) * 2000-05-08 2001-11-14 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Verfahren zur Erzeugung von Gas
WO2001085648A1 (en) * 2000-05-08 2001-11-15 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Process for the generation of a gas
US20050115721A1 (en) * 2003-12-02 2005-06-02 Blau Reed J. Man-rated fire suppression system
US20050115722A1 (en) * 2003-12-02 2005-06-02 Lund Gary K. Method and apparatus for suppression of fires
US20060278409A1 (en) * 2003-12-02 2006-12-14 Blau Reed J Man-rated fire suppression system and related methods
US7337856B2 (en) 2003-12-02 2008-03-04 Alliant Techsystems Inc. Method and apparatus for suppression of fires
US20080149352A1 (en) * 2003-12-02 2008-06-26 Alliant Techsystems Inc. Method and apparatus for suppression of fires
US8408322B2 (en) 2003-12-02 2013-04-02 Alliant Techsystems Inc. Man-rated fire suppression system and related methods
US7845423B2 (en) 2003-12-02 2010-12-07 Alliant Techsystems Inc. Method and apparatus for suppression of fires
US9919173B2 (en) 2003-12-02 2018-03-20 Orbital Atk, Inc. Man-rated fire suppression system and related methods
US20110226493A1 (en) * 2003-12-02 2011-09-22 Alliant Techsystems Inc. Man rated fire suppression system and related methods
US20080149232A1 (en) * 2006-12-15 2008-06-26 Jason Newell Gas generant compositions
US8672348B2 (en) 2009-06-04 2014-03-18 Alliant Techsystems Inc. Gas-generating devices with grain-retention structures and related methods and systems
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JP2013523571A (ja) * 2010-03-26 2013-06-17 ドマゼット スラベン ガス生成組成物の製造方法
US20130153098A1 (en) * 2010-03-26 2013-06-20 Sudhakar R. Ganta Gas Generant Compositions
US8939225B2 (en) 2010-10-07 2015-01-27 Alliant Techsystems Inc. Inflator-based fire suppression
US8616128B2 (en) 2011-10-06 2013-12-31 Alliant Techsystems Inc. Gas generator
US8967284B2 (en) 2011-10-06 2015-03-03 Alliant Techsystems Inc. Liquid-augmented, generated-gas fire suppression systems and related methods
US9682259B2 (en) 2011-10-06 2017-06-20 Orbital Atk, Inc. Fire suppression systems and methods of suppressing a fire
US11040229B2 (en) * 2012-01-18 2021-06-22 Acell Industries Limited Fire suppression system

Also Published As

Publication number Publication date
GB644073A (en) 1950-10-04
ES184896A1 (es) 1949-01-01
AT171721B (de) 1952-06-25
DE909424C (de) 1954-04-15
CH277311A (de) 1951-08-31
FR970531A (fr) 1951-01-05

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