EP0723530A1 - Procede de preparation de compositions a base de tetrazole anhydre generatrices de gaz - Google Patents

Procede de preparation de compositions a base de tetrazole anhydre generatrices de gaz

Info

Publication number
EP0723530A1
EP0723530A1 EP94925726A EP94925726A EP0723530A1 EP 0723530 A1 EP0723530 A1 EP 0723530A1 EP 94925726 A EP94925726 A EP 94925726A EP 94925726 A EP94925726 A EP 94925726A EP 0723530 A1 EP0723530 A1 EP 0723530A1
Authority
EP
European Patent Office
Prior art keywords
oxidizer
fuel
anhydrous
particles
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP94925726A
Other languages
German (de)
English (en)
Other versions
EP0723530A4 (fr
Inventor
Reed J. Blau
Gary K. Lund
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ATK Launch Systems LLC
Original Assignee
Thiokol Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/101,396 external-priority patent/US5682014A/en
Priority claimed from US08/178,572 external-priority patent/US5472647A/en
Application filed by Thiokol Corp filed Critical Thiokol Corp
Publication of EP0723530A1 publication Critical patent/EP0723530A1/fr
Publication of EP0723530A4 publication Critical patent/EP0723530A4/fr
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033—Shaping the mixture
    • C06B21/0066—Shaping the mixture by granulation, e.g. flaking
    • 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

  • the present invention relates to a method for making novel gas generating compositions which are useful for inflating automobile air bags and similar devices. More particularly, the present invention relates to a method for making gas generating pyrotechnic compositions based on anhydrous tetrazole compounds as a primary fuel.
  • the art has been seeking an acceptable non-azide gas generant which has the desired combination of properties for being a drop-in replacement for the conventional sodium azide-fueled gas generating composition used in air bags in passenger vehicles.
  • a proposed replacement for the conventional sodium azide-fueled gas generant must be capable of being manufactured and formed into a pill, pellet, extruded cylinder, or other desired shape charge.
  • the desired shape typically a pellet, must be capable of retaining structural integrity.
  • Various methods have heretofore been proposed for processing gas generant compositions to obtain shaped charges such as pellets.
  • different gas generant compositions behave differently during the pelletizing process, and particular process conditions suitable for fabricating objects composed of one gas generant are not necessarily applicable to processing or fabricating objects, such as pellets, composed of a different gas generant composition.
  • shaped charges such as a pellets, comprised of non-azide tetrazole-fueled gas generating compositions which are based on substantially nontoxic starting materials and which produce substantially nontoxic reaction products. It would be, in particular, an advancement in the art to produce combustion gases which primarily consist of nitrogen, with lesser amounts of carbon dioxide and water vapor so as not to exceed allowable occupant exposure standards for carbon dioxide and carbon monoxide. It would be another advancement in the art to prepare shaped charges, such as pellets, comprised of gas generating compositions which combust to produce limited particulate debris and limited undesir ⁇ able gaseous products. It would also be an advancement in the art to prepare pellets comprised of gas generating compositions which combust and form a readily filterable solid slag upon reaction.
  • the method according to the present invention overcomes or minimizes processing difficulties encountered in manufacturing shaped charges, such as pellets, from anhydrous tetrazole-fueled gas generant compositions.
  • a method according to the present invention involves obtaining a desired quantity of gas generating material comprising particles of at least one oxidizer and particles of at least one tetrazole as the fuel; preparing a wet mixture containing the gas generating material; drying the material to an anhydrous condition having a specified weight average particle size; and pressing the anhydrous material into pellets.
  • the gas generating material is preferably pelletized from anhydrous granules obtained from a wet mixture which can be agglomerated, such as a granulatable slurry or paste.
  • the particle sizes of the oxidizer and the tetrazole fuel can also be controlled within pre-selected number average particle size ranges when preparing the slurry or paste.
  • the present method involves preparing shaped charges, such as pellets, from an anhydrous gas generating composition by forming a quantity of granulated anhydrous gas generating material into a shaped charge wherein the gas generating material comprises an oxidizer and a non-azide fuel which is of the tetrazole class.
  • a preferred method involves preparing pellets from the anhydrous gas generating composition by slurrying a quantity of gas generating material which comprises oxidizer particles having a number average particle size greater than 1 micron and fuel particles having particles sizes greater than 1 micron wherein the fuel is selected from the group consisting of tetrazoles; if necessary, rendering the slurry capable of being made particulate, such as granulatable, such as by drying, for instance, the slurried material; rendering the slurry into particles, such as granules, having sizes of at least about 100 mesh; drying the granulated material to an anhydrous condition; and pelletizing the anhydrous granulated material, i.e., shaping the anhydrous granules into pellets.
  • the slurry can be obtained by blending effective amounts of a fuel from the tetrazole class, and an oxidizer in sufficient amounts of a medium, such as water. It is not necessary nor particularly desirable that the fuel and/or oxidizer be rendered anhydrous prior to mixing.
  • the slurry can be prepared in one step or in a series of steps.
  • the number average particle size of the tetrazole fuel used in preparing the slurry can be in the range of from about 1 micron to about 100 microns, although a range of about 10 microns to about 40 microns is presently preferred.
  • the number average particle size of the oxidizer, such as CuO, used in preparing the slurry can be in the range of from about 1 micron to about 20 microns, although a range of about 3 microns to about 10 microns is presently preferred, such as a number average particle size greater than about 5 microns.
  • Sub- micron sized oxidizer particles are not presently preferred because the pellets ultimately produced have been observed to crumble and lose pellet integrity within 24 hours at Rh 45%.
  • the medium is water.
  • solvents in which the tetrazole exhibits some.solubility may be used such as volatile organic solvents such as, for instance, alcohols such as methanol, ethanol, and propanol, and ketones such as acetone or methylethyl ketone.
  • the amount of water is generally selected to be sufficient to obtain a granulatable slurry, or a compactable powder which can be granulated or rendered granulatable.
  • the slurry can comprise less than about 50 % by weight water with the gas generating ingredients comprising the remainder.
  • the slurry can comprise about 3% to about 40% by weight water and from about 60% to about 97% by weight of the gas generating composition, although it is preferred to use at least about 20 % by weight and up to about 40 % by weight water. Predictability of ballistic performance may be adversely affected by straying substantially beyond the preferred water concentration.
  • a selected amount of water and the gas generating compositions can be mixed to obtain a damp compactable powder.
  • the damp powder can, if desired, be mixed with additional water to obtain a slurry material having a paste-like consistency.
  • obtaining a pulverulent anhydrous gas generant composition before preparing the slurry is neither necessary, nor particularly advantageous in the present process.
  • the particular species of a hydrated tetrazole fuel and the particular oxidizer selected should, however, have an average number particle size as indicated elsewhere herein when preparing the slurry.
  • the fuel species and oxidizer can be added at once, alternatively, or in portions to the slurry medium provided that the materials are in intimate contact, and sufficient compositional uniformity of the slurry is achieved.
  • the water has a pH in the range of about 5 to about 11 prior to being combined with the fuel particles and oxidizer particles.
  • the pH decreases to about pH ⁇ 3.
  • a pH substantially outside the preferred ranges is undesired owing to dissolution of the oxidizer and to avoid complex formation. Poor pH control can be evident in even the final anhydrous product. It is preferable to avoid allowing the slurry or suspension of gas generant particles to remain wet, in water or other solvent, for an extended period of time.
  • Complexes of the tetrazole may form, or complexes of the tetrazole and oxidizer may form. For instance, a BTA-Cu complex is dark green, and a Cu-5AT complex is green.
  • Uncontrolled complex formation during the slurrying step may result in less predictable ballistic properties of the final anhydrous product.
  • the slurry can be dried, if necessary, to obtain a partially dried granulatable material, although it is not desired to render the material anhydrous before granulation.
  • the material is rendered into particulate form having a weight average particle size from about 100 mesh and to about 14 mesh.
  • Crumbs, prills, extruded cylinders, disks, pills, or granules of the appropriate size distribution can be used.
  • General techniques adaptable to agglomerating, i.e., increasing particle size include, granulating, extruding, bricketting, pelleting, tableting, and spray drying, and are described in Perry's Chemical Engineers's Handbook, Section 16 (3rd. Ed. 1950), the complete disclosure of which is incorporated herein by reference, provided that the desired particle sizes are obtained.
  • the material can be wet-meshed or wet-extruded to obtain granules.
  • the granules can have particle sizes in the range of, for instance, from about 14 to about 100 mesh. It is presently preferred that the particles, such granules, have a weight average particle size in the range of from about 14 to about 30 mesh.
  • the material which has been rendered into particulate form is dried to remove solvent to achieve an anhydrous state.
  • the essential absence of free water including water measured as hydrate or unbound but occluded or adventitious moisture, is indicative of the anhydrous state.
  • the material is rendered water-free.
  • a dried tetrazole fueled composition consisting of 22.9% BTAmonohydrate and 77.1% CuO can still lose about 3 to 4 wt% when further dried, and that the additional weight loss reflects removal of principally hydrate and small amounts of unbound but occluded or adventitious moisture.
  • the drying contemplated herein involves removal of the water of hydration and any occluded or unbound or adventitious water.
  • the precise temperature and length of time of drying are not critical to the practice of the invention, as long as anhydrous granules are obtained. For instance, drying the agglomeratable material to constant weight at less than 75°C, generally less than 45°C, followed by further drying, such as at a temperature of from about 110°C to about 140°C, for a sufficient duration of time to remove hydrate, occluded or unbound, and adventitious moisture.
  • the just mentioned sufficient time will be a function of the temperature and pressure conditions prevailing during the drying step.
  • Adequate achievement of the anhydrous state as specified or contemplated herein can be readily determined by subsequently exposing an anhydrous composition to a relative humidity of at least 45% for a minimum of 24 hours. A gain in weight of the composition resulting from this treatment to within about 0.5% of the theoretical amount due to fuel hydration is indicative of sufficient dehydration of the composition.
  • anhydrous means removal of the solvent residue as well as water of hydration and any occluded or unbound or adventitious water.
  • the slurry can, if desired, be converted directly to the desired sized and anhydrous particles, such as granules, by, for instance, extruding the slurry in a heated and vented extruder or spray drying the slurry.
  • anhydrous particles such as granules
  • Other means for converting the slurry directly to the desired sized particles, such as granules, can also be used.
  • Solid shaped charges are prepared from the anhydrous material.
  • the anhydrous granulated material is typically pelletized, i.e. pressed into pellet form to meet the specific requirements for use in automotive safety restraint systems.
  • the solid shaped charges produced according to the method of the present invention have at least one compound of the tetrazole class (sometimes referred to herein as simply "tetrazole”) as a fuel and at least one appropriate oxidizer.
  • the pellets of the gas generant composition are based on anhydrous tetrazoles, such as 5-aminotetrazole and bitetrazoleamines, or a salt or a complex thereof or mixtures thereof.
  • One presently preferred bitetrazoleam- ine is bis- (1(2)H-tetrazol-5-yl)-amine (hereinafter sometimes referred to as "BTA”) .
  • BTA (1(2)H-tetrazol-5-yl)-amine
  • bitetrazole-amines such as those having the following structure:
  • X, R ⁇ and R 2 each independently, represent hydrogen, methyl, ethyl, cyano, nitro, amino, tetrazolyl, a metal from Group la, lb, Ila, lib. Ilia, IVb, VIb, Vllb or VIII of the Periodic Table (Merck Index (11th Edition 1989) ) , or a nonmetallic cation of a high nitrogen- content base.
  • tetrazoles include tetrazole, 5-aminotetrazole
  • bitetrazole the n-substituted derivatives of aminotetrazole such as nitro, cyano, guanyl, and the like, and c-substituted tetrazoles such as cyano, nitro, hydrazino, and the like.
  • Salts or complexes of any of these tetrazoles including those of transition metals such as copper, cobalt, iron, titanium, and zinc; alkali metals such as potassium and sodium; alkaline earth metals such as strontium, magnesium, and calcium; boron; aluminum; and nonmetallic cations such as ammonium, hydroxylammonium, hydraziniu , guanidinium, aminoguanidinium, diaminoguanidinium, triaminoguanidinium, orbiguanidinium can also serve as the fuel in the pellets produced in accordance with the present invention.
  • transition metals such as copper, cobalt, iron, titanium, and zinc
  • alkali metals such as potassium and sodium
  • alkaline earth metals such as strontium, magnesium, and calcium
  • boron aluminum
  • nonmetallic cations such as ammonium, hydroxylammonium, hydraziniu , guanidinium, aminoguanidinium, diamin
  • oxidizer is included in the composition.
  • Inorganic oxidizing agents are preferred because they produce a lower flame temperature and an improved filterable slag.
  • Such oxidizers include metal oxides and metal hydroxides, such as transition metal oxides and transition metal hydroxides.
  • oxidizers include a metal nitrate such as, for instance, an alkali metal nitrate or strontium nitrate, a metal nitrite such as, for instance, an alkali metal nitrite or a nitrite of, for instance, strontium, cobalt or chromium, a metal chlorate such as, for instance, KC10 3 , a metal perchlorate such as, for instance, NaC10 4 , KC10 4 and the like, a metal peroxide such as, for instance, an alkaline earth peroxide, ammonium nitrate, ammonium perchlorate and the like.
  • a metal nitrate such as, for instance, an alkali metal nitrate or strontium nitrate
  • a metal nitrite such as, for instance, an alkali metal nitrite or a nitrite of, for instance, strontium, cobalt or chromium
  • a metal chlorate
  • metal oxides or hydroxides as oxidizers is particularly useful and such materials include for instance, the oxides and hydroxides of copper, cobalt, manganese, tungsten, bismuth, molybdenum, and iron, such as CuO, Co 2 0 3 , Fe 2 0 3 , Mo0 3 , Bi 2 Mo0 6 , Bi 2 0 3 , and Cu(OH) 2 .
  • oxide and hydroxide oxidizing agents mentioned above can, if desired, be combined with other conventional oxidizers such as Sr(N0 3 ) 2 , NH 4 C10 4 , and KN0 3 , for a particular application, such as, for instance, to provide increased flame temperature or to modify the gas product yields.
  • the tetrazole fuel is combined, in a fuel-effective amount, with an appropriate oxidizing agent to obtain a gas generating composition.
  • the tetrazole fuel comprises from about 10 to about 50 weight percent of the composition and the oxidizer comprises from about 50 to about 90 weight percent thereof. More particularly, a composition can comprise from about 15 to about 35 weight percent fuel and from about 65 to about 85 weight percent oxidizer.
  • Additives conventionally used in gas generating compositions, propellants, and explosives such as binders, burn rate modifiers, slag formers, release agents, and additives which effectively remove NO x can, if desired, be included in the anhydrous compositions obtained in accordance with the present invention.
  • the additives can be introduced when the slurry is being prepared or at another step in the present process.
  • Typical binders include lactose, boric acid, silicates including magnesium silicate, polypropylene carbonate, polyethylene glycol, and other conventional polymeric binders.
  • the binder can be added at any convenient stage of the process.
  • Typical burn rate modifiers include Fe 2 0 3 , K 2 B 12 H 12/ Bi 2 Mo0 6 , and graphite carbon fibers.
  • a number of slag forming agents are known and include, for example, clays, talcs, silicon oxides, alkaline earth oxides, hydroxides, oxalates, of which magnesium carbonate, and magnesium hydroxide are exempla ⁇ ry.
  • a number of additives and/or agents are also known to reduce or eliminate the oxides of nitrogen from the combustion products of a gas generant composition, including alkali metal salts and complexes of tetrazoles, aminotetrazoles, triazoles and related nitrogen heterocycles of which potassium aminotetrazole, sodium carbonate and potassium carbonate are exemplary.
  • the composition can also include materials which facilitate the release of the composition from a mold such as graphite, molybdenum sulfide, calcium stearate, or boron nitride.
  • Tetrazoles are commercially available or can be readily synthesized.
  • a synthesis of BTA is disclosed by Norris, et al., Cyanoguanyl Azide Chemistry, Journal of Organic Chemistry. 29: 650 (1964) .
  • Substituted tetrazole derivatives can be prepared from suitable starting materials, such as substituted tetrazoles, according to techniques available to those skilled in the art.
  • suitable starting materials such as substituted tetrazoles
  • derivatives containing lower alkyl, such as methyl or ethyl, cyano, or tetrazolyl can be prepared by adapting the procedures described in Journal of Organic Chemistry, 29: 650 (1964), the disclosure of which is incorporated by reference.
  • Amino-containing derivatives can be prepared by adapting the procedures described in Canadian Journal of Chemistry, 7:3677 (1969), the disclosure of which is incorporated herein by reference.
  • Nitro-containing derivatives can be prepared by adapting the procedures described in Journal of the American Chemical Society, 21:2327 (1951), the disclosure of which is incorporated herein by reference.
  • Other radical-containing deriva ⁇ tives such as those containing ammonium, hydroxylammonium, hydrazinium, guanidinium, amino- guanidinium, diaminoguanidinium, triaminoguanidinium or biguanidinium radicals, can be prepared by adapting the procedures detailed in Boyer, Nitroazoles, Organic Nitro Chemistry (1986) , the disclosure of which is incorporated by reference.
  • An embodiment of the present invention relates specifically to preparing anhydrous gas generant compositions in the form of pellets.
  • Anhydrous tetrazole compositions produce advantages over the hydrated forms. For example, a higher (more acceptable) burn rate is generally observed.
  • the methods of the present invention allow for pressing the composition in the anhydrous form such that pellets with good integrity are produced.
  • the pellet may be placed within a sealed container, or coated with a water impermeable material.
  • burn rate performance of an anhydrous tetrazole-fueled gas generant composition is good. Burn rates above 0.5 inch per second (ips) are preferred. Ideally, burn rates are in the range of from about 1.0 ips to about 1.2 ips at 1,000 psi. Burn rates in these ranges can be achieved. The burn rates compare favorably with the burn rates observed for sodium azide compositions.
  • pellets prepared by a preferred method are capable of exhibiting crush strengths in excess of 10 lb load in a typical configuration (3/8 inch diameter by
  • gas generants in pellet form are generally used for placement in gas generating devices, such as automobile supplemental restraint systems.
  • Gas generant pellets should have sufficient crush strength to maintain their shape and configuration during normal use and withstand loads produced upon ignition since pellet failure results in uncontrollable internal ballistics.
  • the compositions are capable of generating large quantities of gas while overcoming various problems associated with conventional gas generating compositions.
  • the compositions produce substantially nontoxic reaction products.
  • the compositions are particularly useful for generating large quantities of a nontoxic gas, such as nitrogen gas.
  • the compositions also avoid the use of azides, produce no sodium hydroxide by ⁇ products, and generate no sulfur compounds such as hydrogen sulfide and sulfur oxides.
  • compositions also produce only limited particulate debris, provide good slag formation and substantially avoid, if not avoid, the formation of nonfilterable particulate debris. At the same time, the compositions achieve a relatively high burn rate, while producing a reasonably low temperature gas.
  • the gas produced by the present invention is readily adaptable for use in deploying supplemental restraint systems, such as automobile air bags.
  • Suitable means for generating gas include gas generating devices which are used in supplemental safety restraint systems used in the automotive industry.
  • the supplemental safety restraint system may, if desired, include conventional screen packs to remove particulates, if any, formed while the gas generant is combusted.
  • the compactable powder is blended in a Hobart mixer with water (400.0 grams) for about 15 minutes to obtain a paste.
  • the paste is allowed to air dry at about 40°C until it achieves a consistency suitable for agglomeration, such as by granulation, corresponding to about 20 to 25 % by weight water.
  • the partially dried paste is suitable for granulation, and is forced through a 16 mesh screen to produce small granules.
  • the granules are then dried to constant weight at a temperature of about 31°C. An amount of the dried granules is removed and split into two portions of equal amounts. Both portions are further dried at about 120°C for about 24 hours to remove remaining water. To one portion is added calcium stearate (0.20 % by wt.) . Pill- shaped pellets (3/8" diameter) are pressed from each of the further dried portions. The pellets are subjected to a Rh 45% treatment for 24 hours at 25°C, and the pellet condition is monitored. The pellets retain their pellet shape after 24 hours exposure to Rh 45%.
  • a non-azide gas generating composition is prepared by blending 274.8 grams of the non-azide fuel, BTA monohydrate, having a nominal particle size of about 100 microns with 925.4 grams of copper oxide (CuO) having a nominal particle size of about 6 microns and 480 grams of water for about 90 minutes in a Hobart blender/mixer to obtain a past.
  • the paste is dried at 40°C to a consistency suitable for granulation.
  • the mixture is then meshed through a 18-mesh screen to produce granules which were then allowed to dry in the air at ambient conditions.
  • the granules are then pulverized for 30 minutes in a muller mixer to obtain a powder having an average particle size of substantially less than 100 microns.
  • a portion of the resultant powder is further dried at 120°C for an additional 24 hours to achieve an anhydrous composition.
  • the anhydrous powder is then pressed to produce 3/8-inch diameter pellets which are subsequently exposed to a Rh of 45% at 25 °C. The pellets lose all integrity within four hours.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Air Bags (AREA)

Abstract

Le procédé de l'invention consiste à préparer un générateur de gaz anhydre par transformation d'une quantité de matière génératrice de gaz anhydride granulaire en une charge façonnée dans laquelle la matière génératrice de gaz est un oxydant ainsi qu'au moins un combustible choisi dans le groupe constitué de tétrazoles. Plus spécifiquement, un procédé préféré de préparation d'une composition génératrice de gaz anhydride consiste à obtenir une boue d'une matière génératrice de gaz comprenant des particules oxydantes d'une taille supérieure à 1 micron, et des particules de combustible d'une taille supérieure à 1 micron, l'oxydant étant sélectionné dans le groupe comprenant un peroxyde de métal, un nitrate inorganique, un nitrite inorganique, un oxyde de métal, un hydroxyde de métal, un chlorate inorganique, un perchlorate inorganique, ou un mélange de ceux-ci, et le combustible étant sélectionné dans le groupe comprenant des tétrazoles; à granuler la boue afin d'obtenir des granulés d'une grosseur particulaire moyenne au poids sélectionnée; à sécher les granulés jusqu'à obtention d'un état anhydride; et à transformer en boulettes les granulés anhydres.
EP94925726A 1993-08-02 1994-08-02 Procede de preparation de compositions a base de tetrazole anhydre generatrices de gaz Ceased EP0723530A4 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US101396 1993-08-02
US08/101,396 US5682014A (en) 1993-08-02 1993-08-02 Bitetrazoleamine gas generant compositions
US08/162,596 US5501823A (en) 1993-08-02 1993-12-03 Preparation of anhydrous tetrazole gas generant compositions
US162596 1993-12-03
US178572 1994-01-07
US08/178,572 US5472647A (en) 1993-08-02 1994-01-07 Method for preparing anhydrous tetrazole gas generant compositions
PCT/US1994/008781 WO1995004014A1 (fr) 1993-08-02 1994-08-02 Procede de preparation de compositions a base de tetrazole anhydre generatrices de gaz

Publications (2)

Publication Number Publication Date
EP0723530A1 true EP0723530A1 (fr) 1996-07-31
EP0723530A4 EP0723530A4 (fr) 1996-09-25

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EP94925726A Ceased EP0723530A4 (fr) 1993-08-02 1994-08-02 Procede de preparation de compositions a base de tetrazole anhydre generatrices de gaz

Country Status (5)

Country Link
EP (1) EP0723530A4 (fr)
JP (1) JPH09501138A (fr)
AU (1) AU7553794A (fr)
CA (1) CA2167386C (fr)
WO (1) WO1995004014A1 (fr)

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Also Published As

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CA2167386C (fr) 1999-10-05
CA2167386A1 (fr) 1995-02-09
JPH09501138A (ja) 1997-02-04
EP0723530A4 (fr) 1996-09-25
WO1995004014A1 (fr) 1995-02-09
AU7553794A (en) 1995-02-28

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