EP0665201B1 - Gas generating mixture - Google Patents

Gas generating mixture Download PDF

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Publication number
EP0665201B1
EP0665201B1 EP19940119382 EP94119382A EP0665201B1 EP 0665201 B1 EP0665201 B1 EP 0665201B1 EP 19940119382 EP19940119382 EP 19940119382 EP 94119382 A EP94119382 A EP 94119382A EP 0665201 B1 EP0665201 B1 EP 0665201B1
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EP
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Prior art keywords
catalyst
characterized
mixture according
mixture
gzt
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EP19940119382
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German (de)
French (fr)
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EP0665201A1 (en
Inventor
Klaus Martin Dr. Bucerius
Helmut Schmid
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Priority to DE19944401213 priority Critical patent/DE4401213C1/en
Priority to DE4401213 priority
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Publication of EP0665201A1 publication Critical patent/EP0665201A1/en
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    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06DMEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/007Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating

Description

  • The invention relates to a gas-generating mixture of a fuel, an oxidizer and a catalyst.
  • Gas-generating mixtures of the aforementioned type - also called gas generator sets - are characterized in that they enable a high gas yield (> 14 mol / kg) during combustion. They are used for rocket and barrel weapon drives as well as for inflatable restraint (airbag) and rescue systems. In the civil sector in particular, thermal-mechanical insensitivity and non-toxicity of the starting mixtures, but also a lack of toxicity in the resulting gases are required. Many systems in use do not meet these requirements, or meet them only very inadequately.
  • The reaction of these fuels with the previously used catalysts and oxidizers shows an unsatisfactory gas composition and / or inadequate combustion behavior. Add to that many Reaction mixtures have such a high combustion temperature that - in airbag applications - the thermally sensitive sack materials are damaged.
  • The invention has for its object to lower the combustion temperature and increase the rate of combustion in a mixture of the structure mentioned in the introduction.
  • According to the invention, these contradictory requirements are met in that the oxidizer Cu (NO 3 ) 2 * 3Cu (OH) 2 and the catalyst consist of a metal oxide.
  • The oxidizer provided according to the invention results in cold and rapid combustion. The maximum pressure is reached within milliseconds, with the gas temperature remaining below harmful limits. Hitherto necessary slag formers, which in known systems for binding pollutants, e.g. Alkali oxides, required, can be omitted in the mixture according to the invention, so that a higher gas yield can be achieved.
  • The catalyst which is also used according to the invention is primarily used to reduce harmful gas (CO and NO), the term "catalyst" in the broader sense here denoting an active reaction component which can be implemented itself and has a reaction-guiding and / or reaction-accelerating effect. In a phase of the reaction determined by the thermal stability of the metal oxides, these oxides act as oxygen donors. The catalytic effect in the conversion of harmful gases CO + 1/2 O 2nd → CO 2nd
    Figure imgb0001
    can be determined by the particle size distribution or the average particle size of the oxides below 25 µm should affect. Not only the metal oxide catalyst, but also the oxidizer are thermally and mechanically stable and especially not hygroscopic.
  • Oxides or mixed oxides of the transition metals are particularly suitable as catalysts, but preferably V 2 O 5 / MoO 3 mixed oxides are used which contain portions of the thermally unstable phase V 2 O 4 , which can be prepared by partial reduction of V 2 O 5 . Further oxides, for example TiO 2 , can be used as promoters.
  • In civil applications in particular, non-toxic starting compounds and non-toxic reaction products are required. These requirements are met by N-rich and C-poor fuels. These include the well-known fuels TAGN (triaminoguanidine nitrate), NIGU (nitroguanidine), NTO (3-nitro-1,2,3-triazol-5-one) and the particularly high nitrogen content of the GZT (diguanidinium 5,5'- azotetrezolate) (DE 4 108 225). For this reason, TAGN, NIGU, NTO, but in particular GZT, are preferably used in the mixture according to the invention when used for rescue and restraint systems.
  • A preferred mixture consists of GZT and Cu (NO 3 ) 2 * 3Cu (OH) 2 with a balanced oxygen balance and up to 30% by mass of the catalyst.
  • The mixture can contain Fe 2 O 3 as the coolant, the oxidative properties of which can additionally be used in the reaction mixture (DE 41 33 655, EP 0 536 525).
  • example
  • It is a mixture consisting of GZT, a mixed oxide of V 2 O 5 and MoO 3 with the empirical formula
    V 6 Mo 15 O 60 as a catalyst and
    Cu (NO 3 ) 2 * 3Cu (OH) 2 as an oxidizer in a ratio of 24.64: 15.07: 60.29% by mass. This formulation is investigated experimentally in the ballistic bomb with regard to its ignition and combustion behavior. A pressure curve diagram according to the system is obtained. The diagram shows that the mixture has good ignition and combustion properties. With a loading density of 0.1 g / cm 3 , the maximum pressure is in the range of 310 bar (31MPa), which is reached after about 28 ms (t (pmax) = 28 ms). The pressure rise time between 30 to 80% of the maximum pressure is t 30-80 = 5.52 ms.
  • The combustion temperature can be determined very precisely by thermodynamic calculation. It is 2122 K. With the same GZT fuel and a balanced oxygen balance, other oxidizers deliver higher combustion temperatures. For example, they are - 2501 K for KNO 3 , 2850 K for NH 4 NO 3 and 3248 K for K Cl O 3 .

Claims (12)

  1. A gas generating mixture of a fuel, an oxidant and a catalyst, characterized in that the oxidant is Cu(NO3)2*3Cu(OH)2 and the catalyst is a metal oxide.
  2. A mixture according to claim 1, characterized in that the catalyst is a metal oxide mixture.
  3. A mixture according to claim 1, characterized in that the catalyst is a metal mixed oxide.
  4. A mixture according to claim 1 or 2, characterized in that the catalyst is a mixture of transition metal oxides.
  5. A mixture according to claim 1 or 3, characterized in that the catalyst is a transition metal mixed oxide.
  6. A mixture according to claim 5, characterized in that the catalyst consists of V2O5/MoO3 mixed oxides.
  7. A mixture according to claim 6, characterized in that the catalyst contains proportions of the thermodynamically unstable V2O4 phase.
  8. A mixture according to any of claims 1 to 7, characterized in that the catalyst also contains TiO2.
  9. A mixture according to any of claims 1 to 8, characterized in that the catalyst has a mean grain size < 25 µm.
  10. A mixture according to any of claims 1 to 9, characterized in that TAGN (triaminoguanidine nitrate), NIGU (nitroguanidine), NTO (3-nitro-1,2,3-triazol-5-one) or GZT (diguanidinium-5,5'-azotetrazolate) serves as the fuel.
  11. A mixture according to any of claims 1 to 10, consisting of a mixture of GZT, Cu(NO3)2*3Cu(OH)2 with equalised oxygen balance and a catalyst content to the reaction mixture up to 30% by mass.
  12. A mixture according to any of claims 1 to 11, characterized in that it includes Fe2O3 as a coolant.
EP19940119382 1994-01-18 1994-12-08 Gas generating mixture Expired - Lifetime EP0665201B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE19944401213 DE4401213C1 (en) 1994-01-18 1994-01-18 Gas-generating mixture
DE4401213 1994-01-18

Publications (2)

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EP0665201A1 EP0665201A1 (en) 1995-08-02
EP0665201B1 true EP0665201B1 (en) 1996-11-20

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EP19940119382 Expired - Lifetime EP0665201B1 (en) 1994-01-18 1994-12-08 Gas generating mixture

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EP (1) EP0665201B1 (en)
DE (1) DE4401213C1 (en)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5883330A (en) * 1994-02-15 1999-03-16 Nippon Koki Co., Ltd. Azodicarbonamide containing gas generating composition
DE4442170C1 (en) * 1994-11-26 1995-12-21 Fraunhofer Ges Forschung Non-toxic gas-generating mixt. with thermal-mechanical stability
DE4442169C1 (en) * 1994-11-26 1995-12-21 Fraunhofer Ges Forschung Non-toxic gas-generating mixt. with thermal-mechanical stability
DE19531288A1 (en) * 1995-08-25 1997-02-27 Temic Bayern Chem Airbag Gmbh Airbag propellant gas generator
US6497774B2 (en) 1996-07-22 2002-12-24 Daicel Chemical Industries, Ltd. Gas generant for air bag
US6527886B1 (en) 1996-07-22 2003-03-04 Daicel Chemical Industries, Ltd. Gas generant for air bag
US5608183A (en) * 1996-03-15 1997-03-04 Morton International, Inc. Gas generant compositions containing amine nitrates plus basic copper (II) nitrate and/or cobalt(III) triammine trinitrate
US6306232B1 (en) 1996-07-29 2001-10-23 Automotive Systems Laboratory, Inc. Thermally stable nonazide automotive airbag propellants
DE19712820A1 (en) * 1997-03-26 1998-10-01 Basf Ag Burning moderators for gas-generating mixtures
US6132538A (en) * 1998-07-30 2000-10-17 Autoliv Development Ab High gas yield generant compositions
JP2000319085A (en) * 1999-04-30 2000-11-21 Daicel Chem Ind Ltd Gas generating agent composition
US6143102A (en) * 1999-05-06 2000-11-07 Autoliv Asp, Inc. Burn rate-enhanced basic copper nitrate-containing gas generant compositions and methods
CZ20021056A3 (en) * 1999-09-27 2002-10-16 Daicel Chemical Industries, Ltd. Basic metal nitrate, process of its preparation and preparation with a gas-producing agent
US6224697B1 (en) 1999-12-03 2001-05-01 Autoliv Development Ab Gas generant manufacture
US6372191B1 (en) 1999-12-03 2002-04-16 Autoliv Asp, Inc. Phase stabilized ammonium nitrate and method of making the same
US6436211B1 (en) 2000-07-18 2002-08-20 Autoliv Asp, Inc. Gas generant manufacture
US6591752B2 (en) 2001-02-12 2003-07-15 Trw Inc. Ignition material for an igniter
US6589375B2 (en) 2001-03-02 2003-07-08 Talley Defense Systems, Inc. Low solids gas generant having a low flame temperature
US6875295B2 (en) 2001-12-27 2005-04-05 Trw Inc. Cool burning gas generating material for a vehicle occupant protection apparatus
US6964716B2 (en) 2002-09-12 2005-11-15 Daicel Chemical Industries, Ltd. Gas generating composition
US6872265B2 (en) 2003-01-30 2005-03-29 Autoliv Asp, Inc. Phase-stabilized ammonium nitrate
US20050257866A1 (en) * 2004-03-29 2005-11-24 Williams Graylon K Gas generant and manufacturing method thereof
WO2012087995A1 (en) * 2010-12-22 2012-06-28 3M Innovative Properties Company Recessed adhesive binding systems and methods of making same

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2604391A (en) * 1946-11-08 1952-07-22 Ici Ltd Gas-producing nondetonating composition
GB658643A (en) * 1949-01-12 1951-10-10 Alexander Cantlay Hutchison Improvements in or relating to solid gas generating charges
US3664898A (en) * 1969-08-04 1972-05-23 Us Navy Pyrotechnic composition
US4336085A (en) * 1975-09-04 1982-06-22 Walker Franklin E Explosive composition with group VIII metal nitroso halide getter
US4632714A (en) * 1985-09-19 1986-12-30 Megabar Corporation Microcellular composite energetic materials and method for making same
US4931112A (en) * 1989-11-20 1990-06-05 Morton International, Inc. Gas generating compositions containing nitrotriazalone
US4994123A (en) * 1990-05-29 1991-02-19 The United States Of America As Represented By The Secretary Of The Air Force Polymeric intermolecular emulsion explosive
US5145535A (en) * 1991-02-25 1992-09-08 United States Of America As Represented By The Secretary Of The Air Force Method for intermolecular explosive with viscosity modifier
DE4108225C1 (en) * 1991-03-14 1992-04-09 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De
DE4218531C1 (en) * 1991-10-11 1993-07-15 Bayern-Chemie Gesellschaft Fuer Flugchemische Antriebe Mbh, 8261 Aschau, De

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EP0665201A1 (en) 1995-08-02
US5542998A (en) 1996-08-06
DE4401213C1 (en) 1995-03-02

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