EP1006096A1 - Composition génératrice de gaz exempt d'azoture - Google Patents
Composition génératrice de gaz exempt d'azoture Download PDFInfo
- Publication number
- EP1006096A1 EP1006096A1 EP99123906A EP99123906A EP1006096A1 EP 1006096 A1 EP1006096 A1 EP 1006096A1 EP 99123906 A EP99123906 A EP 99123906A EP 99123906 A EP99123906 A EP 99123906A EP 1006096 A1 EP1006096 A1 EP 1006096A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- nitrate
- proportion
- composition according
- guanidine
- 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.)
- Granted
Links
Classifications
-
- 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
- Gas generating compositions used in safety devices used for motor vehicles mostly consist of a fuel based on sodium azide and an oxidizing agent. However, due to the toxicity of sodium azide, it was premature started looking for alternatives to the azide-containing gas generators To look for mixtures.
- US-A-5 608 183 describes a gas generating mixture containing between about 30 and 85 percent by weight of a fuel and between about 15 and about 70 percent by weight of an oxidizing agent.
- At least 60% by weight of the fuel consists of the nitrate of an acidic polyamine or a C 2 -C 3 -alkyldiamine, such as, for example, the nitrates of urea, guanidine, aminoguanidine, diaminoguanidine, semicarbazide, ethylenediamine, 1,3-propanediamine or 1, 2-propanediamine, or mixtures thereof.
- the oxidizing agent comprises at least 60% by weight of basic copper nitrate and / or cobalt triamine trinitrate. The mixture is processed in a wet process.
- the gas generating mixture known from US-A-5 608 183 has however, an insufficient willingness to ignite and a too low Burn-up speed. Due to the high proportion of basic Copper nitrate is also an increased proportion of toxic gases in the released Detectable gas mixture. Processing the mixture in A wet process requires additional drying stages and is therefore expensive.
- the German utility model No. 298 06 504 represents a gas-generating Composition ready, the one of at least two components existing fuel mixture in a proportion of 20 to 60 wt .-% and an oxidizer mixture consisting of at least three components in a proportion of 40 to 80% by weight, based in each case on the total composition, includes.
- the fuel mixture of the known composition is from 5 to 95% by weight of a guanidine compound, 5 to 95 % By weight of a heterocyclic organic acid, for example Cyanuric acid, as well as 0 to 20% by weight of other fuels.
- the oxidizer mixture of the known composition consists of one or more transition metal oxides in a proportion of 20 to 70% by weight and 10 to 50% by weight of basic copper nitrate and 2 to 30 % By weight metal chlorate, metal perchlorate, ammonium perchlorate, alkali nitrate, Alkaline earth nitrate or mixtures thereof.
- an additional fuel such as However, cyanuric acid
- the Composition is therefore for use in gas generators for the Driver's side unsuitable because of the shorter distance between high burn-up speeds for the vehicle occupant and the vehicle internals to be favoured.
- the additional fuels used must have a lower oxygen balance than guanidine nitrate also a higher proportion of oxidizer to balance the mixture and to achieve an optimally reduced harmful gas emission be used.
- the higher proportion of oxidizer leads to a increased solids content in the gas mixture and thus to an increased Particle emission.
- gas generating compositions for use in security devices for motor vehicles with a high burning rate can be achieved with low particle emissions at the same time.
- the oxidizer mixture consists of one or more transition metal oxides in a proportion of 20 to 80 wt .-%, basic copper nitrate in a proportion of 0 to 50% by weight, metal chlorate, metal perchlorate, Ammonium perchlorate or mixtures thereof in a proportion of 1 to 15 % By weight and alkali nitrate, alkaline earth nitrate or mixtures thereof a proportion of 1 to 15 wt .-%, each based on the oxidizer mixture.
- Preferred guanidine compounds are guanidine carbonate, guanidine nitrate, Guanidine perchlorate, aminoguanidine nitrate, diaminoguanidine nitrate, Triaminoguanidine nitrate, nitroguanidine or mixtures thereof used.
- the further fuel component is preferably an organic one Compound that has an oxygen balance of more than -90%.
- Cyanuric acid is particularly preferred as a further fuel component, Urea, oxamide, urazole, alloxan, alloxantin and parabanic acid or mixtures thereof.
- oxygen balance is to be understood as the amount of oxygen in percent by weight which is released when a compound or a mixture is completely converted to CO 2 , H 2 O, Al 2 O 3 , B 2 O 3 , etc. (O 2 overbalancing) . If the available oxygen is not sufficient for this, the shortfall necessary for complete conversion is given with a negative sign (O 2 under-balancing).
- the oxidizer mixture preferably contains a mixture of Fe 2 O 3 and CuO, in addition to the other components of the oxidizer mixture.
- the Fe 2 O 3 is preferably present in a proportion of at least 4% by weight, particularly preferably in a proportion of at least 9%, based on the overall composition.
- the simultaneous use of Fe 2 O 3 and CuO enables a further reduction in the proportion of toxic gases in the combustion products.
- the composition may also include conventional processing aids a proportion of up to 5% by weight, based on the total composition, included, the processing aids preferably from the consisting of the flow aids, pressing aids and / or lubricants Group are selected.
- compositions according to the invention stand out the previously known mixtures due to improved combustion behavior, and in particular through an extremely low particle emission in combination with a high burning rate. they are therefore particularly suitable for use in driver airbag systems.
- the improved burning behavior of the compositions according to the invention is achieved through the use of at least one organic compound favored as a fuel from the group of guanidine compounds.
- the use of guanidine nitrate is particularly preferred because of its favorable oxygen balance of - 26.2%. Compared to others organic compounds or their mixtures with guanidine nitrate less oxidizer is thus required to balance the mixture. This measure therefore already results in lower particle emissions reached.
- the proportion of basic copper nitrate in the oxidizer mixture should in any case be at most 50% by weight, based on the oxidizer mixture.
- the mixture In addition to a high combustion rate and extremely low carbon monoxide and NO x emissions, the mixture is easy to ignite and has excellent retention properties with regard to solid combustion residues. A higher proportion of basic copper nitrate is undesirable since this would in particular increase the NO x proportions in the gas inadmissibly.
- a mixture of 47.1 parts guanidine nitrate and 52.9 parts basic copper nitrate was prepared according to the procedure described in Example 1 of US-A-5,608,183. The mixture showed poor ignitability and only a slow burning rate. The NO x portion of the gas generated measured in the test jug was 1300 ppm.
- the analysis of the toxic component of the combustion gases showed that the combination of iron oxide (Fe 2 O 3 ) and copper oxide (CuO) as a metal oxide component in the blowing agent mixture has a particularly favorable influence on the emissions of carbon monoxide (CO) and ammonia (NH 3 ) .
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Air Bags (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE29821541U DE29821541U1 (de) | 1998-12-02 | 1998-12-02 | Azidfreie, gaserzeugende Zusammensetzung |
DE29821541U | 1998-12-02 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1006096A1 true EP1006096A1 (fr) | 2000-06-07 |
EP1006096B1 EP1006096B1 (fr) | 2002-09-25 |
Family
ID=8066128
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99123906A Expired - Lifetime EP1006096B1 (fr) | 1998-12-02 | 1999-12-01 | Composition génératrice de gaz exempt d'azoture |
Country Status (3)
Country | Link |
---|---|
US (1) | US20050189052A1 (fr) |
EP (1) | EP1006096B1 (fr) |
DE (2) | DE29821541U1 (fr) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1051373B1 (fr) * | 1998-12-02 | 2004-05-26 | TRW Airbag Systems GmbH | Composition sans azide generatrice de gaz |
WO2007012348A1 (fr) * | 2005-07-26 | 2007-02-01 | Dalphi Metal España, S.A. | Composition generatrice de gaz destinee a une utilisation automobile fabriquee par formation de granules |
FR2949778A1 (fr) * | 2009-09-10 | 2011-03-11 | Snpe Materiaux Energetiques | Composes pyrotechniques generateurs de gaz |
WO2012153062A2 (fr) | 2011-05-09 | 2012-11-15 | Sme | Composes pyrotechniques generateurs de gaz. |
DE102012004468A1 (de) | 2012-03-08 | 2013-09-12 | Trw Airbag Systems Gmbh | Gaserzeugende Zusammensetzung und deren Verwendung in Fußgängerschutzeinrichtungen |
DE102012005759A1 (de) | 2012-03-23 | 2013-09-26 | Trw Airbag Systems Gmbh | Gaserzeugende zusammensetzung |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE29806504U1 (de) * | 1998-04-08 | 1998-08-06 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azidfreie, gaserzeugende Zusammensetzung |
US5985060A (en) * | 1998-07-25 | 1999-11-16 | Breed Automotive Technology, Inc. | Gas generant compositions containing guanidines |
JP2000319085A (ja) * | 1999-04-30 | 2000-11-21 | Daicel Chem Ind Ltd | ガス発生剤組成物 |
DE10064285C1 (de) * | 2000-12-22 | 2002-10-17 | Nigu Chemie Gmbh | Gasgeneratortreibstoff-Zusammensetzung und deren Verwendung |
US7618506B2 (en) | 2002-10-31 | 2009-11-17 | Daicel Chemical Industries, Ltd. | Gas generating composition |
JP4672975B2 (ja) * | 2002-10-31 | 2011-04-20 | ダイセル化学工業株式会社 | ガス発生剤組成物 |
FR2857359B1 (fr) * | 2003-07-10 | 2006-12-01 | Snpe Materiaux Energetiques | Composition pyrotechnique generatrice de gaz destinee a la securite automobile et brulant a des temperatures de combustion inferieures a 2200 k |
JP4767487B2 (ja) * | 2003-10-20 | 2011-09-07 | ダイセル化学工業株式会社 | ガス発生剤組成物 |
FR2866022B1 (fr) * | 2004-02-10 | 2006-07-28 | Snpe Materiaux Energetiques | Composition pyrotechnique generatrice de gaz destinee a la securite automobile |
FR2964656B1 (fr) * | 2010-09-15 | 2012-10-12 | Snpe Materiaux Energetiques | Composes pyrotechniques generateurs de gaz |
JP5785768B2 (ja) * | 2011-03-23 | 2015-09-30 | 株式会社ダイセル | ガス発生剤組成物 |
JP5663369B2 (ja) * | 2011-03-31 | 2015-02-04 | 株式会社ダイセル | ガス発生剤組成物 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE9416112U1 (de) * | 1993-10-06 | 1994-12-15 | Contec - Chemieanlagen GmbH, 84544 Aschau | Gasgeneratortreibstoff |
US5629494A (en) * | 1996-02-29 | 1997-05-13 | Morton International, Inc. | Hydrogen-less, non-azide gas generants |
WO1997029927A2 (fr) * | 1996-02-14 | 1997-08-21 | Automotive Systems Laboratory, Inc. | Compositions generatrices de gaz nonazide |
EP0801045A1 (fr) * | 1995-09-29 | 1997-10-15 | Otsuka Kagaku Kabushiki Kaisha | Generateur de gaz pour airbag |
DE29722912U1 (de) * | 1997-12-29 | 1998-02-19 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azidfreie gaserzeugende Zusammensetzung |
DE19643468A1 (de) * | 1996-10-22 | 1998-04-23 | Temic Bayern Chem Airbag Gmbh | Gaserzeugendes, azidfreies Feststoffgemisch |
US5780768A (en) * | 1995-03-10 | 1998-07-14 | Talley Defense Systems, Inc. | Gas generating compositions |
DE29806504U1 (de) * | 1998-04-08 | 1998-08-06 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azidfreie, gaserzeugende Zusammensetzung |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4366010A (en) * | 1978-09-21 | 1982-12-28 | Sedat Georges A | Smoke-producing pyrotechnic composition and its application |
FR2531071B1 (fr) * | 1982-07-28 | 1984-12-21 | France Etat | |
US5482579A (en) * | 1993-04-15 | 1996-01-09 | Nof Corporation | Gas generator compositions |
US5518054A (en) * | 1993-12-10 | 1996-05-21 | Morton International, Inc. | Processing aids for gas generants |
US5431103A (en) * | 1993-12-10 | 1995-07-11 | Morton International, Inc. | Gas generant compositions |
US5538567A (en) * | 1994-03-18 | 1996-07-23 | Olin Corporation | Gas generating propellant |
DE4423088A1 (de) | 1994-07-01 | 1996-01-04 | Temic Bayern Chem Airbag Gmbh | Gaserzeugendes, azidfreies Stoffgemisch |
DE4442037C1 (de) | 1994-11-25 | 1995-12-21 | Fraunhofer Ges Forschung | Gaserzeugende Mischung |
DE19505568A1 (de) | 1995-02-18 | 1996-08-22 | Dynamit Nobel Ag | Gaserzeugende Mischungen |
US5670740A (en) * | 1995-10-06 | 1997-09-23 | Morton International, Inc. | Heterogeneous gas generant charges |
US5817972A (en) | 1995-11-13 | 1998-10-06 | Trw Inc. | Iron oxide as a coolant and residue former in an organic propellant |
US5844164A (en) * | 1996-02-23 | 1998-12-01 | Breed Automotive Technologies, Inc. | Gas generating device with specific composition |
US5661261A (en) * | 1996-02-23 | 1997-08-26 | Breed Automotive Technology, Inc. | Gas generating composition |
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 |
US5959242A (en) * | 1996-05-14 | 1999-09-28 | Talley Defense Systems, Inc. | Autoignition composition |
JPH09328387A (ja) * | 1996-06-03 | 1997-12-22 | Daicel Chem Ind Ltd | ガス発生剤組成物 |
EP0914306A1 (fr) | 1996-07-20 | 1999-05-12 | Dynamit Nobel GmbH Explosivstoff- und Systemtechnik | Melange pyrotechnique servant d'agent propulseur ou de charge gazeuse avec des vapeurs a teneur reduite en monoxyde de carbone |
US5962808A (en) * | 1997-03-05 | 1999-10-05 | Automotive Systems Laboratory, Inc. | Gas generant complex oxidizers |
US5841065A (en) * | 1997-04-15 | 1998-11-24 | Autoliv Asp, Inc. | Gas generants containing zeolites |
US5861571A (en) * | 1997-04-18 | 1999-01-19 | Atlantic Research Corporation | Gas-generative composition consisting essentially of ammonium perchlorate plus a chlorine scavenger and an organic fuel |
DE19742203A1 (de) | 1997-09-24 | 1999-03-25 | Trw Airbag Sys Gmbh | Partikelfreies gaserzeugendes Gemisch |
US6096147A (en) * | 1998-07-30 | 2000-08-01 | Autoliv Asp, Inc. | Ignition enhanced gas generant and method |
-
1998
- 1998-12-02 DE DE29821541U patent/DE29821541U1/de not_active Expired - Lifetime
-
1999
- 1999-12-01 EP EP99123906A patent/EP1006096B1/fr not_active Expired - Lifetime
- 1999-12-01 DE DE59902827T patent/DE59902827D1/de not_active Expired - Lifetime
-
2005
- 2005-03-14 US US11/079,718 patent/US20050189052A1/en not_active Abandoned
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE9416112U1 (de) * | 1993-10-06 | 1994-12-15 | Contec - Chemieanlagen GmbH, 84544 Aschau | Gasgeneratortreibstoff |
US5780768A (en) * | 1995-03-10 | 1998-07-14 | Talley Defense Systems, Inc. | Gas generating compositions |
EP0801045A1 (fr) * | 1995-09-29 | 1997-10-15 | Otsuka Kagaku Kabushiki Kaisha | Generateur de gaz pour airbag |
WO1997029927A2 (fr) * | 1996-02-14 | 1997-08-21 | Automotive Systems Laboratory, Inc. | Compositions generatrices de gaz nonazide |
US5629494A (en) * | 1996-02-29 | 1997-05-13 | Morton International, Inc. | Hydrogen-less, non-azide gas generants |
DE19643468A1 (de) * | 1996-10-22 | 1998-04-23 | Temic Bayern Chem Airbag Gmbh | Gaserzeugendes, azidfreies Feststoffgemisch |
DE29722912U1 (de) * | 1997-12-29 | 1998-02-19 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azidfreie gaserzeugende Zusammensetzung |
DE29806504U1 (de) * | 1998-04-08 | 1998-08-06 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azidfreie, gaserzeugende Zusammensetzung |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1051373B1 (fr) * | 1998-12-02 | 2004-05-26 | TRW Airbag Systems GmbH | Composition sans azide generatrice de gaz |
WO2007012348A1 (fr) * | 2005-07-26 | 2007-02-01 | Dalphi Metal España, S.A. | Composition generatrice de gaz destinee a une utilisation automobile fabriquee par formation de granules |
FR2949778A1 (fr) * | 2009-09-10 | 2011-03-11 | Snpe Materiaux Energetiques | Composes pyrotechniques generateurs de gaz |
WO2011030071A3 (fr) * | 2009-09-10 | 2011-05-19 | Snpe Materiaux Energetiques | Composes pyrotechniques generateurs de gaz |
WO2012153062A2 (fr) | 2011-05-09 | 2012-11-15 | Sme | Composes pyrotechniques generateurs de gaz. |
FR2975097A1 (fr) * | 2011-05-09 | 2012-11-16 | Sme | Composes pyrotechniques generateurs de gaz |
US9249063B2 (en) | 2011-05-09 | 2016-02-02 | Herakles | Pyrotechnic gas generator compounds |
DE102012004468A1 (de) | 2012-03-08 | 2013-09-12 | Trw Airbag Systems Gmbh | Gaserzeugende Zusammensetzung und deren Verwendung in Fußgängerschutzeinrichtungen |
US10343954B2 (en) | 2012-03-08 | 2019-07-09 | Trw Airbag Systems Gmbh | Gas generating composition and use thereof in pedestrian protection devices |
DE102012005759A1 (de) | 2012-03-23 | 2013-09-26 | Trw Airbag Systems Gmbh | Gaserzeugende zusammensetzung |
Also Published As
Publication number | Publication date |
---|---|
DE29821541U1 (de) | 1999-02-18 |
EP1006096B1 (fr) | 2002-09-25 |
DE59902827D1 (de) | 2002-10-31 |
US20050189052A1 (en) | 2005-09-01 |
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