EP0666248A1 - Gas generating mixture - Google Patents
Gas generating mixture Download PDFInfo
- Publication number
- EP0666248A1 EP0666248A1 EP94119383A EP94119383A EP0666248A1 EP 0666248 A1 EP0666248 A1 EP 0666248A1 EP 94119383 A EP94119383 A EP 94119383A EP 94119383 A EP94119383 A EP 94119383A EP 0666248 A1 EP0666248 A1 EP 0666248A1
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- EP
- European Patent Office
- Prior art keywords
- catalyst
- mixture according
- mixture
- gzt
- support
- 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.)
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Classifications
-
- 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
- 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 invention relates to a gas-generating mixture of a fuel, an oxidizer, a catalyst and a coolant.
- 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 oxidizer is Cu (NO3) 2 * 3Cu (OH) 2 and the catalyst consists of a metal or a metal alloy on a support.
- 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.
- the carrier serves to present the main component with a large specific surface and a defined grain size distribution. Another property of the carrier is to develop a cooling effect through physical and / or chemical processes - in a special phase of the reaction, that goes beyond a pure capacitive cooling effect.
- the carrier can also act as a promoter of the main component. Not only the metal catalyst, but also the oxidizer are thermally and mechanically stable and in particular also not hygroscopic.
- N-rich and C-poor fuels include the well-known fuels TAGN (triaminoguanidine nitrate), NIGU (nitroguanidine), NTO (3-nitro-1,2,3-triazol-5-one) and the GZT (diguanidinium-5,5 '), which is characterized by a particularly high nitrogen content. -azotetrazolate) (DE 4 108 225).
- TAGN, NIGU, NTO, but in particular GZT are preferably used in the mixture according to the invention when used for rescue and restraint systems.
- the combustion temperature can be determined very precisely by thermodynamic calculation. It is 2345 K. With the same GZT fuel and a balanced oxygen balance, other oxidizers deliver higher combustion temperatures. For example, they are at KNO3 at 2501 K, at N H4 NO3 at 2850 K and at K Cl O3 at 3248 K.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Eine gaserzeugende Mischung für Rettungs- und Rückhaltesysteme (Airbag) sowie für Raketen- und Rohrwaffenantriebe, besteht aus den stickstoffreichen und kohlenstoffarmen Brennstoffen GZT, TAGN, NIGU oder NTO, dem kalt- und schnellverbrennenden Oxidator, Cu(NO3)2*3Cu(OH)2 und einem Katalysator zur Schadgasreduzierung, Reaktionsbeschleunigung und Kühlung aus einem pyrophoren Metall oder einer solchen Legierung auf einem Träger.A gas-producing mixture for rescue and restraint systems (airbag) as well as for rocket and barrel weapon drives, consists of the nitrogen-rich and low-carbon fuels GZT, TAGN, NIGU or NTO, the cold and fast-burning oxidizer, Cu (NO3) 2 * 3Cu (OH) 2 and a catalyst for reducing harmful gas, accelerating the reaction and cooling from a pyrophoric metal or such an alloy on a support.
Description
Die Erfindung betrifft eine gaserzeugende Mischung aus einem Brennstoff, einem Oxidator, einem Katalysator und einem Kühlmittel.The invention relates to a gas-generating mixture of a fuel, an oxidizer, a catalyst and a coolant.
Gaserzeugende Mischungen der vorgenannten Art - auch Gasgeneratorsätze genannt - zeichnen sich dadurch aus, daß sie bei Verbrennung eine hohe Gasausbeute (> 14 mol/kg) ermöglichen. Sie werden für Raketen- und Rohrwaffenantriebe sowie für aufblasbare Rückhalte- (Airbag) und Rettungssysteme verwendet. Besonders im zivilen Bereich werden thermisch-mechanische Unempfindlichkeit und Ungiftigkeit der Ausgangsmischungen, aber auch fehlende Toxizität bei den entstehenden Gasen gefordert. Viele im Einsatz befindlichen Systeme erfüllen diese Forderungen nicht oder nur sehr unzulänglich.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.
Die Reaktion dieser Brennstoffe mit den bisher eingesetzten Katalysatoren und Oxidatoren zeigen eine unbefriedigende Gaszusammensetzung und/oder ein ungenügendes Abbrandverhalten. Hinzu kommt, daß viele Reaktionsmischungen eine so hohe Verbrennungstemperatur besitzen, daß - bei Airbag-Anwendungen - die thermisch empfindlichen Sackmaterialien geschädigt werden.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.
Der Erfindung liegt die Aufgabe zugrunde, bei einer Mischung des eingangs genannten Aufbaus, die Verbrennungstemperatur abzusenken und die Abbrandgeschwindigkeit zu erhöhen.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.
Diese an sich konträren Anforderungen werden erfindungsgemäß dadurch erfüllt, daß der Oxidator Cu(NO₃)₂*3Cu(OH)₂ ist und der Katalysator aus einem Metall oder einer Metallegierung auf einem Träger besteht .According to the invention, these contradictory requirements are met in that the oxidizer is Cu (NO₃) ₂ * 3Cu (OH) ₂ and the catalyst consists of a metal or a metal alloy on a support.
Durch den erfindungsgemäß vorgesehenen Oxidator ergibt sich eine halte und schnelle Verbrennung. Der Maximaldruck wird innerhalb Millisekunden erreicht, wobei die Gastemperatur unterhalb schädlicher Grenzen bleibt. Bisher notwendige Schlackenbildner, die bei bekannten Systemen zur Bindung von Schadstoffen, z.B. Alkalioxiden, benötigt werden, können bei der erfindungsgemäßen Mischung entfallen, so daß eine höhere Gasausbeute erzielbar ist.The oxidizer provided according to the invention results in sustained 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.
Der weiterhin erfindungsgemäß eingesetzte Katalysator dient vornehmlich der Schadgasreduzierung (CO und NO), wobei hier der Begriff "Katalysator" im erweiterten Sinn einen aktiven Reaktionsbestandteil bezeichnet, der selbst umgesetzt werden kann und reaktionslenkend und/oder reaktionsbeschleunigend wirkt. Der Träger dient dazu, die Hauptkomponente mit einer großen spezifischen Oberfläche und einer definierten Korngrößenverteilung vorzulegen. Eine weitere Eigenschaft des Trägers besteht darin, durch physikalische und/oder chemische Prozesse - in einer speziellen Phase der Reaktion - eine Kühlwirkung zu entfalten, die über eine reine kapazitive Kühlwirkung hinausgeht. Der Träger kann ferner als Promotor der Hauptkomponente wirken. Nicht nur der Metallkatalysator, sondern auch der Oxidator sind thermisch und mechanisch stabil und insbesondere auch nicht hygroskopisch.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. The carrier serves to present the main component with a large specific surface and a defined grain size distribution. Another property of the carrier is to develop a cooling effect through physical and / or chemical processes - in a special phase of the reaction, that goes beyond a pure capacitive cooling effect. The carrier can also act as a promoter of the main component. Not only the metal catalyst, but also the oxidizer are thermally and mechanically stable and in particular also not hygroscopic.
Der Katalysator ist vorzugsweise ein pyrophores Metall oder eine solche Metallegierung auf einem Träger, der nach dem Abbrand als Feststoff verbleibt. Es kann sich hierbei um ein Silikat, vorzugsweise ein Schicht- oder Gerüstsilikat, handeln.The catalyst is preferably a pyrophoric metal or such a metal alloy on a support which remains as a solid after the combustion. This can be a silicate, preferably a layered or framework silicate.
Als Metall hat sich insbesondere Ag hervorragend bewährt. Bei insbesondere zivilen Anwendungen werden ungiftige Ausgangsverbindungen und ungiftige Reaktionsprodukte gefordert. Diese Forderungen werden von N-reichen und C-armen Brennstoffen erfüllt. Hierzu zählen die bekannten Brennstoffe TAGN (Triaminoguanidinnitrat), NIGU (Nitroguanidin), NTO (3-Nitro-1,2,3-triazol-5-on) und das sich durch einen besonders hohen Stickstoffgehalt auszeichnende GZT (Diguanidinium-5,5'-azotetrazolat) (DE 4 108 225). Es werden deshalb im Rahmen der erfindungsgemäßen Mischung bei Verwendung für Rettungs- und Rückhaltsysteme vorzugsweise TAGN, NIGU, NTO, insbesondere aber GZT eingesetzt.Ag, in particular, has proven to be an excellent metal. 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 GZT (diguanidinium-5,5 '), which is characterized by a particularly high nitrogen content. -azotetrazolate) (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.
Eine bevorzugte Mischung besteht aus GZT und Cu(NO₃)₂*3Cu(OH)₂ mit ausgeglichener Sauerstoffbilanz und bis zu 30 Mass.-% des Katalysators.A preferred mixture consists of GZT and Cu (NO₃) ₂ * 3Cu (OH) ₂ with a balanced oxygen balance and up to 30 mass .-% of the catalyst.
Das Kühlmittel kann ganz oder teilweise aus Fe₂O₃ bestehen, dessen oxidative Eigenschaften in der Reaktionsmischung zusätzlich genutzt werden können (DE 41 33 655, EP 0 536 525).The coolant can consist entirely or partially of Fe₂O₃, the oxidative properties of which can additionally be used in the reaction mixture (DE 41 33 655, EP 0 536 525).
Es wird eine Mischung bestehend aus GZT, pyrophorem Ag auf einem Schicht- oder Gerüstsilikatträger als Katalysator und Cu(NO₃)₂*3Cu(OH)₂ als Oxidator im Verhältnis 22,05 : 20,0 : 57,95 Mass.-% hergestellt. Diese Formulierung wird bezüglich ihres Anzünd- und Verbrennungsverhaltens experimentell in der ballistischen Bombe untersucht. Dabei wird ein Druckverlaufsdiagramm gemäß Anlage erhalten. Das Diagramm zeigt, daß die Mischung gute Anzünd- und Verbrennungseigenschaften besitzt. Bei einer Ladedichte von 0,1 g/cm³ liegt der maximale Druck im Bereich von 250 bar (25MPa), der nach etwa 21 ms erreicht wird (t(pmax) = 21 ms). Die Druckanstiegszeit zwischen 30 bis 80 % des Maximaldrucks beträgt t₃₀₋₈₀ = 4,35 ms.It is a mixture consisting of GZT, pyrophoric Ag on a layer or framework silicate support as a catalyst and Cu (NO₃) ₂ * 3Cu (OH) ₂ as an oxidizer in a ratio of 22.05: 20.0: 57.95% 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 / cm³ the maximum pressure is in the range of 250 bar (25MPa), which is reached after about 21 ms (t (pmax) = 21 ms). The pressure rise time between 30 to 80% of the maximum pressure is t₃₀₋₈₀ = 4.35 ms.
Die Verbrennungstemperatur läßt sich sehr exakt durch thermodynamische Berechnung ermitteln. Sie liegt bei 2345 K. Bei gleichem Brennstoff GZT und ausgeglichener Sauerstoffbilanz liefern andere Oxidatoren höhere Verbrennungstemperaturen. Beispielsweise liegen sie bei KNO₃ bei 2501 K, bei N H₄ NO₃ bei 2850 K und bei K Cl O₃ bei 3248 K.The combustion temperature can be determined very precisely by thermodynamic calculation. It is 2345 K. With the same GZT fuel and a balanced oxygen balance, other oxidizers deliver higher combustion temperatures. For example, they are at KNO₃ at 2501 K, at N H₄ NO₃ at 2850 K and at K Cl O₃ at 3248 K.
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4401214 | 1994-01-18 | ||
| DE4401214A DE4401214C1 (en) | 1994-01-18 | 1994-01-18 | Gas-generating mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0666248A1 true EP0666248A1 (en) | 1995-08-09 |
| EP0666248B1 EP0666248B1 (en) | 1996-10-23 |
Family
ID=6508092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94119383A Expired - Lifetime EP0666248B1 (en) | 1994-01-18 | 1994-12-08 | Gas generating mixture |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US5542999A (en) |
| EP (1) | EP0666248B1 (en) |
| DE (2) | DE4401214C1 (en) |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4442169C1 (en) * | 1994-11-26 | 1995-12-21 | Fraunhofer Ges Forschung | Non-toxic gas-generating mixt. with thermal-mechanical stability |
| DE4442170C1 (en) * | 1994-11-26 | 1995-12-21 | Fraunhofer Ges Forschung | Non-toxic gas-generating mixt. with thermal-mechanical stability |
| JPH08231291A (en) * | 1994-12-27 | 1996-09-10 | Daicel Chem Ind Ltd | Gas generating agent composition |
| DE19531288A1 (en) * | 1995-08-25 | 1997-02-27 | Temic Bayern Chem Airbag Gmbh | Airbag propellant gas generator |
| 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 |
| DE59711752D1 (en) † | 1996-07-20 | 2004-08-05 | Dynamit Nobel Ag | THERMAL FUSE |
| 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 |
| US6306232B1 (en) | 1996-07-29 | 2001-10-23 | Automotive Systems Laboratory, Inc. | Thermally stable nonazide automotive airbag propellants |
| WO1998039275A1 (en) * | 1997-03-05 | 1998-09-11 | Automotive Systems Laboratory, Inc. | Gas generants comprising carbonato metal ammine complexes |
| DE19812372C2 (en) * | 1998-03-20 | 2001-10-04 | Nigu Chemie Gmbh | Gas generator fuels |
| US6132538A (en) * | 1998-07-30 | 2000-10-17 | Autoliv Development Ab | High gas yield generant compositions |
| DE29821544U1 (en) | 1998-12-02 | 1999-02-18 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azide-free, gas generating composition |
| US6143102A (en) * | 1999-05-06 | 2000-11-07 | Autoliv Asp, Inc. | Burn rate-enhanced basic copper nitrate-containing gas generant compositions and methods |
| CN100465097C (en) * | 1999-09-27 | 2009-03-04 | 大赛璐化学工业株式会社 | Basic metal nitrate, method for producing the same and gas-generating agent composition |
| JP4800469B2 (en) * | 1999-10-08 | 2011-10-26 | ダイセル化学工業株式会社 | Gas generant composition |
| US6372191B1 (en) | 1999-12-03 | 2002-04-16 | Autoliv Asp, Inc. | Phase stabilized ammonium nitrate and method of making the same |
| US6224697B1 (en) | 1999-12-03 | 2001-05-01 | Autoliv Development Ab | Gas generant manufacture |
| JP4500399B2 (en) * | 2000-02-04 | 2010-07-14 | ダイセル化学工業株式会社 | Gas generant composition containing triazine derivative |
| US6436211B1 (en) | 2000-07-18 | 2002-08-20 | Autoliv Asp, Inc. | Gas generant manufacture |
| US6589375B2 (en) | 2001-03-02 | 2003-07-08 | Talley Defense Systems, Inc. | Low solids gas generant having a low flame temperature |
| CN1285547C (en) * | 2001-05-10 | 2006-11-22 | 日本化药株式会社 | Igniting agent composition and ignitor using same |
| US6854395B2 (en) | 2001-08-10 | 2005-02-15 | Daicel Chemical Industries, Ltd. | Inflator for an air bag |
| US6875295B2 (en) | 2001-12-27 | 2005-04-05 | Trw Inc. | Cool burning gas generating material for a vehicle occupant protection apparatus |
| US20040154710A1 (en) * | 2002-07-25 | 2004-08-12 | Mamoru Watabiki | Gas generating composition |
| US20050263224A1 (en) * | 2002-08-05 | 2005-12-01 | Jianzhou Wu | Gas generating composition for inflator containing melamine cyanurate |
| US6964716B2 (en) * | 2002-09-12 | 2005-11-15 | Daicel Chemical Industries, Ltd. | Gas generating composition |
| US7618506B2 (en) * | 2002-10-31 | 2009-11-17 | Daicel Chemical Industries, Ltd. | Gas generating composition |
| US6872265B2 (en) | 2003-01-30 | 2005-03-29 | Autoliv Asp, Inc. | Phase-stabilized ammonium nitrate |
| US20050127324A1 (en) * | 2003-10-22 | 2005-06-16 | Jianzhou Wu | Gas generating composition |
| US20050257866A1 (en) * | 2004-03-29 | 2005-11-24 | Williams Graylon K | Gas generant and manufacturing method thereof |
| JP4610266B2 (en) | 2004-09-09 | 2011-01-12 | ダイセル化学工業株式会社 | Gas generant composition |
| US8137771B2 (en) * | 2004-09-09 | 2012-03-20 | Daicel Chemical Industries, Ltd. | Gas generating composition |
| US20060191614A1 (en) * | 2005-02-10 | 2006-08-31 | Daicel Chemical Industries, Ltd. | Gas generating composition |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB658643A (en) * | 1949-01-12 | 1951-10-10 | Alexander Cantlay Hutchison | Improvements in or relating to solid gas generating charges |
| US2604391A (en) * | 1946-11-08 | 1952-07-22 | Ici Ltd | Gas-producing nondetonating composition |
| FR2240199A1 (en) * | 1973-08-08 | 1975-03-07 | Dow Chemical Co | |
| EP0430463A2 (en) * | 1989-11-20 | 1991-06-05 | Morton International, Inc. | Gas generating compositions containing nitrotriazalone |
| DE4108225C1 (en) * | 1991-03-14 | 1992-04-09 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| DE4218531C1 (en) * | 1991-10-11 | 1993-07-15 | Bayern-Chemie Gesellschaft Fuer Flugchemische Antriebe Mbh, 8261 Aschau, De |
-
1994
- 1994-01-18 DE DE4401214A patent/DE4401214C1/en not_active Expired - Fee Related
- 1994-12-08 DE DE59400902T patent/DE59400902D1/en not_active Expired - Fee Related
- 1994-12-08 EP EP94119383A patent/EP0666248B1/en not_active Expired - Lifetime
-
1995
- 1995-01-17 US US08/373,023 patent/US5542999A/en not_active Expired - Fee Related
Patent Citations (6)
| 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 |
| FR2240199A1 (en) * | 1973-08-08 | 1975-03-07 | Dow Chemical Co | |
| EP0430463A2 (en) * | 1989-11-20 | 1991-06-05 | Morton International, Inc. | Gas generating compositions containing nitrotriazalone |
| DE4108225C1 (en) * | 1991-03-14 | 1992-04-09 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De | |
| EP0503341A1 (en) * | 1991-03-14 | 1992-09-16 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Stable nitrogen-rich compound |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4401214C1 (en) | 1995-03-02 |
| US5542999A (en) | 1996-08-06 |
| DE59400902D1 (en) | 1996-11-28 |
| EP0666248B1 (en) | 1996-10-23 |
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