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EP0716060B1 - Gas generating mixture - Google Patents

Gas generating mixture Download PDF

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Publication number
EP0716060B1
EP0716060B1 EP95116147A EP95116147A EP0716060B1 EP 0716060 B1 EP0716060 B1 EP 0716060B1 EP 95116147 A EP95116147 A EP 95116147A EP 95116147 A EP95116147 A EP 95116147A EP 0716060 B1 EP0716060 B1 EP 0716060B1
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EP
European Patent Office
Prior art keywords
mixture
mixture according
gas generating
fuel
metal powder
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.)
Expired - Lifetime
Application number
EP95116147A
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German (de)
French (fr)
Other versions
EP0716060A1 (en
Inventor
Klaus Martin Dr. Bucerius
Walter Dr. Engel
Helmut Schmid
Norbert Dr. Eisenreich
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.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Publication of EP0716060A1 publication Critical patent/EP0716060A1/en
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
    • C06B33/04—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide the material being an inorganic nitrogen-oxygen salt
    • 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 and optionally a coolant.
  • Gas-generating mixtures of the aforementioned type - also called gas generator sets - are distinguished by the fact that they enable a high gas yield (> 14 mol / kg) when burned. They are used for inflatable restraint (airbag) and rescue systems, fire extinguishing systems and for insensitive solid fuels for rocket and barrel weapon drives. 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 do so only inadequately.
  • the invention is based on the object of proposing a gas-generating mixture which itself and its combustion products are non-toxic and which, at a high rate of combustion, has a long service life and functionality even under extreme operating conditions.
  • the fuel consists of a mixture of copper tetrammine dinitrate [Cu (NH 3 ) 4 ] (NO 3 ) 2 and a powdery metal or semimetal or alloy thereof which has a high oxygen reactivity.
  • the inorganic fuel mixture proposed according to the invention offers the advantage that during combustion no CO 2 or CO harmful gases are generated.
  • the burn-up behavior of the reaction mixture can be adjusted over a wide range by using the metal powder.
  • the maximum pressure builds up within a few milliseconds, and the combustion temperature is also relatively low, so that thermally sensitive bag materials are not endangered, particularly in airbag systems.
  • the metal powder is preferably amorphous boron with a grain size ⁇ 20 microns.
  • the oxidizer is a basic copper nitrate, namely Cu (NO 3 ) 2 * 3Cu (OH 2 ).
  • the proposed oxidizer is distinguished by the fact that it is not hygroscopic and the mixture therefore remains functional for a long time even under moist environmental conditions. Furthermore, this oxidizer contributes to a relatively low combustion temperature. Coolants, such as Fe 2 O 3 powder, can optionally also be added, the oxidative properties of which can also be used in the reaction mixture (EP 0 536 525).
  • a mixture that has proven itself in practice is characterized by the fact that it consists of boron, [Cu (NH 3 ) 4 ] (NO 3 ) 2 and Cu (NO 3 ) 2 * 3Cu (OH) 2 with a balanced oxygen balance and the composition 3, 65 / 69.33 / 27.02% by mass exists.
  • This formulation is investigated experimentally in the ballistic bomb with regard to its ignition and combustion behavior.
  • the attached pressure curve diagram is obtained.
  • the diagram shows that the mixture has good ignition and combustion properties.
  • the pressure rise time between 30 to 80% of the maximum pressure t 30-80 is 1.76 ms.
  • a combustion temperature of 2000 K was determined by radiation measurements.
  • the gases developed in a calorimetric bomb consisted of 99.05% by volume of N 2 and had only 10 ppm of NH 3 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Air Bags (AREA)
  • Catalysts (AREA)
  • Percussion Or Vibration Massage (AREA)

Abstract

A gas-generating mixt. consists of a fuel, oxidant and opt. coolant. The fuel comprises a mixt. of Cu(NH3)2(NO3)2 (I) and metal, metalloid or alloy powder (II) with great O2 reactivity.

Description

Die Erfindung betrifft eine gaserzeugende Mischung aus einem Brennstoff, einem Oxidator und gegebenenfalls einem Kühlmittel.The invention relates to a gas-generating mixture of a fuel, an oxidizer and optionally 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 aufblasbare Rückhalte- (Airbag) und Rettungssysteme, Feuerlöscheinrichtungen sowie für unempfindliche Festtreibstoffe für Raketen- und Rohrwaffenantriebe eingesetzt. Besonders im zivilen Bereich werden thermisch-mechanische Unempfindlichkeit und Ungiftigkeit der Ausgangsmischungen, aber auch fehlende Toxizität bei den entstehenden Gasen gefordert. Viele im Einsatz befindliche Systeme erfüllen diese Forderungen nicht oder nur sehr unzulänglich.Gas-generating mixtures of the aforementioned type - also called gas generator sets - are distinguished by the fact that they enable a high gas yield (> 14 mol / kg) when burned. They are used for inflatable restraint (airbag) and rescue systems, fire extinguishing systems and for insensitive solid fuels for rocket and barrel weapon drives. 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 do so only inadequately.

Bei Airbag-Systemen wurden zunächst gaserzeugende Mischungen auf der Basis von Natriumazid eingesetzt und erprobt, das jedoch wegen seiner Toxizität und der entstehenden Feststoffpartikel problematisch ist. Ähnliche Probleme ergeben sich auch bei den sogenannten Hybrid-Gasgeneratoren, bei denen Nitramine oder Perchlorate eingesetzt werden.In airbag systems, gas-generating mixtures based on sodium azide were initially used and tried, but is problematic because of its toxicity and the resulting solid particles. Similar problems also arise with the so-called hybrid gas generators, in which nitramines or perchlorates are used.

Es hat deshalb nicht an Anstrengungen gefehlt, insbesondere ungiftige Ausgangsverbindungen bereitzustellen. Hierzu zählen vor allem stickstoffreiche und kohlenstoffarme Brennstoffe, wie TAGN, NIGU und NTO. Besonders gute Ergebnisse konnten mit Diguanidinium 5,5'-azotetrazolat (GZT) erzielt werden (DE 41 08 225). Sowohl die Ausgangsmischung, als auch die entstehenden Gase sind weitgehend ungiftig und bestehen zum überwiegenden Teil aus Stickstoff. Auch zeigt diese Substanz ein gutes Abbrandverhalten. Nachteilig ist allerdings auch hierbei die Tatsache, daß die CO- und NOx-Problematik simultan gelöst werden muß.Efforts have therefore not been lacking, in particular to provide non-toxic starting compounds. These include above all nitrogen-rich and low-carbon fuels, such as TAGN, NIGU and NTO. Particularly good results were achieved with diguanidinium 5,5'-azotetrazolate (GZT) (DE 41 08 225). Both the starting mixture and the resulting gases are largely non-toxic and mainly consist of nitrogen. This substance also shows good burning behavior. However, the fact that the CO and NO x problems have to be solved simultaneously is also disadvantageous.

Der Erfindung liegt die Aufgabe zugrunde, eine gaserzeugende Mischung vorzuschlagen, die selbst und deren Verbrennungsprodukte ungiftig sind und die bei hoher Abbrandgeschwindigkeit eine lange Lebensdauer und Funktionstüchtigkeit auch unter extremen Einsatzbedingungen aufweist.The invention is based on the object of proposing a gas-generating mixture which itself and its combustion products are non-toxic and which, at a high rate of combustion, has a long service life and functionality even under extreme operating conditions.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß der Brennstoff aus einer Mischung aus Kupfertetrammindinitrat [Cu(NH3)4](NO3)2 und einem eine große Sauerstoff-Reaktionsfähigkeit aufweisenden, pulverförmigen Metall oder Halbmetall bzw. Legierung derselben besteht.This object is achieved according to the invention in that the fuel consists of a mixture of copper tetrammine dinitrate [Cu (NH 3 ) 4 ] (NO 3 ) 2 and a powdery metal or semimetal or alloy thereof which has a high oxygen reactivity.

Die erfindungsgemäß vorgeschlagene anorganische Brennstoff-Mischung bietet den Vorteil, daß bei der Verbrennung keine CO2- bzw. CO-Schadgase entstehen. Durch die Verwendung des Metallpulvers läßt sich das Abbrandverhalten der Reaktionsmischung in weiten Bereichen einstellen. Bei der Verbrennung baut sich der Maximaldruck innerhalb weniger Millisekunden auf, wobei ferner die Verbrennungstemperatur relativ niedrig liegt, so daß insbesondere bei Airbag-Systemen auch thermisch empfindliche Sackmaterialien nicht gefährdet werden.The inorganic fuel mixture proposed according to the invention offers the advantage that during combustion no CO 2 or CO harmful gases are generated. The burn-up behavior of the reaction mixture can be adjusted over a wide range by using the metal powder. During combustion, the maximum pressure builds up within a few milliseconds, and the combustion temperature is also relatively low, so that thermally sensitive bag materials are not endangered, particularly in airbag systems.

Das Metallpulver ist vorzugsweise amorphes Bor in einer Korngröße < 20 µm.The metal powder is preferably amorphous boron with a grain size <20 microns.

In weiterhin bevorzugter Ausführung ist vorgesehen, daß der Oxidator ein basisches Kupfernitrat, nämlich Cu(NO3)2*3Cu(OH2) ist.In a further preferred embodiment it is provided that the oxidizer is a basic copper nitrate, namely Cu (NO 3 ) 2 * 3Cu (OH 2 ).

Der vorgeschlagene Oxidator zeichnet sich dadurch aus, daß er nicht hygroskopisch ist und damit die Mischung auch unter feuchten Umgebungsbedingungen lange funktionstüchtig bleibt. Ferner trägt dieser Oxidator zu einer relativ niedrigen Verbrennungstemperatur bei. Dabei können gegebenenfalls zusätzlich noch Kühlmittel, wie Fe2O3-Pulver, zugesetzt werden, wobei zusätzlich dessen oxidative Eigenschaften in der Reaktionsmischung genutzt werden können (EP 0 536 525).The proposed oxidizer is distinguished by the fact that it is not hygroscopic and the mixture therefore remains functional for a long time even under moist environmental conditions. Furthermore, this oxidizer contributes to a relatively low combustion temperature. Coolants, such as Fe 2 O 3 powder, can optionally also be added, the oxidative properties of which can also be used in the reaction mixture (EP 0 536 525).

Eine in der Praxis bewährte Mischung zeichnet sich dadurch aus, daß sie aus Bor, [Cu(NH3)4](NO3)2 und Cu(NO3)2*3Cu(OH)2 mit ausgeglichener Sauerstoffbilanz und der Zusammensetzung 3,65/69,33/27,02 Mass-% besteht.A mixture that has proven itself in practice is characterized by the fact that it consists of boron, [Cu (NH 3 ) 4 ] (NO 3 ) 2 and Cu (NO 3 ) 2 * 3Cu (OH) 2 with a balanced oxygen balance and the composition 3, 65 / 69.33 / 27.02% by mass exists.

Beispiel:Example:

Es wird eine Mischung bestehend aus amorphem Bor, [Cu(NH3)4](NO3)2 und Cu(NO3)2*3Cu(OH)2 im Verhältnis 3,65 : 69,33 : 27,02 Mass-% hergestellt. Diese Formulierung wird bezüglich ihres Anzünd- und Verbrennungsverhaltens experimentell in der ballistischen Bombe untersucht. Dabei wird das beigefügte Druckverlaufsdiagramm 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 55,2 MPa, der nach etwa 23,8 ms erreicht wird (t(pmax)= 23,8 ms). Die Druckanstiegszeit zwischen 30 bis 80 % des Maximaldrucks t30-80 beträgt 1,76 ms. Durch Strahlungsmessungen wurde eine Verbrennungstemperatur von 2000 K ermittelt. Die in einer kalorimetrischen Bombe entwickelten Gase bestanden zu 99,05 Vol.-% aus N2 und wiesen nur 10 ppm NH3 auf.A mixture consisting of amorphous boron, [Cu (NH 3 ) 4 ] (NO 3 ) 2 and Cu (NO 3 ) 2 * 3Cu (OH) 2 in a ratio of 3.65: 69.33: 27.02 mass. % manufactured. This formulation is investigated experimentally in the ballistic bomb with regard to its ignition and combustion behavior. The attached pressure curve diagram 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 55.2 MPa, which is reached after about 23.8 ms (t (pmax) = 23.8 ms). The pressure rise time between 30 to 80% of the maximum pressure t 30-80 is 1.76 ms. A combustion temperature of 2000 K was determined by radiation measurements. The gases developed in a calorimetric bomb consisted of 99.05% by volume of N 2 and had only 10 ppm of NH 3 .

Claims (7)

  1. A gas generating mixture comprising a fuel, an oxidiser and optionally a coolant, characterized in that the fuel consists of a mixture of copper tetraammoniumdinitrate [Cu(NH3)4](NO3)2 and a powdered metal, semi-metal or alloy having a large ability to react with oxygen.
  2. A mixture according to claim 1, characterized in that the semi-metal powder is amorphous boron.
  3. A mixture according to claim 1, characterized in that the metal powder is Mg or Al.
  4. A mixture according to claim 1, characterized in that the metal powder has a grain size smaller than 20 µm.
  5. A mixture according to claim 4, characterized in that the oxidiser is Cu(NO3)2*3Cu(OH2).
  6. A mixture according to any of claims 1 to 5, characterized in that it consists of boron, [Cu(NH3)4](NO3)2 and Cu(NO3)2*3Cu(OH2) with equalized oxygen balance and a composition by mass % 3.65/69.33/27.02.
  7. A mixture according to any of claims 1 to 6, characterized in that the coolant consists wholly or partially of Fe2O3.
EP95116147A 1994-11-25 1995-10-13 Gas generating mixture Expired - Lifetime EP0716060B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4442037 1994-11-25
DE4442037A DE4442037C1 (en) 1994-11-25 1994-11-25 Non-toxic gas-generating mixt. with low combustion temp.

Publications (2)

Publication Number Publication Date
EP0716060A1 EP0716060A1 (en) 1996-06-12
EP0716060B1 true EP0716060B1 (en) 1997-07-30

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EP95116147A Expired - Lifetime EP0716060B1 (en) 1994-11-25 1995-10-13 Gas generating mixture

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AT (1) ATE156111T1 (en)
DE (2) DE4442037C1 (en)
ES (1) ES2106609T3 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9199886B2 (en) 1994-01-19 2015-12-01 Orbital Atk, Inc. Metal complexes for use as gas generants

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5725699A (en) * 1994-01-19 1998-03-10 Thiokol Corporation Metal complexes for use as gas generants
KR100767838B1 (en) 1996-07-25 2007-10-17 앨리언트 테크시스템즈 인코포레이티드 Metal complexes for use as gas generants
FR2772370B1 (en) * 1997-12-12 2000-01-07 Poudres & Explosifs Ste Nale PYROTECHNIC COMPOSITIONS GENERATING NON-TOXIC GASES BASED ON AMMONIUM PERCHLORATE
DE29821541U1 (en) 1998-12-02 1999-02-18 TRW Airbag Systems GmbH & Co. KG, 84544 Aschau Azide-free, gas generating composition
DE10204268A1 (en) * 2002-02-02 2003-08-14 Fraunhofer Ges Forschung Gas generating compositions free of metal aerosol release, for use e.g. in rocket propulsion, airbags, high-pressure metal forming or explosives, contain zinc ammine nitrate as oxidizer

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US5429691A (en) * 1993-08-10 1995-07-04 Thiokol Corporation Thermite compositions for use as gas generants comprising basic metal carbonates and/or basic metal nitrates
WO1995019944A1 (en) * 1994-01-19 1995-07-27 Thiokol Corporation Metal complexes for use as gas generants

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9199886B2 (en) 1994-01-19 2015-12-01 Orbital Atk, Inc. Metal complexes for use as gas generants

Also Published As

Publication number Publication date
ES2106609T3 (en) 1997-11-01
EP0716060A1 (en) 1996-06-12
DE4442037C1 (en) 1995-12-21
ATE156111T1 (en) 1997-08-15
DE59500442D1 (en) 1997-09-04

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