EP0536525A1 - Gaserzeugendes Gemisch - Google Patents

Gaserzeugendes Gemisch Download PDF

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Publication number
EP0536525A1
EP0536525A1 EP92114600A EP92114600A EP0536525A1 EP 0536525 A1 EP0536525 A1 EP 0536525A1 EP 92114600 A EP92114600 A EP 92114600A EP 92114600 A EP92114600 A EP 92114600A EP 0536525 A1 EP0536525 A1 EP 0536525A1
Authority
EP
European Patent Office
Prior art keywords
mixture
weight
mixture according
metal
silicon dioxide
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.)
Withdrawn
Application number
EP92114600A
Other languages
German (de)
English (en)
French (fr)
Inventor
Siegfried Dr. Zeuner
Joachim Dr. Sans
Uwe Dölling
Karl-Heinz Rödig
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.)
ZF Airbag Germany GmbH
Original Assignee
Bayern Chemie Airbag GmbH
Temic Bayern Chemie Airbag GmbH
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
Application filed by Bayern Chemie Airbag GmbH, Temic Bayern Chemie Airbag GmbH filed Critical Bayern Chemie Airbag GmbH
Publication of EP0536525A1 publication Critical patent/EP0536525A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B35/00—Compositions containing a metal azide
    • 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, in particular for inflating air bags (airbags) for occupant protection devices in motor vehicles.
  • DE-PS 22 36 175 discloses a gas-generating mixture for airbags made of sodium azide as the main gas-supplying component, potassium nitrate as the oxidizer and silicon dioxide.
  • the task of the silicon dioxide is to bind sodium and potassium formed in the reaction of the azide with the nitrate as slag, ie to prevent these metals or their oxides from entering the propellant gas as fine dust particles.
  • a burning rate of more than 40 mm / s can be achieved, so that an airbag is inflated within a few 100 / s. It also exhibits satisfactory ignitability.
  • the known mixture has a very high combustion temperature, which places a high thermal load on the gas generator.
  • gas-generating compositions consist of an alkali metal azide and a metal oxide, usually iron oxide (cf. US Pat. No. 3,895,098).
  • the metal oxide serves both as an oxidizer and as a slag former.
  • Example 5 of US Pat. No. 4,931,111 a mixture of 62.0% sodium azide, 0.5% graphite, 4.36% potassium nitrate, 13.14% iron oxide and 20% bentonite leads to a burning rate of 29 mm / s. If, according to Example 9 of US Pat. No. 4,931,111, the bentonite is replaced by silicon dioxide for this mass, the burn-off rate drops drastically to 8.1 mm / s.
  • the object of the invention is to provide a gas-generating mixture which, at a relatively low combustion temperature, leads to a minimal emission of very fine dust particles and has a sufficient burn-off rate and good ignition quality.
  • the burning rate is more than 40 mm / s and a perfect ignitability is obtained if no graphite is added and the proportion of silicon dioxide in the mixture is at most 18 % By weight, i. H. the proportion of the accelerator made of metal nitrate and silicon dioxide is at most 23% by weight of the mixture, the silicon dioxide being at most four times the metal nitrate.
  • the proportion of silicon dioxide in the mixture according to the invention is overall significantly lower than in Example 9 of US Pat. No. 4,931,111.
  • the silicon dioxide content of the mixture must be at least 3% by weight in order to ensure that the rate of combustion is sufficient and that it is ready to ignite. More than 4% by weight is preferably used.
  • the burn-off rate of more than 40 mm / s achievable with the mixture according to the invention is thus 25% higher than that according to US Pat. No. 4,931,111 when using bentonite max. achievable burning rate and even almost five times the burning rate of the mixture according to Example 9 of US Pat. No. 4,931,111, which contains 20% silicon dioxide, 4.36% potassium nitrate and 0.50% graphite.
  • the mixture according to the invention has excellent ignitability.
  • the mixture according to the invention preferably also contains one or more substances to improve processability and / or chemical stability.
  • This can be a substance that improves both the processability and the chemical stability, but two or more substances can also be used together.
  • B. improves processability, while the other or the other substances improve the chemical stability.
  • the content of all these substances together is preferably at most 5% by weight, based on the total weight of the mixture, particularly preferably 0.1 to 3% by weight.
  • These substances include pouring and pressing aids, which have neutral to basic properties and / or hydrophobic properties, since this increases the chemical stability of the compacts produced compared to the usual air components (CO2, H2O).
  • these substances include: graphite, tricalcium phosphate, alkylene naphthalenesulfonic acid salts, talc, metal stearates, silicates, metal soaps, waxes and silicones. Many of these substances act as antistatic agents at the same time, thereby reducing the risk of electrostatically induced self-ignition of the mixture.
  • the content of the alkali and / or alkaline earth azide of the mixture according to the invention is preferably 58 to 65% by weight.
  • Sodium azide is preferably used as the alkali azide.
  • the content of the metal oxide in the mixture according to the invention is 15 to 35% by weight, preferably 20 to 30% by weight. Due to the metal oxide as oxidizer and slag former, the mixture according to the invention leads to a relatively low combustion temperature. At the same time, dirt emissions are minimal. Not only is the proportion of slag particles in the propellant gas low, i.e. the proportion of relatively coarse particles that result from atomizing molten components, but above all the proportion of fine dust particles made from alkali or alkaline earth metals and oxides, which are particularly harmful because they lead to an etching of the mucous membranes and the respiratory tract.
  • the proportion of the accelerator in the mixture is preferably 5 to 19% by weight, and if the mixture contains at least one substance for improving processability and / or chemical stability, the proportion of the accelerator is preferably 8 to 12% by weight.
  • the ratio of the metal nitrate to the silicon dioxide of the mixture according to the invention is preferably 1: 1 to 1: 3 and, if there is at least one substance to improve processability and / or chemical stability, 1: 1 to 1: 2.
  • the mixture according to the invention is formed by mixing the powdery components, that is to say the alkali metal or alkaline earth metal azide, metal oxide, metal nitrate and silicon dioxide.
  • the particle size of the particles of the total mixture is preferably adjusted so that 50 wt .-% of the particles of the Total mixture have a size of less than 10 microns. If the proportion of particles with a particle size of 10 ⁇ m or less does not reach 50% by weight, the mixture is ground until this value is set. The mixture is then compressed, for example into tablets.
  • Fumed silica with a specific surface area of at least 50 m2 / g (according to BET), preferably with a specific surface area of more than 200 m2 / g, is preferably used as silicon dioxide.
  • the silicon oxide also serves as a trickle and pressing aid in the manufacture of the tablets.
  • Oxides of the metals of the fourth period of the transition elements ie. H. with atomic numbers 21 (scandium) to 30 (zinc).
  • the use of iron oxide (Fe2O3) is particularly preferred.
  • the iron oxide is preferably used with an average particle size of less than 3 ⁇ m, in particular less than 1 ⁇ m.
  • the iron oxide has a specific surface area (according to BET) of more than 5 m 2 / g, preferably of more than 8 m 2 / g.
  • the metal nitrate can be an alkali and / or alkaline earth nitrate, for example strontium or barium nitrate.
  • the following powdery substances are mixed together: 60.3 wt .-% (14 mol) NaN3 11.9% by weight (3 mol) of SiO2 21.1 wt .-% (2 mol) Fe2O3 6.7 wt .-% (1 mol) of KNO3
  • SiO2 is fumed silica (Aerosil 380 from Degussa) with a BET specific surface area of approx. 380 m2 / g used.
  • the Fe2O3 has an average particle size of about 0.4 microns and a specific surface area of 10.4 m2 / g and is commercially available under the name "Mapico Red 297".
  • the mixture is ground until 50% by weight of the particles have a particle size of less than 7 ⁇ m. Then part of the mixture is pressed into tablets.
  • the tablets have the same good willingness to ignite as tablets according to DE-PS 22 36 175.
  • the burning rate is 44 mm / s.
  • the ignitability of the tablets is also documented by the course of the combustion chamber pressure (at 20 ° C.), which is shown in the diagram in FIG. 1. It can be seen from this diagram that the mixture immediately changes to a stable burn-up after ignition.
  • the following powdery substances are mixed together: 62.0 wt .-% NaN3 27.5 wt .-% Fe2O3 4.0 wt .-% KNO3 6.0% by weight SiO2 0.5% by weight graphite
  • the same SiO2 and the same Fe2O3 were used as in Example 1.
  • the mixture was ground until 50% by weight of the particles had a particle size of less than 7 ⁇ m.
  • the mixture was then compressed into tablets.
  • the tablets produced in this way have the same good ignitability as the tablets according to Example 1. The burning rate is sufficiently high.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Air Bags (AREA)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP92114600A 1991-10-11 1992-08-27 Gaserzeugendes Gemisch Withdrawn EP0536525A1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4133655 1991-10-11
DE4133655 1991-10-11
DE4218531A DE4218531C1 (enrdf_load_stackoverflow) 1991-10-11 1992-06-05
DE4218531 1992-06-05

Publications (1)

Publication Number Publication Date
EP0536525A1 true EP0536525A1 (de) 1993-04-14

Family

ID=25908121

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92114600A Withdrawn EP0536525A1 (de) 1991-10-11 1992-08-27 Gaserzeugendes Gemisch

Country Status (5)

Country Link
US (1) US5542997A (enrdf_load_stackoverflow)
EP (1) EP0536525A1 (enrdf_load_stackoverflow)
JP (1) JPH05238867A (enrdf_load_stackoverflow)
KR (1) KR100249286B1 (enrdf_load_stackoverflow)
DE (1) DE4218531C1 (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4401213C1 (de) * 1994-01-18 1995-03-02 Fraunhofer Ges Forschung Gaserzeugende Mischung
DE4401214C1 (de) * 1994-01-18 1995-03-02 Fraunhofer Ges Forschung Gaserzeugende Mischung
EP0659711A3 (en) * 1993-12-10 1995-08-09 Morton Int Inc Processing aids for gas generating compositions.
DE19516818A1 (de) * 1994-05-09 1995-11-16 Nof Corp Gasentwickler-Zusammensetzungen
DE4442037C1 (de) * 1994-11-25 1995-12-21 Fraunhofer Ges Forschung Gaserzeugende Mischung
EP0749946A1 (en) * 1995-06-22 1996-12-27 Nippon Koki Co., Ltd. Gas generating agent composition

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9505623D0 (en) * 1995-03-21 1995-05-10 Ici Plc Process for the preparation of gas-generating compositions
US7914633B1 (en) * 2003-01-28 2011-03-29 Hodgdon Powder Company, Inc. White propellant compositions
US8137771B2 (en) * 2004-09-09 2012-03-20 Daicel Chemical Industries, Ltd. Gas generating composition
JP4610266B2 (ja) 2004-09-09 2011-01-12 ダイセル化学工業株式会社 ガス発生剤組成物
NL2027858B1 (en) * 2021-03-29 2022-10-12 Exxfire Bv A nitrogen gas generator

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2193800A1 (enrdf_load_stackoverflow) * 1972-07-24 1974-02-22 Bayern Chemie Gmbh Flugchemie
US4243443A (en) * 1978-07-17 1981-01-06 C-I-L Inc. Azide and doped iron oxide gas generating composition
US4547235A (en) * 1984-06-14 1985-10-15 Morton Thiokol, Inc. Gas generant for air bag inflators
US4604151A (en) * 1985-01-30 1986-08-05 Talley Defense Systems, Inc. Method and compositions for generating nitrogen gas
EP0329293A1 (en) * 1988-02-19 1989-08-23 Morton International, Inc. Azide gas generant formulations
US4931111A (en) * 1989-11-06 1990-06-05 Automotive Systems Laboratory, Inc. Azide gas generating composition for inflatable devices

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3895098A (en) * 1972-05-31 1975-07-15 Talley Industries Method and composition for generating nitrogen gas
GB1443547A (en) * 1973-12-17 1976-07-21 Canadian Ind Metal oxide/azide gas generating compositions
DE2551921A1 (de) * 1974-11-29 1976-08-12 Eaton Corp Gaserzeugendes azid-verbindungsgemisch
CA1146756A (en) * 1980-06-20 1983-05-24 Lechoslaw A.M. Utracki Multi-ingredient gas generants
US4696705A (en) * 1986-12-24 1987-09-29 Trw Automotive Products, Inc. Gas generating material
DE3842838C1 (enrdf_load_stackoverflow) * 1988-12-20 1990-01-11 Dynamit Nobel Ag, 5210 Troisdorf, De
US5089069A (en) * 1990-06-22 1992-02-18 Breed Automotive Technology, Inc. Gas generating composition for air bags
US5051143A (en) * 1990-06-28 1991-09-24 Trw Vehicle Safety Systems Inc. Water based coating for gas generating material and method
US5143567A (en) * 1991-08-23 1992-09-01 Morton International, Inc. Additive approach to ballistic and slag melting point control of azide-based gas generant compositions
US5387296A (en) * 1991-08-23 1995-02-07 Morton International, Inc. Additive approach to ballistic and slag melting point control of azide-based gas generant compositions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2193800A1 (enrdf_load_stackoverflow) * 1972-07-24 1974-02-22 Bayern Chemie Gmbh Flugchemie
US4243443A (en) * 1978-07-17 1981-01-06 C-I-L Inc. Azide and doped iron oxide gas generating composition
US4547235A (en) * 1984-06-14 1985-10-15 Morton Thiokol, Inc. Gas generant for air bag inflators
US4604151A (en) * 1985-01-30 1986-08-05 Talley Defense Systems, Inc. Method and compositions for generating nitrogen gas
EP0329293A1 (en) * 1988-02-19 1989-08-23 Morton International, Inc. Azide gas generant formulations
US4931111A (en) * 1989-11-06 1990-06-05 Automotive Systems Laboratory, Inc. Azide gas generating composition for inflatable devices

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0659711A3 (en) * 1993-12-10 1995-08-09 Morton Int Inc Processing aids for gas generating compositions.
US5518054A (en) * 1993-12-10 1996-05-21 Morton International, Inc. Processing aids for gas generants
DE4401213C1 (de) * 1994-01-18 1995-03-02 Fraunhofer Ges Forschung Gaserzeugende Mischung
DE4401214C1 (de) * 1994-01-18 1995-03-02 Fraunhofer Ges Forschung Gaserzeugende Mischung
DE19516818A1 (de) * 1994-05-09 1995-11-16 Nof Corp Gasentwickler-Zusammensetzungen
DE4442037C1 (de) * 1994-11-25 1995-12-21 Fraunhofer Ges Forschung Gaserzeugende Mischung
EP0716060A1 (de) 1994-11-25 1996-06-12 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. Gaserzeugende Mischung
EP0749946A1 (en) * 1995-06-22 1996-12-27 Nippon Koki Co., Ltd. Gas generating agent composition

Also Published As

Publication number Publication date
KR100249286B1 (ko) 2000-03-15
JPH05238867A (ja) 1993-09-17
US5542997A (en) 1996-08-06
DE4218531C1 (enrdf_load_stackoverflow) 1993-07-15
KR930007866A (ko) 1993-05-20

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