EP0905108A1 - Particle-free gas generating mixture - Google Patents
Particle-free gas generating mixture Download PDFInfo
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- EP0905108A1 EP0905108A1 EP98118023A EP98118023A EP0905108A1 EP 0905108 A1 EP0905108 A1 EP 0905108A1 EP 98118023 A EP98118023 A EP 98118023A EP 98118023 A EP98118023 A EP 98118023A EP 0905108 A1 EP0905108 A1 EP 0905108A1
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- 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
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- the invention relates to a particle-free gas-generating mixture for use in gas generators for safety devices, in particular in gas generators for vehicle occupant restraint systems.
- Gas generators for safety devices usually contain a solid fuel based on sodium azide as a gas supplier Main component.
- sodium azide is toxic and can become easily with heavy metals forming extremely dangerous and violent implement reacting connections. Therefore, both in manufacturing the gas-generating mixtures as well as in the disposal Defective or unused gas generators require special measures.
- blowing agents containing sodium azide also a range of solids through suitable filter devices removed from the gas flow in the gas generator or in the gas generator have to be held back. There have therefore been attempts to Production of blowing agents which burn off essentially without residues undertaken.
- US-A-5 545 272 describes a gas generating composition which consists essentially of 35 to 55 wt .-% nitroguanidine and about 45 to 65 wt .-% phase-stabilized ammonium nitrate.
- phase stabilizing agents are potassium salts, e.g. Potassium nitrate and potassium perchlorate, but also potassium dichromate, Potassium oxalate and mixtures thereof in an amount from 5 to about 25 % By weight, preferably 10 to 15%.
- the gas generating composition of US-A-5 545 272 can due to the relatively high proportion of phase stabilizing additives not residue-free for the ammonium nitrate, i.e. without solid combustion residues burn down.
- phase stabilizing additives not residue-free for the ammonium nitrate, i.e. without solid combustion residues burn down.
- smoke formation caused by filter devices in the gas generator can only be suppressed incompletely.
- the known mixture is difficult to ignite and has a relative low burning rate.
- the high proportion of ammonium nitrate also leads to a high hygroscopicity, which occurs during processing. Storage and use in the gas generator an increased Effort requires an undesirable change in the fuel mixture to prevent.
- DE 195 05 568 A1 discloses a propellant for gas generators, the fuel as at least one compound from the group Tetrazoles, triazoles, triazines, cyanic acid, urea, their derivatives, Descendants or their salts, at least three as oxidizing agents Compounds from the group of peroxides, nitrates, chlorates or Perchlorate, as well as combustion moderators and the proportion of toxic Contains gas reducing supplements. Can be used as urea derivatives Biuret, guanidine, nitroguanidine, guanidine nitrate, aminoguanidine, Aminoguanidine nitrate, thiourea and triaminoguanidine nitrate be used.
- the invention accordingly provides an acid-free, particle-free burning, gas generating mixture for use in a gas generator ready for a safety device, which consists of a high-energy Fuel with an oxygen value of not less than -35%, with an oxidizer mixture of ammonium nitrate and ammonium perchlorate an ammonium nitrate content of 35 to 50 wt .-% and an ammonium perchlorate content of between 3 and 10% by weight, based in each case on the Total weight of the mixture, possibly a phase stabilizing one Additive for the ammonium nitrate in a proportion of at most 5% by weight, based on the weight of the ammonium nitrate, Burning moderators in a proportion of 0 to 3 wt .-%, based on the Total weight of the mixture and processing aids in one Proportion of 0 to 5% by weight, based on the total weight of the mixture, consists.
- the total water content of the gas-generating mixture is at most 0.3%.
- the ammonium nitrate content is preferably between 40 and 50%, particularly preferably between 40 and 45%.
- the ammonium perchlorate content is preferably in the range between 3 and 7% by weight.
- the high-energy fuel is preferably from guanidine nitrate, Nitroguanidine, triaminoguanidine nitrate, urea nitrate, Nitro urea, nitropenta, nitrotriazalon, hexogen, octogen or their mixtures selected existing group. Particularly preferred is the fuel guanidine nitrate and / or nitroguanidine. The latter is the most preferred fuel.
- the ammonium nitrate used in the invention can be small amounts contain phase stabilizing additives to increase storage stability, those made of copper oxide, zinc oxide, complex zinc compounds or mixtures of existing groups are selected. It it has been found that, in contrast to those in US-A-5 545 272 required amounts of 10 to 15% of potassium compounds for phase stabilization in the application according to the invention at most 5% of the mentioned additives are needed. Surprisingly, was found. that while controlling the water content of the overall mixture the proportion of phase-stabilizing additives reduced to zero can be. While phase stabilizing at water contents of 0.1 to 0.3% Additions of 3 to 5% to ensure storage stability can be used if the water content is below 0.1% phase-stabilizing additives are completely dispensed with. All in all this results in a reduction in solid emissions compared to US Pat. No. 5,545,272 by the mixture according to the invention from 50 to 100%.
- the compounds known in the art can be used as the combustion moderator. These include transition metal compounds and carbon black.
- the transition metal compounds can be selected from the group of transition metal oxides, hydroxides, nitrates, carbonates and organometallic compounds of the transition metals. Exemplary examples of this are iron oxides, copper oxides, chromium oxides, zinc oxide, copper chromite, basic copper nitrate, zinc carbonate, copper resorcylate and ferrocene.
- carbon black as a combustion moderator, optionally in a mixture with transition metal compounds, is preferred, however, because carbon black is inexpensive on the one hand and burns off without residue with the formation of CO 2 .
- processing aids are added, which from the from the Pressing aids, trickling aids or lubricants existing group selected are.
- processing aids are Polyethylene glycol, cellulose, methyl cellulose, graphite, wax, magnesium stearate, Zinc stearate, boron nitride, talc, bentonite, silicon dioxide or molybdenum sulfide.
- Ammonium nitrate content ensures that the inherently unfavorable properties, such as. the low structural stability, hygroscopicity, the poor willingness to ignite and the slow burning rate of mixtures containing ammonium nitrate through the addition of ammonium perchlorate can be compensated.
- an ammonium perchlorate content of less than 3% there is no significant improvement with regard to the willingness to ignite and the burning rate of the Fuel.
- An ammonium perchlorate content of above 10% by weight leads to the formation of free hydrogen chloride, which is due to the strict toxicity requirements for propellant gases for occupant protection systems is undesirable.
- ammonium perchlorate leads also in the small proportion of 3 to 10% by weight Increase in the willingness to ignite and burning rate of the invention Propellant. Due to the higher oxygen content of Ammonium perchlorate can also the ammonium nitrate in the Mixture can be reduced more.
- the invention thus creates a gas yield of up to 100 percent burning gas-generating mixture from which an essentially particle-free gas mixture is released and that physiologically is harmless.
- the use of an oxidizer mixture Ammonium nitrate and ammonium perchlorate also ensure good Willingness to ignite and a high burning rate. At the same time points the mixture according to the invention has high thermal and chemical stability on.
- a temperature storage test at 110 ° C. was also carried out with the mixture carried out over 400 h.
- the measured weight loss was below 0.8%; the mixture is therefore sufficiently stable.
- a thermal shock test was also carried out on tablets with different moisture contents.
- the tablets were first dried in vacuo ( ⁇ 1 mbar) at 100 ° C for 18 hours, then part of it was in a desiccator over 8 hours at 45% rel. Moisture again moistened in a defined way.
- the H 2 O content of the dried tablets was 0.08%, the H 2 O content of the moistened tablets was 0.30%.
- the tablets were hermetically sealed in an aluminum container and subjected to a temperature change between - 35 ° C and + 85 ° C (56 cycles). While the tablets with the increased moisture content swelled strongly after the test, were partially broken and thus had become unusable for the intended use, the dry tablets showed no change in their mechanical properties.
- Example 1 The tablets with a moisture content of 0.20% were the in Example 1 subjected to thermal cycling. After The tablets showed no change when the stress was complete their mechanical properties.
- Example 1 Tablets processed and ignited in a gas generator 51.5 g dried nitroguanidine, 40.0 g dried ammonium nitrate, 8.0 g of dried ammonium perchlorate, 2 g of copper chromite and 0.5 g of carbon black was added in the manner described in Example 1 Tablets processed and ignited in a gas generator.
- the average burning rate at 200 bar was 23 mm / s.
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Abstract
Description
Die Erfindung betrifft ein partikelfreies gaserzeugendes Gemisch zur Verwendung in Gasgeneratoren für Sicherheitseinrichtungen, insbesondere in Gasgeneratoren für Fahrzeuginsassen-Rückhaltesysteme.The invention relates to a particle-free gas-generating mixture for use in gas generators for safety devices, in particular in gas generators for vehicle occupant restraint systems.
Gasgeneratoren für Sicherheitseinrichtungen enthalten üblicherweise einen Festtreibstoff auf der Grundlage von Natriumazid als gasliefernde Hauptkomponente. Natriumazid ist jedoch giftig und kann sich leicht mit Schwermetallen unter Bildung extrem gefährlicher und heftig reagierender Verbindungen umsetzen. Daher sind sowohl bei der Herstellung der gaserzeugenden Gemische als auch bei der Entsorgung defekter oder unverbrauchter Gasgeneratoren besondere Maßnahmen erforderlich.Gas generators for safety devices usually contain a solid fuel based on sodium azide as a gas supplier Main component. However, sodium azide is toxic and can become easily with heavy metals forming extremely dangerous and violent implement reacting connections. Therefore, both in manufacturing the gas-generating mixtures as well as in the disposal Defective or unused gas generators require special measures.
Bei der Verbrennung von natriumazidhaltigen Treibmitteln entstehen zudem eine Reihe von Feststoffen, die durch geeignete Filtereinrichtungen im Gasgenerator aus dem Gasstrom entfernt bzw. im Gasgenerator zurückgehalten werden müssen. Es wurden daher bereits Versuche zur Herstellung von im wesentlichen rückstandsfrei abbrennenden Treibmitteln unternommen. Combustion of blowing agents containing sodium azide also a range of solids through suitable filter devices removed from the gas flow in the gas generator or in the gas generator have to be held back. There have therefore been attempts to Production of blowing agents which burn off essentially without residues undertaken.
In der US-A-5 545 272 ist eine gaserzeugende Zusammensetzung beschrieben, die im wesentlichen aus 35 bis 55 Gew.-% Nitroguanidin und etwa 45 bis 65 Gew.-% phasenstabilisiertem Ammoniumnitrat besteht. Der Zusatz von phasenstabilisierenden Mitteln zu dem Ammoniumnitrat wird als notwendig erachtet, da eine in reinem Ammoniumnitrat bei 32,3°C auftretende Strukturänderung mit einer Volumenzunahme verbunden ist, die gemäß der genannten Patentschrift verhindert werden soll. Als phasenstabilisierende Zusätze werden Kaliumsalze, wie z.B. Kaliumnitrat und Kaliumperchlorat, aber auch Kaliumdichromat, Kaliumoxalat und deren Mischungen in einer Menge von 5 bis etwa 25 Gew.-%, bevorzugt 10 bis 15%, genannt.US-A-5 545 272 describes a gas generating composition which consists essentially of 35 to 55 wt .-% nitroguanidine and about 45 to 65 wt .-% phase-stabilized ammonium nitrate. Of the Addition of phase stabilizing agents to the ammonium nitrate considered necessary because one in pure ammonium nitrate at 32.3 ° C occurring structural change is associated with an increase in volume, which is to be prevented according to the cited patent. As phase stabilizing additives are potassium salts, e.g. Potassium nitrate and potassium perchlorate, but also potassium dichromate, Potassium oxalate and mixtures thereof in an amount from 5 to about 25 % By weight, preferably 10 to 15%.
Die gaserzeugende Zusammensetzung der US-A-5 545 272 kann jedoch aufgrund des relativ hohen Anteils an phasenstabilisierenden Zusätzen für das Ammoniumnitrat nicht rückstandsfrei, d.h. ohne feste Verbrennungsrückstände abbrennen. Beim Abbrand dieses Treibstoffs tritt somit eine Rauchbildung ein, die durch Filtereinrichtungen im Gasgenerator nur unvollständig unterdrückt werden kann. Zudem ist die bekannte Mischung nur schlecht anzündbar und weist eine relativ geringe Abbrandgeschwindigkeit auf. Der hohe Anteil an Ammoniumnitrat führt überdies zu einer hohen Hygroskopizität, die bei der Verarbeitung. Lagerung und dem Einsatz im Gasgenerator einen erhöhten Aufwand erfordert, um eine unerwünschte Veränderung des Treibstoffgemischs zu verhindern.However, the gas generating composition of US-A-5 545 272 can due to the relatively high proportion of phase stabilizing additives not residue-free for the ammonium nitrate, i.e. without solid combustion residues burn down. When this fuel burns up thus smoke formation caused by filter devices in the gas generator can only be suppressed incompletely. In addition, the known mixture is difficult to ignite and has a relative low burning rate. The high proportion of ammonium nitrate also leads to a high hygroscopicity, which occurs during processing. Storage and use in the gas generator an increased Effort requires an undesirable change in the fuel mixture to prevent.
Die DE 195 05 568 A1 offenbart ein Treibmittel für Gasgeneratoren, die als Brennstoff wenigstens eine Verbindung aus der Gruppe Tetrazole, Triazole, Triazine, Cyansäure, Harnstoff, deren Derivate, Abkömmlinge oder deren Salze, als Oxidationsmittel wenigstens drei Verbindungen aus der Gruppe der Peroxide, Nitrate, Chlorate oder Perchlorate, sowie Abbrandmoderatoren und den Anteil der toxischen Gase reduzierende Zuschläge enthält. Als Harnstoffderivate können Biuret, Guanidin, Nitroguanidin, Guanidinnitrat, Aminoguanidin, Aminoguanidinnitrat, Thioharnstoff und Triaminoguanidinnitrat eingesetzt werden. Als Oxidationsmittel werden, unabhängig voneinander, unter anderem Ammoniumnitrat oder Ammoniumperchlorat genannt. Die DE 195 05 568 A1 enthält jedoch keinerlei Angaben zum Anteil der Feststoffe in der nach dem Abbrand der Treibmittel freigesetzten Gasmischung.DE 195 05 568 A1 discloses a propellant for gas generators, the fuel as at least one compound from the group Tetrazoles, triazoles, triazines, cyanic acid, urea, their derivatives, Descendants or their salts, at least three as oxidizing agents Compounds from the group of peroxides, nitrates, chlorates or Perchlorate, as well as combustion moderators and the proportion of toxic Contains gas reducing supplements. Can be used as urea derivatives Biuret, guanidine, nitroguanidine, guanidine nitrate, aminoguanidine, Aminoguanidine nitrate, thiourea and triaminoguanidine nitrate be used. As an oxidizer, become independent from each other, including ammonium nitrate or ammonium perchlorate called. However, DE 195 05 568 A1 does not contain any information on Proportion of solids in the after the propellant burns released gas mixture.
Es besteht daher weiterhin Bedarf an rückstandsfrei abbrennenden Treibmitteln für Gasgeneratoren, die ungiftig, d.h. azid- und schwermetallfrei sind, unter Bildung eines partikelfreien, ungiftigen Verbrennungsgases mit hunderprozentiger Gasausbeute abbrennen und eine ausreichend hohe Abbrandgeschwindigkeit sowie eine gute thermische und chemische Stabilität aufweisen.There is therefore still a need for residue-free burning Blowing agents for gas generators that are non-toxic, i.e. free of azide and heavy metals are, forming a particle-free, non-toxic combustion gas burn with 100% gas yield and one sufficiently high burn rate and good thermal and have chemical stability.
Die Erfindung stellt demgemäß ein azidfreies, partikelfrei abbrennendes, gaserzeugendes Gemisch zur Verwendung in einem Gasgenerator für eine Sicherheitseinrichtung bereit, welches aus einem energiereichen Brennstoff mit einem Sauerstoffwert von nicht unter -35%, einem Oxidatorgemisch aus Ammoniumnitrat und Ammoniumperchlorat mit einem Ammoniumnitratanteil von 35 bis 50 Gew.-% und einem Ammoniumperchloratanteil von zwischen 3 und 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Gemischs, gegebenenfalls einem phasenstabilisierenden Zusatz für das Ammoniumnitrat in einem Anteil von höchstens 5 Gew.-%, bezogen auf das Gewicht des Ammoniumnitrats, Abbrandmoderatoren in einem Anteil von 0 bis 3 Gew.-%, bezogen auf das Gesamtgewicht des Gemischs und Verarbeitungshilfsmittel in einem Anteil von 0 bis 5 Gew.-%, bezogen auf das Gesamtgewicht des Gemischs, besteht. Der Gesamtwassergehalt des gaserzeugenden Gemischs beträgt höchstens 0,3%. Der Ammoniumnitratanteil liegt bevorzugt zwischen 40 und 50%, besonders bevorzugt zwischen 40 und 45%. Der Ammoniumperchloratanteil liegt bevorzugt im Bereich zwischen 3 und 7 Gew.-%.The invention accordingly provides an acid-free, particle-free burning, gas generating mixture for use in a gas generator ready for a safety device, which consists of a high-energy Fuel with an oxygen value of not less than -35%, with an oxidizer mixture of ammonium nitrate and ammonium perchlorate an ammonium nitrate content of 35 to 50 wt .-% and an ammonium perchlorate content of between 3 and 10% by weight, based in each case on the Total weight of the mixture, possibly a phase stabilizing one Additive for the ammonium nitrate in a proportion of at most 5% by weight, based on the weight of the ammonium nitrate, Burning moderators in a proportion of 0 to 3 wt .-%, based on the Total weight of the mixture and processing aids in one Proportion of 0 to 5% by weight, based on the total weight of the mixture, consists. The total water content of the gas-generating mixture is at most 0.3%. The ammonium nitrate content is preferably between 40 and 50%, particularly preferably between 40 and 45%. The ammonium perchlorate content is preferably in the range between 3 and 7% by weight.
Der energiereiche Brennstoff ist vorzugsweise aus der aus Guanidinnitrat, Nitroguanidin, Triaminoguanidinnitrat, Harnstoffnitrat, Nitroharnstoff, Nitropenta, Nitrotriazalon, Hexogen, Oktogen oder deren Mischungen bestehenden Gruppe ausgewählt. Besonders bevorzugt ist der Brennstoff Guanidinnitrat und/oder Nitroguanidin. Letzteres ist der am meisten bevorzugte Brennstoff.The high-energy fuel is preferably from guanidine nitrate, Nitroguanidine, triaminoguanidine nitrate, urea nitrate, Nitro urea, nitropenta, nitrotriazalon, hexogen, octogen or their mixtures selected existing group. Particularly preferred is the fuel guanidine nitrate and / or nitroguanidine. The latter is the most preferred fuel.
Das erfindungsgemäß verwendete Ammoniumnitrat kann geringe Mengen phasenstabilisierender Zusätze zur Erhöhung der Lagerstabilität enthalten, die aus der aus Kupferoxid, Zinkoxid, komplexen Zinkverbindungen oder deren Gemische bestehenden Gruppe ausgewählt sind. Es hat sich herausgestellt, daß im Gegensatz zu den in der US-A-5 545 272 benötigten Mengen von 10 bis 15% an Kaliumverbindungen zur Phasenstabilisierung im erfindungsgemässen Anwendungsfall höchstens 5% der genannten Zusätze benötigt werden. Überraschenderweise wurde gefunden. daß bei gleichzeitiger Kontrolle des Wassergehaltes der Gesamtmischung der Anteil an phasenstabilisierenden Zusätzen bis auf Null reduziert werden kann. Während bei Wassergehalten von 0,1 bis 0,3% phasenstabilisierende Zusätze von 3 bis 5% zur Gewährleistung der Lagerstabilität eingesetzt werden, kann bei Wassergehalten von unter 0,1% auf phasenstabilisierende Zusätze völlig verzichtet werden. Insgesamt ergibt sich so gegenüber der US-A-5 545 272 eine Reduktion der Feststoffemissionen durch das erfindungsgemässe Gemisch von 50 bis 100%.The ammonium nitrate used in the invention can be small amounts contain phase stabilizing additives to increase storage stability, those made of copper oxide, zinc oxide, complex zinc compounds or mixtures of existing groups are selected. It it has been found that, in contrast to those in US-A-5 545 272 required amounts of 10 to 15% of potassium compounds for phase stabilization in the application according to the invention at most 5% of the mentioned additives are needed. Surprisingly, was found. that while controlling the water content of the overall mixture the proportion of phase-stabilizing additives reduced to zero can be. While phase stabilizing at water contents of 0.1 to 0.3% Additions of 3 to 5% to ensure storage stability can be used if the water content is below 0.1% phase-stabilizing additives are completely dispensed with. All in all this results in a reduction in solid emissions compared to US Pat. No. 5,545,272 by the mixture according to the invention from 50 to 100%.
Als Abbrandmoderator können die in der Technik bekannten Verbindungen eingesetzt werden. Unter anderem zählen hierzu Übergangsmetallverbindungen und Ruß. Die Übergangsmetallverbindungen können ausgewählt werden aus der Gruppe der Übergangsmetalloxide, -hydroxide, -nitrate, -carbonate und metallorganischer Verbindungen der Übergangsmetalle. Exemplarische Beispiele hierfür sind Eisenoxide, Kupferoxide, Chromoxide, Zinkoxid, Kupferchromit, basisches Kupfernitrat, Zinkcarbonat, Kupferresorcylat und Ferrocen. Eine Verwendung von Ruß als Abbrandmoderator, gegebenenfalls im Gemisch mit Übergangsmetallverbindungen, wird jedoch bevorzugt, da Ruß zum einen kostengünstig ist und zum anderen unter Bildung von CO2 rückstandsfrei abbrennt.The compounds known in the art can be used as the combustion moderator. These include transition metal compounds and carbon black. The transition metal compounds can be selected from the group of transition metal oxides, hydroxides, nitrates, carbonates and organometallic compounds of the transition metals. Exemplary examples of this are iron oxides, copper oxides, chromium oxides, zinc oxide, copper chromite, basic copper nitrate, zinc carbonate, copper resorcylate and ferrocene. The use of carbon black as a combustion moderator, optionally in a mixture with transition metal compounds, is preferred, however, because carbon black is inexpensive on the one hand and burns off without residue with the formation of CO 2 .
Schließlich können dem gaserzeugenden Gemisch in bekannter Weise auch Verarbeitungshilfsmittel beigegeben werden, die aus der aus den Preßhilfen, Rieselhilfen oder Gleitmittel bestehenden Gruppe ausgewählt sind. Beispiele für derartige Verarbeitungshilfsmittel sind Polyethylenglykol, Zellulose, Methylzellulose, Graphit, Wachs, Magnesiumstearat, Zinkstearat, Bornitrid, Talkum, Bentonit, Siliziumdioxid oder Molybdänsulfid.Finally, the gas-generating mixture in a known manner also processing aids are added, which from the from the Pressing aids, trickling aids or lubricants existing group selected are. Examples of such processing aids are Polyethylene glycol, cellulose, methyl cellulose, graphite, wax, magnesium stearate, Zinc stearate, boron nitride, talc, bentonite, silicon dioxide or molybdenum sulfide.
Der erfindungsgemäß unter 50 Gew-%, bevorzugt unter 45%, liegende Ammoniumnitratanteil gewährleistet, daß die an sich ungünstigen Eigenschaften, wie z.B. die geringe Strukturstabilität, Hygroskopizität, die schlechte Anzündwilligkeit und die niedrige Abbrandgeschwindigkeit von Ammoniumnitrat enthaltenden Gemischen durch den Zusatz von Ammoniumperchlorat kompensiert werden können. Bei einem Ammoniumperchloratanteil von unter 3% tritt aber keine wesentliche Verbesserung bezüglich der Anzündwilligkeit und der Abbrandgeschwindigkeit des Treibstoffs ein. Ein Ammoniumperchloratanteil von oberhalb 10 Gew.-% führt zu einer Bildung von freiem Chlorwasserstoff, was aufgrund der strengen Toxizitätsanforderungen an Treibgase für Insassenschutzsysteme unerwünscht ist. Überraschenderweise wurde gefunden, daß eine Verwendung von Ammoniumperchlorat in Anteilen zwischen 3 und 10 Gew.-% im praktischen Einsatz nicht zur Bildung von Chlorwasserstoff führt oder die Chlorwasserstoffkonzentration in der Gasmischung, vermutlich aufgrund von Absorptionseffekten oder einer Niederschlagung mit Wasserdampf, wesentlich geringer ist als nach theoretischen Berechnungen erwartet. Das erfindungsgemäße gaserzeugende Gemisch kann daher als physiologisch unbedenklich eingestuft werden.That according to the invention is less than 50% by weight, preferably less than 45% Ammonium nitrate content ensures that the inherently unfavorable properties, such as. the low structural stability, hygroscopicity, the poor willingness to ignite and the slow burning rate of mixtures containing ammonium nitrate through the addition of ammonium perchlorate can be compensated. With an ammonium perchlorate content of less than 3% there is no significant improvement with regard to the willingness to ignite and the burning rate of the Fuel. An ammonium perchlorate content of above 10% by weight leads to the formation of free hydrogen chloride, which is due to the strict toxicity requirements for propellant gases for occupant protection systems is undesirable. Surprisingly, it was found that a Use of ammonium perchlorate in proportions between 3 and 10% by weight does not lead to the formation of hydrogen chloride in practical use or the concentration of hydrogen chloride in the gas mixture, presumably due to absorption effects or precipitation Water vapor, is significantly lower than according to theoretical calculations expected. The gas-generating mixture according to the invention can therefore can be classified as physiologically harmless.
Darüber hinaus führt aber die Verwendung von Ammoniumperchlorat auch in dem geringen Anteil von 3 bis 10 Gew-% zu einer wesentlichen Steigerung der Anzündwilligkeit und Abbrandgeschwindigkeit des erfindungsgemäßen Treibmittels. Durch den höheren Sauerstoffgehalt von Ammoniumperchlorat kann überdies der Ammoniumnitratanteil in dem Gemisch stärker vermindert werden.In addition, the use of ammonium perchlorate leads also in the small proportion of 3 to 10% by weight Increase in the willingness to ignite and burning rate of the invention Propellant. Due to the higher oxygen content of Ammonium perchlorate can also the ammonium nitrate in the Mixture can be reduced more.
Die Erfindung schafft somit ein mit bis zu hundertprozentiger Gasausbeute abbrennendes gaserzeugendes Gemisch, aus dem ein im wesentlichen partikelfreies Gasgemisch freigesetzt wird und das physiologisch unbedenklich ist. Die Verwendung eines Oxidatorgemischs aus Ammoniumnitrat und Ammoniumperchlorat gewährleistet zudem eine gute Anzündwilligkeit und eine hohe Abbrandgeschwindigkeit. Zugleich weist das erfindungsgemäße Gemisch eine hohe thermische und chemische Stabilität auf.The invention thus creates a gas yield of up to 100 percent burning gas-generating mixture from which an essentially particle-free gas mixture is released and that physiologically is harmless. The use of an oxidizer mixture Ammonium nitrate and ammonium perchlorate also ensure good Willingness to ignite and a high burning rate. At the same time points the mixture according to the invention has high thermal and chemical stability on.
Die Erfindung wird nachfolgend anhand bevorzugter Ausführungsbeispiele beschrieben, die jedoch nicht in einem einschränkenden Sinn zu verstehen sind. The invention is described below using preferred exemplary embodiments described, but not in a restrictive sense are to be understood.
51,5 g getrocknetes Nitroguanidin, 43.0 g getrocknetes Ammoniumnitrat, 5,0 g getrocknetes Ammoniumperchlorat und 0,5 g Ruß wurden gemeinsam in einer Kugelmühle homogenisiert und anschließend zu Treibstofftabletten verpresst. Die so hergestellten Tabletten wurden in einem Gasgenerator zur Zündung gebracht. Der im Gasgenerator erzielte Verbrennungsdruck betrug 350 bar, die Abbranddauer lag im für den vorgesehenen Anwendungszweck benötigten Bereich von 30 ms. Die Schwadenzusammensetzung des so gezündeten Gemischs erwies sich als vollständig partikelfrei. Der Chlorwasserstoffgehalt in der Schwadenzusammensetzung lag mit <50 ppm unterhalb physiologisch bedenklicher Werte.51.5 g dried nitroguanidine, 43.0 g dried Ammonium nitrate, 5.0 g dried ammonium perchlorate and 0.5 g carbon black were homogenized together in a ball mill and then added Compressed fuel tablets. The tablets so produced were ignited in a gas generator. The one in the gas generator achieved combustion pressure was 350 bar, the burn time was in the the intended application range of 30 ms. The The vapor composition of the mixture thus ignited turned out to be completely particle-free. The hydrogen chloride content in the vapor composition was less than 50 ppm below physiologically questionable Values.
Mit dem Gemisch wurde ebenso ein Temperaturlagertest bei 110°C über 400 h durchgeführt. Der gemessene Gewichtsverlust betrug unter 0,8%; das Gemisch ist damit ausreichend stabil.A temperature storage test at 110 ° C. was also carried out with the mixture carried out over 400 h. The measured weight loss was below 0.8%; the mixture is therefore sufficiently stable.
Ferner wurde ein Temperaturwechselbelastungstest mit Tabletten unterschiedlicher Feuchtegehalte durchgeführt. Die Tabletten wurden zunächst im Vakuum ( <1 mbar) bei 100°C 18 Stunden getrocknet, anschließend wurde ein Teil hiervon im Exsikkator über 8 Stunden bei 45% rel. Feuchte wieder definiert befeuchtet. Der H2O-Gehalt der getrockneten Tabletten betrug 0,08%, der H2O-Gehalt der befeuchteten Tabletten 0,30%. Die Tabletten wurden in einem Aluminiumbehälter hermetisch versiegelt und einer Temperaturwechselbelastung zwischen - 35°C und +85°C (56 Zyklen) unterworfen. Während die Tabletten mit dem erhöhten Feuchtegehalt nach dem Test stark aufquollen, teilweise zerbrochen und damit für den vorgesehenen Einsatzzweck unbrauchbar geworden waren, zeigten die trockenen Tabletten keine Änderung ihrer mechanischen Eigenschaften.A thermal shock test was also carried out on tablets with different moisture contents. The tablets were first dried in vacuo (<1 mbar) at 100 ° C for 18 hours, then part of it was in a desiccator over 8 hours at 45% rel. Moisture again moistened in a defined way. The H 2 O content of the dried tablets was 0.08%, the H 2 O content of the moistened tablets was 0.30%. The tablets were hermetically sealed in an aluminum container and subjected to a temperature change between - 35 ° C and + 85 ° C (56 cycles). While the tablets with the increased moisture content swelled strongly after the test, were partially broken and thus had become unusable for the intended use, the dry tablets showed no change in their mechanical properties.
51,5 g getrocknetes Nitroguanidin, 43,0 g Ammoniumnitrat, das mit 4% ZnO als Phasenstabilisator versehen war, 5,0 g getrocknetes Ammoniumperchlorat, und 5,0 g Ruß wurden in der im Beispiel 1 beschriebenen Weise zu Tabletten verarbeitet. 51.5 g dried nitroguanidine, 43.0 g ammonium nitrate, which with 4% ZnO was provided as a phase stabilizer, 5.0 g dried Ammonium perchlorate, and 5.0 g of carbon black were in the in Example 1 described way processed into tablets.
Die Tabletten mit einem Feuchtegehalt von 0,20% wurden der in Beispiel 1 beschriebenen Temperaturwechselbelastung unterzogen. Nach abgeschlossener Belastung zeigten die Tabletten keine Veränderung ihrer mechanischen Eigenschaften.The tablets with a moisture content of 0.20% were the in Example 1 subjected to thermal cycling. After The tablets showed no change when the stress was complete their mechanical properties.
51,5 g getrocknetes Nitroguanidin, 40,0 g getrocknetes Ammoniumnitrat, 8,0 g getrocknetes Ammoniumperchlorat, 2 g Kupferchromit und 0,5 g Ruß wurden in der in Beispiel 1 beschriebenen Art und Weise zu Tabletten verarbeitet und in einem Gasgenerator zur Zündung gebracht. Die mittlere Abbrandgeschwindigkeit bei 200 bar betrug 23 mm/s.51.5 g dried nitroguanidine, 40.0 g dried ammonium nitrate, 8.0 g of dried ammonium perchlorate, 2 g of copper chromite and 0.5 g of carbon black was added in the manner described in Example 1 Tablets processed and ignited in a gas generator. The average burning rate at 200 bar was 23 mm / s.
51,5 g getrocknetes Nitroguanidin, 40,0 g getrocknetes Ammoniumnitrat, 8,0 g getrocknetes Ammoniumperchlorat, 2 g Eisenoxid (γ-Fe2O3) und 0,5 g Ruß wurden in der in Beispiel 1 beschriebenen Art und Weise verarbeitet und einem Temperaturlagertest bei 110°C unterworfen. Der Gewichtsverlust nach 400 h lag bei 0,13%.51.5 g of dried nitroguanidine, 40.0 g of dried ammonium nitrate, 8.0 g of dried ammonium perchlorate, 2 g of iron oxide (γ-Fe 2 O 3 ) and 0.5 g of carbon black were processed in the manner described in Example 1 and subjected to a temperature storage test at 110 ° C. The weight loss after 400 h was 0.13%.
Claims (13)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19742203 | 1997-09-24 | ||
| DE19742203A DE19742203A1 (en) | 1997-09-24 | 1997-09-24 | Particle-free gas-generating mixture |
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| Publication Number | Publication Date |
|---|---|
| EP0905108A1 true EP0905108A1 (en) | 1999-03-31 |
| EP0905108B1 EP0905108B1 (en) | 2002-11-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98118023A Expired - Lifetime EP0905108B1 (en) | 1997-09-24 | 1998-09-23 | Particle-free gas generating mixture |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US5989367A (en) |
| EP (1) | EP0905108B1 (en) |
| DE (2) | DE19742203A1 (en) |
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| WO2000014032A1 (en) * | 1998-09-09 | 2000-03-16 | Daicel Chemical Industries, Ltd. | Gas-evolving composition |
| WO2000015584A1 (en) * | 1998-09-14 | 2000-03-23 | Daicel Chemical Industries, Ltd. | Gas generator composition |
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| US6296724B1 (en) * | 1998-07-21 | 2001-10-02 | Trw Inc. | Gas generating composition for an inflatable vehicle occupant protection device |
| US6132538A (en) * | 1998-07-30 | 2000-10-17 | Autoliv Development Ab | High gas yield generant compositions |
| DE29821541U1 (en) | 1998-12-02 | 1999-02-18 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azide-free, gas generating composition |
| DE29821544U1 (en) | 1998-12-02 | 1999-02-18 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azide-free, gas generating composition |
| US6017404A (en) * | 1998-12-23 | 2000-01-25 | Atlantic Research Corporation | Nonazide ammonium nitrate based gas generant compositions that burn at ambient pressure |
| US6143102A (en) * | 1999-05-06 | 2000-11-07 | Autoliv Asp, Inc. | Burn rate-enhanced basic copper nitrate-containing gas generant compositions and methods |
| US6176950B1 (en) * | 1999-05-17 | 2001-01-23 | James C. Wood | Ammonium nitrate and paraffinic material based gas generating propellants |
| US6149746A (en) * | 1999-08-06 | 2000-11-21 | Trw Inc. | Ammonium nitrate gas generating composition |
| US6361630B2 (en) * | 1999-08-17 | 2002-03-26 | Trw Inc. | Cool burning gas generating composition |
| US20030066584A1 (en) * | 2000-03-01 | 2003-04-10 | Burns Sean P. | Gas generant composition |
| US6550808B1 (en) * | 2000-11-17 | 2003-04-22 | Autoliv Asp. Inc. | Guanylurea nitrate in gas generation |
| US6547900B2 (en) * | 2001-01-24 | 2003-04-15 | Breed Automotive Technology, Inc. | Method of stabilizing the density of gas generant pellets containing nitroguanidine |
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| US6875295B2 (en) | 2001-12-27 | 2005-04-05 | Trw Inc. | Cool burning gas generating material for a vehicle occupant protection apparatus |
| DE10230402B4 (en) * | 2002-07-05 | 2007-01-11 | Trw Airbag Systems Gmbh & Co. Kg | Process for the preparation of a gas generating composition |
| US7758709B2 (en) | 2006-06-21 | 2010-07-20 | Autoliv Asp, Inc. | Monolithic gas generant grains |
| US9193639B2 (en) * | 2007-03-27 | 2015-11-24 | Autoliv Asp, Inc. | Methods of manufacturing monolithic generant grains |
| US8057611B2 (en) * | 2007-08-13 | 2011-11-15 | Autoliv Asp, Inc. | Multi-composition pyrotechnic grain |
| WO2009126182A1 (en) * | 2008-04-10 | 2009-10-15 | Autoliv Asp, Inc. | Monolithic gas generants containing perchlorate-based oxidizers and methods for manufacture thereof |
| US8815029B2 (en) | 2008-04-10 | 2014-08-26 | Autoliv Asp, Inc. | High performance gas generating compositions |
| US8808476B2 (en) | 2008-11-12 | 2014-08-19 | Autoliv Asp, Inc. | Gas generating compositions having glass fibers |
| US9051223B2 (en) | 2013-03-15 | 2015-06-09 | Autoliv Asp, Inc. | Generant grain assembly formed of multiple symmetric pieces |
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Also Published As
| Publication number | Publication date |
|---|---|
| DE19742203A1 (en) | 1999-03-25 |
| EP0905108B1 (en) | 2002-11-27 |
| DE59806422D1 (en) | 2003-01-09 |
| US5989367A (en) | 1999-11-23 |
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