EP1275629B1 - Nitrocellulose-free gas-generating composition - Google Patents

Nitrocellulose-free gas-generating composition Download PDF

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EP1275629B1
EP1275629B1 EP02014052A EP02014052A EP1275629B1 EP 1275629 B1 EP1275629 B1 EP 1275629B1 EP 02014052 A EP02014052 A EP 02014052A EP 02014052 A EP02014052 A EP 02014052A EP 1275629 B1 EP1275629 B1 EP 1275629B1
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composition according
weight
composition
combustion
gas
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French (fr)
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EP1275629A3 (en
EP1275629A2 (en
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Siegfried Dr. Zeuner
Roland Dr. Schropp
Achim Dr. Hofmann
Karl-Heinz Rödig
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ZF Airbag Germany GmbH
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TRW Airbag Systems GmbH
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    • 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 nitrocellulose-free gas-generating composition according to claim 1 for use in vehicle occupant restraint systems consisting essentially of two nitrogen-containing organic fuels in a proportion of 55 to 70 wt .-%, a perchlorate as an inorganic oxidizer in an amount of 30 to 45 wt. % and, optionally, between 2 and 5 wt .-% of a Abbrandmoderators and up to 5 wt .-% of conventional auxiliaries and additives.
  • nitrocellulose fuels show a high burning rate. For this reason, these fuels are mainly used in gas generators for belt tensioners.
  • the US 5,538,567 A discloses a gas generant composition of about 55 to 75 weight percent guanidine nitrate, about 25 to 45 weight percent of an oxidizer, especially potassium perchlorate, about 0.5 to 5 weight percent of a flow improver such as graphite or carbon black and up to 5% by weight of a binder such as calcium resinate.
  • the average particle size of the guanidine nitrate is between about 75 and 350 microns, and the average particle size of the oxidizer is between about 50 and 200 microns.
  • the US-A-5,854,442 describes a gas generating composition of about 30 to 45 wt .-% potassium perchlorate, between about 55 and 70 wt .-% guanidine nitrate and 1 to 3 wt .-% cellulose acetate butyrate as a binder.
  • the particle size of the oxidizer should be between 15 and 20 microns.
  • the compositions described above are only suitable for use in driver or passenger gas generators.
  • the invention provides a nitrocellulose-free gas generating composition having a higher burnup rate and improved ignitability, which can thus also be used in a belt tensioner inflator which requires shorter reaction and service times over the driver and passenger gas generators.
  • a nitrocellulose-free gas-generating composition which consists essentially of two nitrogen-containing organic fuels in a proportion of 55 to 70 wt .-%, a perchlorate as inorganic oxidizer in a proportion of 30 to 45 wt .-%, between 2 and 5 wt .-% of one or more Abbrandmoderatoren and up to 5 wt .-% of conventional auxiliaries and additives, in each case based on the total weight of the composition, wherein the pressure exponent of the composition is less than 0.35 and the Abbrandgeschwindingkeit at 200 bar is at least 40 millimeters per second (mm / s).
  • Such a composition is particularly suitable for use in a belt tensioner gas generator.
  • the oxygen balance of the composition is preferably between -5 and +5%.
  • the oxygen balance is understood to mean that amount of oxygen in percent by weight that is the case when a compound is completely reacted or a mixture to CO 2 , H 2 O, Al 2 O 3 , B 2 O 3 , etc. is released (oxygen overbalancing). If the available oxygen is insufficient for this purpose, the shortfall required for the complete conversion is indicated with a negative sign (oxygen sub-balancing). Due to the advantageous oxygen balance of the gas-generating composition according to the invention, the quantity of noxious gas produced during combustion, in particular the proportion of carbon monoxide, is low.
  • the organic fuel is guanidine nitrate in admixture with at least one other nitrogen-containing compound selected from the group consisting of nitroguanidine, nitrotriazolone (NTO), hexogen (RDX), octogen (HMX), ethylenediamine dinitrate (EDDN), triaminoguanidine nitrate (TAGN), azobisformamidine dinitrate and dinitroammine, wherein the fuel from 75 to 90 wt .-% guanidine nitrate and 10 to 25 wt .-% of the further compound, in each case based on the total weight of the fuel, is composed. More preferably, the further compound is nitroguanidine.
  • the additional nitrogen-containing compound increases the burning rate in the entire pressure range.
  • An addition of more than 25% of the further compound causes an excessive increase in the burning temperature, so that damage to the gas generator is to be feared.
  • the proportion of further connection should be kept as low as possible.
  • the inorganic oxidizer is a perchlorate, especially an alkali metal perchlorate and / or ammonium perchlorate, and most preferably potassium perchlorate.
  • combustion moderators oxygen-containing compounds of iron, copper, manganese, titanium, vanadium, molybdenum and chromium, including combinations thereof, are used.
  • the burn-off moderator is preferably selected from the group consisting of CuO, Cu 2 O, CuCr 2 O 4 , Fe 2 O 3 , 3Cu (OH) 2 x Cu (NO 3 ) 2 and mixtures thereof. Very particularly preferred is the Abbrandmoderator CuO.
  • the above-described consumable moderators are used in a proportion of between 2 and 5% by weight. Higher levels lower the gas yield of the fuel, which is not desirable in all cases.
  • the mean particle size of the Abbrandmoderators is preferably less than 5 microns and more preferably less than 1 micron, with a preferred specific surface of at least 2 m 2 / g, more preferably at least 5 m 2 / g.
  • the addition of such fine-grained Abbrandmoderatoren improves the ignition willingness of the gas-generating compositions of the invention, so that ignition delays of at most 6 milliseconds (ms) and more preferably at most 5 ms can be achieved.
  • the average particle size of the fuel and the oxidizer is preferably less than 15 microns and more preferably less than 10 microns. This contributes to the gas generating composition according to the invention having a sufficiently high burning rate for use in belt tensioner gas generators.
  • Burning rates of at least 40 mm / s under operating conditions can be achieved with the compositions according to the invention.
  • the burning rate at 200 bar is at least 45 mm / s.
  • r represents the burning rate
  • a is a fuel-specific constant
  • p is the pressure
  • n is the pressure exponent. If r and n are known at a certain pressure p, the constant a can be determined.
  • the printing exponent of the compositions according to the invention is less than 0.35 and preferably less than or equal to 0.3. Higher pressure exponents also cause worse ignition at low pressures.
  • the setting of the burning rate of the compositions according to the invention is preferably carried out by selecting the suitable fuel composition, in particular the type and proportion of the further nitrogen-containing compound, the type and proportion of each Abbrandmoderators and the average particle size of the fuel, the oxidizer and, optionally, the Abbrandmoderators.
  • the composition can be optimally adapted for use in belt tensioner gas generators.
  • auxiliaries and additives include processing aids, such as lubricants, pressing and pouring aids.
  • processing aids such as lubricants, pressing and pouring aids.
  • these compounds in particular calcium stearate, silica, graphite or carbon black may be mentioned.
  • the processing aids are preferably used in a proportion of up to 2 wt .-%, based on the total composition.
  • a particularly preferred composition according to the invention consists of 48 to 52 parts by weight of guanidine nitrate, 13 to 17 parts by weight of nitroguanidine, 33 to 37 parts by weight of potassium perchlorate, 2.0 to 5.0 parts by weight of copper oxide (CuO) and up to 1% each by weight of calcium stearate and graphite.
  • CuO copper oxide
  • Guanidine nitrate with a mean particle size of 5 microns, nitroguanidine with an average particle size of 11 microns, potassium perchlorate with a mean particle size of 7 microns, copper oxide (CuO) with an average particle size of 0.5 microns and a specific surface area of 8 m 2 / g as well as calcium stearate and graphite were mixed in the parts by weight given in Table 1 below, ground together in a ball mill and pressed into tablets of 6 x 2.5 mm.
  • Table 1 ⁇ / u> Example no.
  • Example # 3 a firing delay of 11 ms was determined; Examples Nos. 4 and 5 showed an ignition delay of 6 and 5 ms, respectively.
  • Example 5 The composition of Example 5 was further subjected to an aging test at 107 ° C for 400 hours. After this test, a weight loss of 0.07% was found, that is, the composition exhibited aging resistance sufficient to meet vehicle occupant restraint requirements. A comparison experiment with a conventional fuel based on nitrocellulose under the same conditions resulted in a weight loss of 14%. This indicates a complete decomposition and thus a complete malfunction of the fuel.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Air Bags (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Automotive Seat Belt Assembly (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

A nitrocellulose-free gas-generating composition for use in vehicle passenger safety systems (especially seat belt tensioners) has a pressure exponent below 0.35 and a combustion rate at 200 bar of ≥ 40mm/second and comprises by wt. (A) a nitrogen-containing organic fuel (55-70%); (B) an inorganic oxidizer (30-45%); (C) a combustion moderator (up to10%); and (D) conventional additives (up to 5%).

Description

Die Erfindung betrifft eine nitrozellulosefreie gaserzeugende Zusammensetzung gemäß Anspruch 1 zur Verwendung in Fahrzeuginsassenrückhaltesystemen, die im wesentlichen aus zwei stickstoffhaltigen organischen Brennstoffen in einem Anteil von 55 bis 70 Gew.-%, einem Perchlorat als anorganischen Oxidator in einem Anteil von 30 bis 45 Gew.-% sowie, gegebenenfalls, zwischen 2 und 5 Gew.-% eines Abbrandmoderators und bis zu 5 Gew.-% üblichen Hilfs- und Zusatzstoffen besteht.The invention relates to a nitrocellulose-free gas-generating composition according to claim 1 for use in vehicle occupant restraint systems consisting essentially of two nitrogen-containing organic fuels in a proportion of 55 to 70 wt .-%, a perchlorate as an inorganic oxidizer in an amount of 30 to 45 wt. % and, optionally, between 2 and 5 wt .-% of a Abbrandmoderators and up to 5 wt .-% of conventional auxiliaries and additives.

Treibstoffe auf der Grundlage von Nitrozellulose zeigen eine hohe Abbrandgeschwindigkeit. Aus diesem Grund werden diese Treibstoffe überwiegend in Gasgeneratoren für Gurtstraffer verwendet. Nachteilig an Nitrozellulose-Treibstoffen ist jedoch deren schlechte Alterungsbeständigkeit. Außerdem setzen diese Treibstoffe aufgrund ihrer extrem negativen Sauerstoffbilanz beim Abbrand große Mengen an unvollständig oxidierten Reaktionsprodukten, insbesondere Kohlenmonoxid, frei.Propellants based on nitrocellulose show a high burning rate. For this reason, these fuels are mainly used in gas generators for belt tensioners. A disadvantage of nitrocellulose fuels, however, is their poor aging resistance. In addition, these fuels release large amounts of incompletely oxidized reaction products, especially carbon monoxide, due to their extremely negative oxygen balance during combustion.

Die US-5,538,567 A offenbart eine gaserzeugende Zusammensetzung aus etwa 55 bis 75 Gew.-% Guanidinnitrat, etwa 25 bis 45 Gew.-% eines Oxidators, insbesondere Kaliumperchlorat, etwa 0,5 bis 5 Gew.-% eines Fließverbesserers wie Graphit oder Ruß und bis zu 5 Gew.-% eines Binders wie Calciumresinat. Die mittlere Teilchengröße des Guanidinnitrats beträgt zwischen etwa 75 und 350 µm, und die mittlere Teilchegröße des Oxidators liegt zwischen etwa 50 und 200 µm.The US 5,538,567 A discloses a gas generant composition of about 55 to 75 weight percent guanidine nitrate, about 25 to 45 weight percent of an oxidizer, especially potassium perchlorate, about 0.5 to 5 weight percent of a flow improver such as graphite or carbon black and up to 5% by weight of a binder such as calcium resinate. The average particle size of the guanidine nitrate is between about 75 and 350 microns, and the average particle size of the oxidizer is between about 50 and 200 microns.

Die US-A-5 854 442 beschreibt eine gaserzeugende Zusammensetzung aus etwa 30 bis 45 Gew.-% Kaliumperchlorat, zwischen etwa 55 und 70 Gew.-% Guanidinnitrat sowie 1 bis 3 Gew.-% Celluloseacetatbutyrat als Binder. Die Teilchengröße des Oxidators soll zwischen 15 und 20 µm liegen.The US-A-5,854,442 describes a gas generating composition of about 30 to 45 wt .-% potassium perchlorate, between about 55 and 70 wt .-% guanidine nitrate and 1 to 3 wt .-% cellulose acetate butyrate as a binder. The particle size of the oxidizer should be between 15 and 20 microns.

Die oben beschriebenen Zusammensetzungen eignen sich aufgrund ihrer chemischen und physikalischen Eigenschaften nur zur Verwendung in Fahreroder Beifahrergasgeneratoren. Die Erfindung schafft dem gegenüber eine nitrozellulosefreie gaserzeugende Zusammensetzung mit höherer Abbrandgeschwindigkeit und verbesserter Anzündwilligkeit, die somit auch in einem Gurtstraffer-Gasgenerator eingesetzt werden kann, der gegenüber den Fahrer- und Beifahrergasgeneratoren kürzere Reaktions- und Funktionszeiten erfordert.Due to their chemical and physical properties, the compositions described above are only suitable for use in driver or passenger gas generators. In contrast, the invention provides a nitrocellulose-free gas generating composition having a higher burnup rate and improved ignitability, which can thus also be used in a belt tensioner inflator which requires shorter reaction and service times over the driver and passenger gas generators.

Hierzu wird eine nitrozellulosefreie gaserzeugende Zusammensetzung gemäß Anspruch 1 bereitgestellt, die im wesentlichen aus zwei stickstoffhaltigen organischen Brennstoffen in einem Anteil von 55 bis 70 Gew.-%, einem Perchlorat als anorganischen Oxidator in einem Anteil von 30 bis 45 Gew.-%, zwischen 2 und 5 Gew.-% eines oder mehrerer Abbrandmoderatoren und bis zu 5 Gew.-% an üblichen Hilfs- und Zusatzstoffen besteht, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung, wobei der Druckexponent der Zusammensetzung kleiner als 0,35 ist und die Abbrandgeschwindingkeit bei 200 bar mindestens 40 Millimeter pro Sekunde (mm/s) beträgt.For this purpose, a nitrocellulose-free gas-generating composition according to claim 1 is provided which consists essentially of two nitrogen-containing organic fuels in a proportion of 55 to 70 wt .-%, a perchlorate as inorganic oxidizer in a proportion of 30 to 45 wt .-%, between 2 and 5 wt .-% of one or more Abbrandmoderatoren and up to 5 wt .-% of conventional auxiliaries and additives, in each case based on the total weight of the composition, wherein the pressure exponent of the composition is less than 0.35 and the Abbrandgeschwindingkeit at 200 bar is at least 40 millimeters per second (mm / s).

Eine derartige Zusammensetzung ist insbesondere zur Verwendung in einem Gurtstraffer-Gasgenerator geeignet.Such a composition is particularly suitable for use in a belt tensioner gas generator.

Die Sauerstoffbilanz der Zusammensetzung beträgt vorzugsweise zwischen -5 und +5 %. Unter der Sauerstoffbilanz ist dabei diejenige Sauerstoffmenge in Gewichtsprozent zu verstehen, die bei vollständiger Umsetzung einer Verbindung oder eines Gemischs zu CO2, H2O, Al2O3, B2O3, etc. frei wird (Sauerstoffüberbilanzierung). Reicht der vorhandene Sauerstoff hierzu nicht aus, so wird die zum vollständigen Umsatz notwendige Fehlmenge mit negativem Vorzeichen angegeben (Sauerstoffunterbilanzierung). Aufgrund der vorteilhaften Sauerstoffbilanz der erfindungsgemäßen gaserzeugenden Zusammensetzung ist die beim Abbrand entstehende Schadgasmenge, insbesondere der Kohlenmonoxidanteil, gering.The oxygen balance of the composition is preferably between -5 and +5%. The oxygen balance is understood to mean that amount of oxygen in percent by weight that is the case when a compound is completely reacted or a mixture to CO 2 , H 2 O, Al 2 O 3 , B 2 O 3 , etc. is released (oxygen overbalancing). If the available oxygen is insufficient for this purpose, the shortfall required for the complete conversion is indicated with a negative sign (oxygen sub-balancing). Due to the advantageous oxygen balance of the gas-generating composition according to the invention, the quantity of noxious gas produced during combustion, in particular the proportion of carbon monoxide, is low.

Der organische Brennstoff ist Guanidinnitrat, im Gemisch mit mindestens einer weiteren stickstoffhaltigen Verbindung aus der aus Nitroguanidin, Nitrotriazolon (NTO), Hexogen (RDX), Octogen (HMX), Ethylendiamindinitrat (EDDN), Triaminoguanidinnitrat (TAGN), Azobisformamidindinitrat und Dinitroammelin bestehenden Gruppe, wobei der Brennstoff aus 75 bis 90 Gew.-% Guanidinnitrat und 10 bis 25 Gew.-% der weiteren Verbindung, jeweils bezogen auf das Gesamtgewicht des Brennstoffs, zusammengesetzt ist. Besonders bevorzugt ist die weitere Verbindung Nitroguanidin. Die weitere stickstoffhaltige Verbindung erhöht die Abbrandgeschwindigkeit im gesamten Druckbereich. Ein Zusatz von mehr als 25 % der weiteren Verbindung bewirkt allerdings eine zu starke Erhöhung der Abbrandtemperatur, so daß eine Beschädigung des Gasgenerators zu befürchten ist. Auch aus Kostengründen sollte der Anteil der weiteren Verbindung so gering wie möglich gehalten werden.The organic fuel is guanidine nitrate in admixture with at least one other nitrogen-containing compound selected from the group consisting of nitroguanidine, nitrotriazolone (NTO), hexogen (RDX), octogen (HMX), ethylenediamine dinitrate (EDDN), triaminoguanidine nitrate (TAGN), azobisformamidine dinitrate and dinitroammine, wherein the fuel from 75 to 90 wt .-% guanidine nitrate and 10 to 25 wt .-% of the further compound, in each case based on the total weight of the fuel, is composed. More preferably, the further compound is nitroguanidine. The additional nitrogen-containing compound increases the burning rate in the entire pressure range. An addition of more than 25% of the further compound, however, causes an excessive increase in the burning temperature, so that damage to the gas generator is to be feared. Also for cost reasons, the proportion of further connection should be kept as low as possible.

Der anorganische Oxidator ist ein Perchlorat, insbesondere ein Alkalimetallperchlorat und/oder Ammoniumperchlorat, und besonders bevorzugt Kaliumperchlorat. Als Abbrandmoderatoren werden sauerstoffhaltige Verbindungen von Eisen, Kupfer, Mangan, Titan, Vanadium, Molybdän und Chrom, einschließlich Kombinationen davon, eingesetzt. Bevorzugt ist der Abbrandmoderator aus der aus CuO, Cu2O, CuCr2O4, Fe2O3, 3Cu(OH)2 x Cu(NO3)2 und deren Gemischen bestehenden Gruppe ausgewählt. Ganz besonders bevorzugt ist der Abbrandmoderator CuO.The inorganic oxidizer is a perchlorate, especially an alkali metal perchlorate and / or ammonium perchlorate, and most preferably potassium perchlorate. As combustion moderators, oxygen-containing compounds of iron, copper, manganese, titanium, vanadium, molybdenum and chromium, including combinations thereof, are used. The burn-off moderator is preferably selected from the group consisting of CuO, Cu 2 O, CuCr 2 O 4 , Fe 2 O 3 , 3Cu (OH) 2 x Cu (NO 3 ) 2 and mixtures thereof. Very particularly preferred is the Abbrandmoderator CuO.

Die vorbeschriebenen Abbrandmoderatoren werden in einem Anteil von zwischen 2 und 5 Gew.-% verwendet. Höhere Anteile senken die Gasausbeute des Treibstoffs, was nicht in allen Fällen wünschenswert ist.The above-described consumable moderators are used in a proportion of between 2 and 5% by weight. Higher levels lower the gas yield of the fuel, which is not desirable in all cases.

Die mittlere Teilchengröße des Abbrandmoderators ist vorzugsweise kleiner als 5 µm und besonders bevorzugt kleiner als 1 µm, bei einer bevorzugten spezifischen Oberfläche von mindestens 2 m2/g, besonders bevorzugt mindestens 5 m2/g. Der Zusatz von derartigen feinkörnigen Abbrandmoderatoren verbessert die Anzündwilligkeit der erfindungsgemäßen gaserzeugenden Zusammensetzungen, so daß Anzündverzögerungen von höchstens 6 Millisekunden (ms) und besonders bevorzugt höchstens 5 ms erreicht werden können.The mean particle size of the Abbrandmoderators is preferably less than 5 microns and more preferably less than 1 micron, with a preferred specific surface of at least 2 m 2 / g, more preferably at least 5 m 2 / g. The addition of such fine-grained Abbrandmoderatoren improves the ignition willingness of the gas-generating compositions of the invention, so that ignition delays of at most 6 milliseconds (ms) and more preferably at most 5 ms can be achieved.

Die mittlere Teilchengröße des Brennstoffs und des Oxidators ist vorzugsweise kleiner als 15 µm und besonders bevorzugt kleiner als 10 µm. Dies trägt dazu bei, daß die erfindungsgemäße gaserzeugende Zusammensetzung eine ausreichend hohe Abbrandgeschwindigkeit zur Verwendung in Gurtstraffer-Gasgeneratoren aufweist.The average particle size of the fuel and the oxidizer is preferably less than 15 microns and more preferably less than 10 microns. This contributes to the gas generating composition according to the invention having a sufficiently high burning rate for use in belt tensioner gas generators.

Mit den erfindungsgemäßen Zusammensetzungen können Abbrandgeschwindigkeiten von mindestens 40 mm/s unter Betriebsbedingungen, das heißt üblicherweise einem Druck von 200 bar, erreicht werden. Besonders bevorzugt beträgt die Abbrandgeschwindigkeit bei 200 bar mindestens 45 mm/s.Burning rates of at least 40 mm / s under operating conditions, that is usually a pressure of 200 bar, can be achieved with the compositions according to the invention. Particularly preferably, the burning rate at 200 bar is at least 45 mm / s.

Die Abbrandgeschwindigkeit ist druckabhängig und läßt sich gemäß der folgenden Gleichung berechnen: r = a ⋅ p n

Figure imgb0001
The burning rate is pressure dependent and can be calculated according to the following equation: r = a ⋅ p n
Figure imgb0001

Darin bedeutet r die Abbrandgeschwindigkeit, a eine treibstoffspezifische Konstante, p den Druck und n den Druckexponenten. Sind r und n bei einem bestimmten Druck p bekannt, läßt sich die Konstante a ermitteln.In this formula, r represents the burning rate, a is a fuel-specific constant, p is the pressure and n is the pressure exponent. If r and n are known at a certain pressure p, the constant a can be determined.

Der Druckexponent der erfindungsgemäßen Zusammensetzungen ist kleiner als 0,35 und vorzugsweise kleiner oder gleich 0,3. Höhere Druckexponenten bewirken bei niedrigen Drücken auch eine schlechtere Anzündwilligkeit.The printing exponent of the compositions according to the invention is less than 0.35 and preferably less than or equal to 0.3. Higher pressure exponents also cause worse ignition at low pressures.

Die Einstellung der Abbrandgeschwindigkeit der erfindungsgemäßen Zusammensetzungen erfolgt vorzugsweise durch Auswahl der geeigneten Brennstoffzusammensetzung, insbesondere der Art und des Anteils der weiteren stickstoffhaltigen Verbindung, der Art und des Anteils des jeweiligen Abbrandmoderators sowie der mittleren Teilchengröße des Brennstoffs, des Oxidators und, gegebenenfalls, des Abbrandmoderators. Durch eine geeignete Kombination dieser Parameter kann die Zusammensetzung optimal an die Verwendung in Gurtstraffer-Gasgeneratoren angepaßt werden.The setting of the burning rate of the compositions according to the invention is preferably carried out by selecting the suitable fuel composition, in particular the type and proportion of the further nitrogen-containing compound, the type and proportion of each Abbrandmoderators and the average particle size of the fuel, the oxidizer and, optionally, the Abbrandmoderators. By a suitable combination of these parameters, the composition can be optimally adapted for use in belt tensioner gas generators.

Die üblichen Hilfs- und Zusatzstoffe umfassen Verarbeitungshilfen, wie Gleitmittel, Preß- und Rieselhilfen. Als Beispiele für diese Verbindungen können insbesondere Calciumstearat, Siliciumdioxid, Graphit oder Ruß genannt werden. Die Verarbeitungshilfen werden vorzugsweise in einem Anteil von bis zu 2 Gew.-%, bezogen auf die Gesamtzusammensetzung, eingesetzt.The usual auxiliaries and additives include processing aids, such as lubricants, pressing and pouring aids. As examples of these compounds, in particular calcium stearate, silica, graphite or carbon black may be mentioned. The processing aids are preferably used in a proportion of up to 2 wt .-%, based on the total composition.

Eine besonders bevorzugte erfindungsgemäße Zusammensetzung besteht aus 48 bis 52 Gewichtsteilen Guanidinnitrat, 13 bis 17 Gewichtsteilen Nitroguanidin, 33 bis 37 Gewichtsteilen Kaliumperchlorat, 2,0 bis 5,0 Gewichtsteilen Kupferoxid (CuO) und jeweils bis zu 1 Gew.-% Calciumstearat und Graphit.A particularly preferred composition according to the invention consists of 48 to 52 parts by weight of guanidine nitrate, 13 to 17 parts by weight of nitroguanidine, 33 to 37 parts by weight of potassium perchlorate, 2.0 to 5.0 parts by weight of copper oxide (CuO) and up to 1% each by weight of calcium stearate and graphite.

Weitere Merkmale und Vorteile der Erfindung ergeben sich aus der nachfolgenden Beschreibung von besonders bevorzugten Ausführungsbeispielen, die jedoch nicht einschränkend zu verstehen sind.Further features and advantages of the invention will become apparent from the following description of particularly preferred embodiments, which are not to be understood as limiting.

Beispiele 1 bis 5Examples 1 to 5

Guanidinnitrat mit einer mittleren Teilchengröße von 5 µm, Nitroguanidin mit einer mittleren Teilchengröße von 11 µm, Kaliumperchlorat mit einer mittleren Teilchengröße von 7 µm, Kupferoxid (CuO) mit einer mittleren Teilchengröße von 0,5 µm und einer spezifischen Oberfläche von 8 m2/g sowie Calciumstearat und Graphit wurden in den in der nachfolgenden Tabelle 1 angegebenen Gewichtsteilen gemischt, zusammen in einer Kugelmühle aufgemahlen und zu Tabletten von 6 x 2,5 mm verpreßt. Tabelle 1 Beispiel Nr. 1 (Vergleichsbeispiel) 2 (Vergleichsbeispiel) 3 (Vergleichsbeispiel) 4 5 Guanidinnitrat 65 57,5 50,0 50,0 50,0 Nitroguanidin 0 7,5 15,0 15,0 15,0 KClO4 35 35,0 35,0 35,0 35,0 CuO 0 0 0 2,5 5,0 Calciumstearat 0,5 0,5 0,5 0,5 0,5 Graphit 0,4 0,4 0,4 0,4 0,4 O2-Bilanz -3,3 % -3,6 % -4,0 % -3,5 % -3,0 % Guanidine nitrate with a mean particle size of 5 microns, nitroguanidine with an average particle size of 11 microns, potassium perchlorate with a mean particle size of 7 microns, copper oxide (CuO) with an average particle size of 0.5 microns and a specific surface area of 8 m 2 / g as well as calcium stearate and graphite were mixed in the parts by weight given in Table 1 below, ground together in a ball mill and pressed into tablets of 6 x 2.5 mm. <u> Table 1 </ u> Example no. 1 (comparative example) 2 (comparative example) 3 (comparative example) 4 5 guanidine nitrate 65 57.5 50.0 50.0 50.0 nitroguanidine 0 7.5 15.0 15.0 15.0 KClO 4 35 35.0 35.0 35.0 35.0 CuO 0 0 0 2.5 5.0 calcium stearate 0.5 0.5 0.5 0.5 0.5 graphite 0.4 0.4 0.4 0.4 0.4 O 2 balance -3.3% -3.6% -4.0% -3.5% -3.0%

Die Abbrandgeschwindigkeit der Zusammensetzungen gemäß den Beispielen 1 bis 5 wurde durch Beschuß von je 10 Gramm Treibstoff in einer geschlossenen 100 cm3 Bombe bestimmt. Die Versuchsergebnisse sowie weitere Eigenschaften der Zusammensetzungen sind in Tabelle 2 dargestellt. Tabelle 2 Beispiel Nr. Abbrandgeschwindigkeit r bei 200 bar [mm/s] theoretische Abbrandtemperatur [K] Gasausbeute (%) Druckexponent n 1 30,8 2377 81,31 0,374 2 32,5 2419 81,32 0,387 3 34,7 2462 81,32 0,380 4 42,9 2441 79,84 0,289 5 46,2 2438 78,44 0,242 The burning rate of the compositions according to Examples 1 to 5 was determined by bombardment of 10 grams of fuel in a closed 100 cm 3 bomb. The experimental results and other properties of the compositions are shown in Table 2. <u> Table 2 </ u> Example no. Burning rate r at 200 bar [mm / s] theoretical burning temperature [K] Gas yield (%) Pressure exponent n 1 30.8 2377 81.31 0.374 2 32.5 2419 81.32 0.387 3 34.7 2462 81.32 0,380 4 42.9 2441 79.84 0,289 5 46.2 2438 78.44 0,242

Für das Beispiel Nr. 3 wurde eine Anzündverzögerung von 11 ms ermittelt; die Beispiele Nr. 4 und 5 zeigten eine Anzündverzögerung von 6 bzw. 5 ms.For Example # 3, a firing delay of 11 ms was determined; Examples Nos. 4 and 5 showed an ignition delay of 6 and 5 ms, respectively.

Die Zusammensetzung gemäß Beispiel 5 wurde außerdem einem Alterungstest über 400 Stunden bei 107 °C unterzogen. Nach diesem Test wurde ein Gewichtsverlust von 0,07 % festgestellt, das heißt die Zusammensetzung zeigte eine den Anforderungen an Fahrzeuginsassenrückhaltesysteme genügende Alterungsbeständigkeit. Ein Vergleichsversuch mit einem üblichen Treibstoff auf der Grundlage von Nitrozellulose unter den gleichen Bedingungen ergab einen Gewichtsverlust von 14 %. Dies deutet auf eine vollständige Zersetzung und damit einen vollständigen Funktionsausfall des Treibstoffs hin.The composition of Example 5 was further subjected to an aging test at 107 ° C for 400 hours. After this test, a weight loss of 0.07% was found, that is, the composition exhibited aging resistance sufficient to meet vehicle occupant restraint requirements. A comparison experiment with a conventional fuel based on nitrocellulose under the same conditions resulted in a weight loss of 14%. This indicates a complete decomposition and thus a complete malfunction of the fuel.

Die oben dargestellten Abbrandversuche zeigen die Eignung der erfindungsgemäßen Zusammensetzungen zur Verwendung in Gurtstraffer-Gasgeneratoren. Die für die Abbrandgeschwindigkeit und auch die Anzündverzögerung erzielten Werte entsprechen bei Einsatz gleicher Treibstoffmengen denen von herkömmlichen Nitrozellulosetreibstoffen.The burn-up tests shown above show the suitability of the compositions according to the invention for use in belt tensioner gas generators. The values obtained for the combustion rate and the ignition delay correspond to those of conventional nitrocellulose fuels when using the same amounts of fuel.

Claims (21)

  1. A nitrocellulose-free, gas generating composition for use in vehicle occupant restraint systems, in particular in a belt tensioner gas generator, consisting essentially of
    at least one nitrogenous organic fuel in an amount of from 55 to 70 % by weight, the nitrogenous organic fuel consisting of from 75 to 90 % by weight of guanidine nitrate in a mixture with at least one further compound selected from the group consisting of nitroguanidine, nitrotriazolone, hexogen, octogen, ethylenediamine dinitrate, triaminoguanidine nitrate, azobisformamidine dinitrate and dinitroammeline in an amount of from 10 to 25 % by weight,
    a perchlorate as an inorganic oxidant in an amount of from 30 to 45 % by weight,
    one or more combustion moderators in an amount of between 2 and 5 % by weight, the combustion moderator being an oxygenic compound of Fe, Cu, Mn, Ti, V,Mo, Cr or combinations thereof, and
    up to 5 % by weight of usual auxiliary agents and additives, each with respect to the total weight of the composition,
    the composition having a pressure exponent of less than 0.35 and a combustion rate of at least 40 mm/s at 200 bar.
  2. The gas generating composition according to claim 1, characterized in that the oxygen balance of the composition amounts to between -5 and +5 %.
  3. The composition according to claim 1 or 2, characterized in that the fuel consists of from 75 to 90 % by weight of guanidine nitrate and of from 10 to 25 % by weight of nitroguanidine, each with respect to the weight of the fuel.
  4. The composition according to any of claims 1 to 3, characterized in that the oxidant is potassium perchlorate.
  5. The composition according to any of claims 1 to 4, characterized in that the combustion moderator is selected from the group consisting of CuO, Cu2O, CuCr2O4, Fe2O3 and 3Cu(OH)2 × Cu(NO3)2.
  6. The composition according to claim 5, characterized in that the combustion moderator is CuO.
  7. The composition according to any of claims 1 to 6, characterized in that the mean particle size of the fuel and of the oxidant is less than 15 µm.
  8. The composition according to claim 7, characterized in that the mean particle size of the fuel and of the oxidant is less than 10 µm.
  9. The composition according to any of claims 1 to 8, characterized in that the mean particle size of the combustion moderator is less than 5 µm.
  10. The composition according to claim 9, characterized in that the mean particle size of the combustion moderator is less than 1 µm.
  11. The composition according to claim 8 or 9, characterized in that the specific surface of the combustion moderator amounts to at least 2 m2/g.
  12. The composition according to claim 11, characterized in that the specific surface amounts to at least 5 m2/g.
  13. The composition according to any of claims 1 to 12, characterized in that the combustion rate of the composition amounts to at least 45 mm/s.
  14. The composition according to any of claims 1 to 13, characterized in that the pressure exponent is less than or equal to 0.3.
  15. The composition according to any of claims 1 to 14, characterized in that the composition has an ignition delay of 6 ms at the most.
  16. The composition according to claim 15, characterized in that the ignition delay amounts to 5 ms at the most.
  17. The composition according to any of the preceding claims, characterized in that the usual auxiliary agents and additives are contained in an amount of up to 2 % by weight.
  18. The composition according to any of claims 1 to 17, characterized in that the usual auxiliary agents and additives are selected from the group consisting of calcium stearate, silicon dioxide, graphite and soot.
  19. The composition according to any of the preceding claims, consisting of 48 to 52 parts by weight of guanidine nitrate, 13 to 17 parts by weight of nitroguanidine, 33 to 37 parts by weight of potassium perchlorate, 2.0 to 5.0 parts by weight of CuO and up to two parts by weight of at least one of the compounds calcium stearate, silicon dioxide, graphite and soot.
  20. A belt tensioner having a gas generator and a belt tensioner drive, the gas generator containing a composition according to any of claims 1 to 19 generating a gas or a gas mixture upon combustion, and the belt tensioner drive being adapted to be activated by the gas or the gas mixture.
  21. Use of a gas generating composition according to any of claims 1 to 19 in a belt tensioner of a vehicle occupant restraint system.
EP02014052A 2001-07-10 2002-06-28 Nitrocellulose-free gas-generating composition Expired - Lifetime EP1275629B1 (en)

Applications Claiming Priority (2)

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DE20111410U 2001-07-10
DE20111410U DE20111410U1 (en) 2001-07-10 2001-07-10 Nitrocellulose free gas generating composition

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US6893517B2 (en) 2005-05-17
US20030145926A1 (en) 2003-08-07
ATE556042T1 (en) 2012-05-15
EP1275629A3 (en) 2010-09-22
EP1275629A2 (en) 2003-01-15
DE20111410U1 (en) 2001-08-30

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