EP0722429B1 - Gas developing agent - Google Patents

Gas developing agent Download PDF

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Publication number
EP0722429B1
EP0722429B1 EP94928758A EP94928758A EP0722429B1 EP 0722429 B1 EP0722429 B1 EP 0722429B1 EP 94928758 A EP94928758 A EP 94928758A EP 94928758 A EP94928758 A EP 94928758A EP 0722429 B1 EP0722429 B1 EP 0722429B1
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weight
gas generator
component
generator propellant
propellant according
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German (de)
French (fr)
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EP0722429A1 (en
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Eduard Gast
Peter Semmler
Bernhard Schmid
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Nigu Chemie GmbH
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Nigu Chemie GmbH
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/06—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires containing gas-producing, chemically-reactive components
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
    • 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 solid gas generator fuels based on Guanidine compounds on suitable supports.
  • JP H5-254977 is based on gas generator fuels for airbags of triaminoguanidine nitrate (TAGN), which also contains oxidizing agents such as May contain alkali and alkaline earth nitrates, nitrites, chlorates or perchlorates. Molybdenum sulfide can be contained as a further component as a binder.
  • TAGN triaminoguanidine nitrate
  • Molybdenum sulfide can be contained as a further component as a binder.
  • the advantage of using TAGN instead of the known sodium azide is in the non-toxicity and also good stability of TAGN, which is also in Connection with heavy metals, no salts sensitive to friction and impact forms.
  • the rate of combustion of the gas generator fuels is said to vary by Pressing pressure during the production of pellets or tablets from the Component mixture may be possible.
  • the object of the present invention is compared to JP H5-254977 to provide improved gas generator fuels, the Burning behavior can be set in a targeted manner and that is good when burning retain slag and the formation of toxic gases on one Limit the minimum.
  • the gas generator fuels are said to be thermally stable, good ignitable, fast - even at low temperatures - burning and easy to store be and ensure a high gas yield.
  • these should Gas generator fuels reduce the size of the generator housing and thus their weight reduction compared to known with sodium azide enable operated generators.
  • TAGN Carbonates, hydrogen carbonates or nitrates of guanidine, aminoguanidine, diaminoguanidine or triaminoguanidine (TAGN) or mixtures thereof can be used as component (A).
  • TAGN is preferably used.
  • TAGN is practically non-toxic (LD 50 > 3500 mg / kg rat), not hygroscopic, not very water-soluble, thermally stable, burning at low temperature and of low sensitivity to impact and friction.
  • the gas yield from the combustion of TAGN is very high, with a large proportion of nitrogen gas being generated.
  • 1 to 50% by weight of the TAGN can be replaced by nitroguanidine.
  • the cost of component (A) can thus be reduced and favorable combustion behavior can be achieved, since nitroguanidine has a lower combustion rate than TAGN.
  • component (B) alkali metal or alkaline earth metal nitrates, ammonium nitrate and mixtures thereof can be used. Potassium nitrate is preferably used. Potassium nitrate is non-hygroscopic, non-toxic, enables a high gas yield and low burning temperature when burned.
  • Component (A) is in the mixture of (A) and (B) in an amount of about 20 to 55, preferably about 50 to 55% by weight, component (B) in an amount of about 80 to 45, preferably about 50 up to 45% by weight.
  • Component (A) is preferably present in an amount of approximately 50 to 55% by weight and component (B) in an amount of approximately 50 to 45% by weight.
  • component (C) silicon dioxide, alkali metal, alkaline earth metal or aluminosilicates or mixtures thereof are examples of this are Aerosil® 200 and Aerosil® 300, highly disperse silica and diatomaceous earth (Diatomaceous earth).
  • the preferred carrier substance is silica with a pH from about 7.
  • Oxygen-supplying carrier substances such as iron (III) oxide, cobalt oxides, manganese dioxide and copper (II) oxide or mixtures thereof can also be used as component (C).
  • the preferred oxygen-supplying carrier substance is iron (III) oxide.
  • Component (C) is present in an amount of 5 to 45, preferably about 8 to 20% by weight, based on the total amount of components (A) and (B). If iron (III) oxide is used as the oxygen-supplying carrier substance (C), it is present in an amount of about 20 to 40, preferably about 25 to 35,% by weight, based on the total amount of components (A) and (B).
  • Component (C) serves to moderate the burnup, i.e. to adjust the Burning rate At the same time, the slag or Improved melt formation.
  • the slag formation is, for example, at Airbag absolutely necessary.
  • An airbag consists essentially of a gas generator housing that with the gas generator fuel, usually in tablet form, and one Initial igniter (squib) for igniting the gas generator fuel, as well as a Gas bag.
  • Suitable detonators are, for example, in Us-Ps 49 31 111 described.
  • the gas bag which is initially folded into small pieces, is after the initial ignition filled with the gases generated when the gas generator fuel burns and reaches its full volume in a period of about 10-50 ms.
  • the Hot sparks, melts or solids escape from the gas generator in the gas bag must be largely prevented, as it will destroy of the gas bag or injury to vehicle occupants. This is achieved through slag formation.
  • respirable dust-like particles decreased from the gas generator of an airbag could escape.
  • respirable dust particles a diameter of about 6 ⁇ m or less.
  • the oxygen-supplying Carrier substances also suppress the formation of toxic gases such as Carbon monoid when burning.
  • the gas generator fuel may also contain, as component (D), a binder which is soluble in water at room temperature.
  • binders are cellulose compounds or polymers made from one or more polymerizable olefinically unsaturated monomers.
  • cellulose compounds are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose ethers, in particular methyl hydroxyethyl cellulose.
  • a usable methylhydroxyethyl cellulose is CULMINAL (R) MHEC 30000 PR from Firm Aqualon.
  • Suitable binders are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and polycarbonates.
  • Component (D) is based on the total amount of components (A) and (B) in an amount of about 0.1 to 5, preferably about 1.5 to 2.5% by weight in front.
  • the binder (D) serves as a desensitizing agent and as a processing aid in the production of granules or tablets from the gas generator fuel. It also serves to reduce the hydrophilicity and to stabilize the Gas generator fuels.
  • the tablets or pellets used in the gas generators from the Gas generator fuel can be produced by known methods, for example by extrusion, extrusion, in rotary presses or Tableting machines.
  • the size of the pellets or tablets depends on the desired burning time in the respective application.
  • triaminoguanidine nitrate TAGN
  • Nitroguanidine - as well as potassium nitrate and possibly cellulose ether are in possible little water dissolved at 90 ° C and one iron oxide and / or silicon dioxide average grain size of about 1 micron stirred into the solution. After predrying at 60 ° C and 16 hPa with mechanical agitation the mixture is still in crushed wet and then after drying at 60 ° C with a tableting machine for tablets with a diameter of 6 mm and a height of 2 mm pressed.
  • Mix 1 contains no silicon dioxide and Mix 5 contains no iron (III) oxide.
  • Mixture 6 contains neither silicon dioxide nor iron (III) oxide as a comparison mixture.
  • Composition of the mixtures in percent by weight 1 2nd 3rd 4th 5 6 TAGN 39.1 39.1 39.1 29.1 47.3 53.0
  • Nitroguanidine - - - 10.0 - - KNO 3 30.9 30.9 30.9 40.7 47.0 Fe 2 O 3 30.0 20.0 14.0 14.0 - - SiO 2 - 10.0 14.0 14.0 12.0 - Cellulose ether - - 2.0 2.0 - - -
  • Table II shows an overview of the calculated reaction parameters.
  • a high reaction temperature occurs in mixture 5 and especially in mixture 6.
  • Calculated values O 2 balance% + 2.13 + 1.13 - 1.84 - 1.57 + 0.25 + 0.84 Volume ccm 1000 1000 1000 1000 1000 1000 Loading density (g / ccm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
  • Pressure bar 427 444 470 457 654 810 Temperature K 1973 2116 2116 2116 2468 2666 Mole numbers of the combustion gases Mol / kg 21.1 22.6 23.9 23.4 27.5 28.8 Expl. Heat J / g 3369 3092 2998 2913 3852 4566
  • Table III shows an overview of the reaction products formed during the combustion and their amounts. Reaction products at 298 K, freeze-out temp. 1,500 K. Connection (wt%) 1 2nd 3rd 4th 5 6 CO 2 3,604 10,086 11.538 13,228 12.408 3,768 H 2 O 18.952 18.817 18.828 17.711 22,935 26,692 N 2 27,219 27,219 27.217 26.735 33,383 37,596 CO 0.000 0.134 1,283 1,223 0.000 0.000 H 2 0.000 0.017 0.139 0.109 0.000 0.000 NO 0.001 0.000 0.000 0.009 0.018 O 2 0.001 0.000 0.000 0.000 0.248 0.826 HCN 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 NH 3 0.000 0.000 0.003 0.002 0.000 KOH 0.086 0.000 0.003 0.003 0.053 0.101 K 2 CO 3 21.014 0.000 0.000 0.000 0.150 31.997
  • Table IV shows test results on the sensitivity to decomposition, stability, slag formation and the combustion behavior of the various mixtures.
  • Mixtures 1 to 5 showed good to very good burning behavior, especially with regard to a constant high burning rate.
  • Investigation results mixture 1 2nd 3rd 4th 5 6 Decomposition temp. ° C - 207 178 203 - Measurement conditions: Heating rate 2 ° C / min from 15 ° C below decomposition temp.
  • a trial burn of the mixture 1 was carried out in a normal gas generator housing made of aluminum for a 60 liter airbag, provided with a bore for pressure measurement, in a 60 liter can.
  • the test temperature for test 1 was -35 ° C.
  • the propellant weight was 51.0 g.
  • the propellant consisted of tablets with a diameter of 6 mm and a height of 2 mm.
  • FIG. 1 shows the pressure in the combustion chamber in units of 10 5 Pascals as a function of the time after ignition in milliseconds.
  • the pressure builds up within approx. 1.5 ms and the pressure drop to half the maximum pressure occurs after approx. 27 ms.
  • the maximum pressure is 1.88 * 10 7 Pa, it is reached after 12.3 ms.
  • the test burns of mixture 2 was in a Euro gas generator housing made of aluminum for a 35 liter airbag, provided with a hole for pressure measurement, carried out in a 60 liter jug.
  • the test temperature in test 2 was -35 ° C, in test 3 + 20 ° C.
  • the Propellant weight was 41.0 g in test 2 and 30.0 g in test 3.
  • the Propellant consisted of tablets with a diameter of 6 mm and a height of 2 mm.
  • FIG. 2 shows the pressure in the combustion chamber in units of 10 5 Pascals as a function of the time after ignition in milliseconds.
  • the pressure builds up within approx. 1.5 ms and the pressure drop to half the maximum pressure occurs after approx. 27 ms.
  • the maximum pressure was 1.45 * 10 7 Pa, it was reached after 15.7 ms.
  • FIG. 3 shows the pressure in the combustion chamber in units of 10 5 Pascal as a function of the time after ignition in milliseconds.
  • the pressure builds up within approx. 1.5 ms and the pressure drop to half the maximum pressure occurs after approx. 27 ms.
  • the maximum pressure was 1.33 * 10 7 Pa, it was reached after 7.5 ms.
  • the gas generator fuel according to the invention consists of non-toxic, light producible and inexpensive components, their processing is unproblematic. Their thermal stability ensures good shelf life. In spite of at low combustion temperatures, the ignitability of the mixtures is good. she burn quickly and deliver large gas yields with very low CO and NO contents.
  • the mixtures according to the invention are therefore for use as Gas generating agent in the various airbag systems, as an extinguishing agent or blowing agent particularly suitable.
  • the gas generator fuels are also good recyclable.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Air Bags (AREA)
  • Percussion Or Vibration Massage (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Medicinal Preparation (AREA)
  • Fats And Perfumes (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

A gas developing agent, in particular for airbags, contains (A) at least one carbonate, hydrogen carbonate or nitrate of guanidine, aminoguanidine, diaminoguanidine or triaminoguanidine; (B) at least one alkaline or alkaline earth nitrate or ammonium nitrate as oxidising agent; and (C) at least one carrier selected among silicon dioxide, alkaline, alkaline earth or aluminosilicates, and/or at least one oxygen-supplying carrier selected among ferric oxide, cobalt oxides, manganese dioxide and cupric oxide, to moderate combustion and improve ash formation. This gas developing agent has improved combustion and ash formation.

Description

Die Erfindung betrifft feste Gasgeneratortreibstoffe auf Basis von Guanidinverbindungen auf geeigneten Trägern.The invention relates to solid gas generator fuels based on Guanidine compounds on suitable supports.

Aus der JP H5-254977 sind Gasgeneratortreibstoffe für Airbags auf der Basis von Triaminoguanidinnitrat (TAGN) bekannt, die zusätzlich Oxidationsmittel wie Alkali- und Eralkalinitrate, -nitrite, -chlorate oder -perchlorate enthalten können. Als weitere Komponente kann als Bindemittel Molybdänsulfid enthalten sein. Der Vorteil der Verwendung von TAGN anstelle des bekannten Natriumazids liegt in der Ungiftigkeit und ebenfalls guten Stabilität von TAGN, das zudem in Verbindung mit Schwermetallen keine reib- und schlagempfindlichen Salze bildet. Die Abbrandrate der Gasgeneratortreibstoffe soll über eine Variation des Verpressdrucks während der Herstellung von Pellets oder Tabletten aus dem Komponentengemisch möglich sein.JP H5-254977 is based on gas generator fuels for airbags of triaminoguanidine nitrate (TAGN), which also contains oxidizing agents such as May contain alkali and alkaline earth nitrates, nitrites, chlorates or perchlorates. Molybdenum sulfide can be contained as a further component as a binder. The The advantage of using TAGN instead of the known sodium azide is in the non-toxicity and also good stability of TAGN, which is also in Connection with heavy metals, no salts sensitive to friction and impact forms. The rate of combustion of the gas generator fuels is said to vary by Pressing pressure during the production of pellets or tablets from the Component mixture may be possible.

Nachteile derartiger Gasgeneratortreibstoffe sind eine immer noch unzureichende Steuerbarkeit des Abbrandes, die Entwicklung toxischer Gase wie CO und eine mangelhafte Schlackenbildung beim Abbrand, die zu einer erhöhten Entwicklung von Stäuben führt, die teilweise lungengängig sind.Disadvantages of such gas generator fuels are still insufficient Controllability of the burnup, the development of toxic gases such as CO and a deficient slag formation when burning, which leads to increased development of dusts, some of which are respirable.

Der vorliegenden Erfindung liegt gegenüber der JP H5-254977 die Aufgabe zugrunde, verbesserte Gasgeneratortreibstoffe bereitzustellen, deren Abbrandverhalten sich gezielt einstellen läßt und die beim Abbrand eine gut zurückhaltbare Schlacke bilden und die Entstehung toxischer Gase auf ein Minimum beschränken. Die Gasgeneratortreibstoffe sollen thermisch stabil, gut anzündbar, schnell - auch bei niedriger Temperatur - brennend und gut lagerfähig sein und eine hohe Gasausbeute gewährleisten. Zudem sollen diese Gasgeneratortreibstoffe eine Verkleinerung der Generatorgehäuse und somit deren Gewichtsverminderung im Vergleich zu bekannten mit Natriumazid betriebenen Generatoren ermöglichen.The object of the present invention is compared to JP H5-254977 to provide improved gas generator fuels, the Burning behavior can be set in a targeted manner and that is good when burning retain slag and the formation of toxic gases on one Limit the minimum. The gas generator fuels are said to be thermally stable, good ignitable, fast - even at low temperatures - burning and easy to store be and ensure a high gas yield. In addition, these should Gas generator fuels reduce the size of the generator housing and thus their weight reduction compared to known with sodium azide enable operated generators.

Erfindungsgemäß werden diese Aufgaben durch einen Gasgeneratortreibstoff gelöst, umfassend

  • (A) mindestens ein Carbonat, Hydrogencarbonat oder Nitrat von Guanidin, Aminoguanidin, Diaminoguanidin oder Triaminoguanidin,
  • (B) mindestens ein Alkali- oder Erdalkalinitrat oder Ammoniumnitrat als Oxidationsmittel, und
  • (C) mindestens eine Trägersubstanz, ausgewählt aus Siliciumdioxid, Alkali-, Erdalkali- oder Alumosilikaten und/oder mindestens eine sauerstoffliefernde Trägersubstanz, ausgewählt aus Eisen(III)oxid, Kobaltoxiden, Mangandioxid und Kupfer(II)oxid, zur Moderation des Abbrandes und zur Verbesserung der Schlackenbildung.
    • According to the invention, these objects are achieved by a gas generator fuel, comprising
  • (A) at least one carbonate, hydrogen carbonate or nitrate of guanidine, aminoguanidine, diaminoguanidine or triaminoguanidine,
  • (B) at least one alkali or alkaline earth nitrate or ammonium nitrate as the oxidizing agent, and
  • (C) at least one carrier substance selected from silicon dioxide, alkali metal, alkaline earth metal or aluminosilicates and / or at least one oxygen-supplying carrier substance selected from iron (III) oxide, cobalt oxides, manganese dioxide and copper (II) oxide, for moderating the burnup and for Improvement in slag formation.

    • Als Komponnte (A) können Carbonate, Hydrogencarbonate oder Nitrate von Guanidin, Aminoguanidin, Diaminoguanidin oder Triaminoguanidin (TAGN) oder deren Gemische verwendet werden. Bevorzugt wird TAGN verwendet. TAGN ist praktisch ungiftig (LD50 > 3500 mg/kg Ratte), nicht hygroskopisch, wenig wasserlöslich, thermisch stabil, bei niedriger Temperatur verbrennend und von geringer Schlag- und Reibempfindlichkeit. Die Gasausbeute bei der Verbrennung von TAGN ist sehr hoch, wobei ein großer Anteil an Stickstoffgas entsteht. Wahlweise kann das TAGN zu 1 bis 50 Gew.-% durch Nitroguanidin ersetzt werden. Damit können die Kosten der Komponente (A) vermindert werden und ein günstiges Abbrandverhalten erzielt werden, da Nitroguanidin eine geringere Abbrandrate aufweist als TAGN. Carbonates, hydrogen carbonates or nitrates of guanidine, aminoguanidine, diaminoguanidine or triaminoguanidine (TAGN) or mixtures thereof can be used as component (A). TAGN is preferably used. TAGN is practically non-toxic (LD 50 > 3500 mg / kg rat), not hygroscopic, not very water-soluble, thermally stable, burning at low temperature and of low sensitivity to impact and friction. The gas yield from the combustion of TAGN is very high, with a large proportion of nitrogen gas being generated. Optionally, 1 to 50% by weight of the TAGN can be replaced by nitroguanidine. The cost of component (A) can thus be reduced and favorable combustion behavior can be achieved, since nitroguanidine has a lower combustion rate than TAGN.

    Als Oxidationsmittel, -Komponente (B), können Alkali- oder Erdalkalinitrate, Ammoniumnitrat und deren Gemische verwendet werden. Vorzugsweise wird Kaliumnitrat verwendet. Kaliumnitrat ist nicht hygroskopisch, nicht toxisch, ermöglicht beim Abbrand eine hohe Gasausbeute und niedrige Abbrandtemperatur.
    Komponente (A) liegt im Gemisch von (A) und (B) in einer Menge von etwa 20 bis 55, vorzugsweise etwa 50 bis 55 Gew.-%, Komponente (B) in einer Menge von etwa 80 bis 45, vorzugsweise etwa 50 bis 45 Gew.-% vor. Bevorzugt liegt Komponente (A) in einer Menge von etwa 50 bis 55 Gew.-% und Komponente (B) in einer Menge von etwa 50 bis 45 Gew.-% vor.    As the oxidizing agent, component (B), alkali metal or alkaline earth metal nitrates, ammonium nitrate and mixtures thereof can be used. Potassium nitrate is preferably used. Potassium nitrate is non-hygroscopic, non-toxic, enables a high gas yield and low burning temperature when burned.
    Component (A) is in the mixture of (A) and (B) in an amount of about 20 to 55, preferably about 50 to 55% by weight, component (B) in an amount of about 80 to 45, preferably about 50 up to 45% by weight. Component (A) is preferably present in an amount of approximately 50 to 55% by weight and component (B) in an amount of approximately 50 to 45% by weight.

    Als Trägersubstanz, Komponente (C), können Siliciumdioxid, Alkali-, Erdalkali- oder Alumosilikate oder deren Gemische verwendet werden Beispiele hierfür sind Aerosil® 200 und Aerosil® 300, hochdisperse Kieselsäure und Kieselgur (Diatomeenerde). Bevorzugte Trägersubstanz ist Kieselsäure mit einem pH-Wert von etwa 7.As the carrier substance, component (C), silicon dioxide, alkali metal, alkaline earth metal or aluminosilicates or mixtures thereof are examples of this are Aerosil® 200 and Aerosil® 300, highly disperse silica and diatomaceous earth (Diatomaceous earth). The preferred carrier substance is silica with a pH from about 7.

    Als Komponente (C) können auch sauerstoffliefernde Trägersubstanzen wie Eisen(III)oxid, Kobaltoxide, Mangandioxid und Kupfer(II)oxid oder deren Gemische verwendet werden. Die bevorzugte sauerstoffliefernde Trägersubstanz ist Eisen(III)oxid.
    Komponente (C) liegt bezogen auf die Gesamtmenge der Komponenten (A) und (B) in einer Menge von 5 bis 45, vorzugsweise etwa 8 bis 20 Gew.-% vor. wird Eisen(III)oxid als sauerstoffliefernde Trägersubstanz (C) verwendet, so liegt sie bezogen auf die Gesamtmenge der Komponenten (A) und (B) in einer Menge von etwa 20 bis 40, vorzugsweise etwa 25 bis 35 Gew.-% vor.    Oxygen-supplying carrier substances such as iron (III) oxide, cobalt oxides, manganese dioxide and copper (II) oxide or mixtures thereof can also be used as component (C). The preferred oxygen-supplying carrier substance is iron (III) oxide.
    Component (C) is present in an amount of 5 to 45, preferably about 8 to 20% by weight, based on the total amount of components (A) and (B). If iron (III) oxide is used as the oxygen-supplying carrier substance (C), it is present in an amount of about 20 to 40, preferably about 25 to 35,% by weight, based on the total amount of components (A) and (B).

    Komponente (C) dient zur Moderation des Abbrandes, d.h. zur Einstellung der Abbrandgeschwindigkeit Gleichzeitig wird die Schlacken- oder Schmelzenbildung verbessert. Die Schlackenbildung ist beispielsweise beim Airbag unbedingt nötig. Component (C) serves to moderate the burnup, i.e. to adjust the Burning rate At the same time, the slag or Improved melt formation. The slag formation is, for example, at Airbag absolutely necessary.

    Ein Airbag besteht im wesentlichen aus einem Gasgeneratorgehäuse, das mit dem Gasgeneratortreibstoff, in der Regel in Tablettenform, gefüllt ist, und einem Initialzünder (squib) zur Zündung des Gasgeneratortreibstoff, sowie einem Gassack. Geeignete Zünder sind beispielsweise in der Us-Ps 49 31 111 beschrieben. Der zunächst kleingefaltete Gassack wird nach der Initialzündung von den beim Abbrand des Gasgeneratortreibstoffs entstehenden Gasen gefüllt und erreicht in einem Zeitraum von etwa 10-50 ms sein volles Volumen. Der Austritt von heißen Funken, Schmelzen oder Festkörpern aus dem Gasgenerator in den Gassack muß weitgehend verhindert werden, da er zu einer Zerstörung des Gassacks oder zur Verletzung von Fahrzeuginsassen führen könnte. Dies wird durch die Schlackenbildung erreicht.An airbag consists essentially of a gas generator housing that with the gas generator fuel, usually in tablet form, and one Initial igniter (squib) for igniting the gas generator fuel, as well as a Gas bag. Suitable detonators are, for example, in Us-Ps 49 31 111 described. The gas bag, which is initially folded into small pieces, is after the initial ignition filled with the gases generated when the gas generator fuel burns and reaches its full volume in a period of about 10-50 ms. The Hot sparks, melts or solids escape from the gas generator in the gas bag must be largely prevented, as it will destroy of the gas bag or injury to vehicle occupants. This is achieved through slag formation.

    Gleichzeitig wird durch Bildung von Schlacken das Entstehen von lungengängigen staubförmigen Anteilen vermindert, die aus dem Gasgenerator eines Airbags austreten könnten. Lungengängige staubförmige Teilchen haben einen Durchmesser von etwa 6 µm oder weniger. Die sauerstoffliefernden Trägersubstanzen unterdrücken zusätzlich die Bildung toxischer Gase wie Kohlenmonoid beim Abbrand.At the same time, the formation of slags prevents the formation of respirable dust-like particles decreased from the gas generator of an airbag could escape. Have respirable dust particles a diameter of about 6 µm or less. The oxygen-supplying Carrier substances also suppress the formation of toxic gases such as Carbon monoid when burning.

    Wahlweise kann der Gasgeneratortreibstoff ferner als Komponente (D) ein in Wasser bei Raumtemperatur lösliches Bindemittel enthalten. Bevorzugte Bindemittel sind Celluloseverbindungen oder Polymerisate aus einem oder mehreren polymerisierbaren olefinisch ungesättigten Monomeren. Beispiel für Celluloseverbindungen sind Celluloseether, wie Carboxymethylcellulose, Methylcelluloseether, insbesondere Methylhydroxyethylcellulose. Eine gut verwendbare Methylhydroxyethylcellulose ist CULMINAL(R) MHEC 30000 PR der Firm Aqualon. Geeignete Polymerisate mit Binderwirkung sind Polyvinylpyrrolidon, Polyvinylacetat, Polyvinylalkohol und Polycarbonate.Optionally, the gas generator fuel may also contain, as component (D), a binder which is soluble in water at room temperature. Preferred binders are cellulose compounds or polymers made from one or more polymerizable olefinically unsaturated monomers. Examples of cellulose compounds are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose ethers, in particular methyl hydroxyethyl cellulose. A usable methylhydroxyethyl cellulose is CULMINAL (R) MHEC 30000 PR from Firm Aqualon. Suitable binders are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and polycarbonates.

    Komponente (D) liegt bezogen auf die Gesamtmenge der Komponenten (A) und (B) in einer Menge von etwa 0,1 bis 5, vorzugsweise etwa 1,5 bis 2,5 Gew.-% vor.Component (D) is based on the total amount of components (A) and (B) in an amount of about 0.1 to 5, preferably about 1.5 to 2.5% by weight in front.

    Das Bindemittel (D) dient als Desensibilisierungsmittel und als Verarbeitungshilfe bei der Herstellung von Granulat oder Tabletten aus dem Gasgeneratortreibstoff. Es dient ferner zur Verminderung der Hydrophilie und zur Stabilisierung der Gasgeneratortreibstoffe.The binder (D) serves as a desensitizing agent and as a processing aid in the production of granules or tablets from the gas generator fuel. It also serves to reduce the hydrophilicity and to stabilize the Gas generator fuels.

    Die in den Gasgeneratoren verwendeten Tabletten oder Pellets aus dem Gasgeneratortreibstoff können nach bekannten Verfahren hergestellt werden, etwa durch Strangpressen, Extrudieren, in Rundläuferpressen oder Tablettiermaschinen. Die Größe der Pellets oder Tabletten hängt von der gewünschten Brennzeit im jeweiligen Anwendungsfall ab.The tablets or pellets used in the gas generators from the Gas generator fuel can be produced by known methods, for example by extrusion, extrusion, in rotary presses or Tableting machines. The size of the pellets or tablets depends on the desired burning time in the respective application.

    AusführungsbeispieleEmbodiments

    Die berechneten Mengen Triaminoguanidinnitrat (TAGN) - ggf. auch Nitroguanidin - sowie Kaliumnitrat und ggf. Celluloseether werden in möglichst wenig Wasser bei 90°C gelöst und Eisenoxid und/oder Siliciumdioxid einer mittleren Korngröße von ca. 1 µm in die Lösung eingerührt. Nach Vortrocknen bei 60°C und 16 hPa unter mechanischem Bewegen wird die Mischung in noch feuchtem Zustand zerkleinert und anschließend nach Trocknen bei 60°C mit einer Tablettiermaschine zu Tabletten von 6 mm Durchmesser und 2 mm Höhe verpresst.The calculated amounts of triaminoguanidine nitrate (TAGN) - if necessary also Nitroguanidine - as well as potassium nitrate and possibly cellulose ether are in possible little water dissolved at 90 ° C and one iron oxide and / or silicon dioxide average grain size of about 1 micron stirred into the solution. After predrying at 60 ° C and 16 hPa with mechanical agitation the mixture is still in crushed wet and then after drying at 60 ° C with a tableting machine for tablets with a diameter of 6 mm and a height of 2 mm pressed.

    In Tabelle 1 sind die untersuchten Gemische aufgeführt. Mischung 1 enthält kein Siliciumdioxid und Mischung 5 kein Eisen(III)oxid. Mischung 6 enthält als Vergleichsmischung weder Siliciumdioxid noch Eisen(III)oxid. Zusammensetzung der Gemische in Gewichtsprozent 1 2 3 4 5 6 TAGN 39,1 39,1 39,1 29,1 47,3 53,0 Nitroguanidin - - - 10,0 - - KNO3 30,9 30,9 30,9 30,9 40,7 47,0 Fe2O3 30,0 20,0 14,0 14,0 - - SiO2 - 10,0 14,0 14,0 12,0 - Celluloseether - - 2,0 2,0 - - The mixtures examined are listed in Table 1. Mix 1 contains no silicon dioxide and Mix 5 contains no iron (III) oxide. Mixture 6 contains neither silicon dioxide nor iron (III) oxide as a comparison mixture. Composition of the mixtures in percent by weight 1 2nd 3rd 4th 5 6 TAGN 39.1 39.1 39.1 29.1 47.3 53.0 Nitroguanidine - - - 10.0 - - KNO 3 30.9 30.9 30.9 30.9 40.7 47.0 Fe 2 O 3 30.0 20.0 14.0 14.0 - - SiO 2 - 10.0 14.0 14.0 12.0 - Cellulose ether - - 2.0 2.0 - -

    Tabelle II zeigt eine Übersicht über die rechnerisch ermittelten Reaktionsparameter. Bei Gemisch 5 und besonders bei Gemisch 6 tritt eine hohe Reaktionstemperatur auf. Errechnete Werte O2-Bilanz % + 2,13 + 1,13 - 1,84 - 1,57 + 0,25 + 0,84 Volumen ccm 1000 1000 1000 1000 1000 1000 Ladedichte (g/ccm) 0,1 0,1 0,1 0,1 0,1 0,1 Druck bar 427 444 470 457 654 810 Temperatur K 1973 2116 2116 2116 2468 2666 Molzahlen der Verbr. Gase Mol/kg 21,1 22,6 23,9 23,4 27,5 28,8 Expl. Wärme J/g 3369 3092 2998 2913 3852 4566 Table II shows an overview of the calculated reaction parameters. A high reaction temperature occurs in mixture 5 and especially in mixture 6. Calculated values O 2 balance% + 2.13 + 1.13 - 1.84 - 1.57 + 0.25 + 0.84 Volume ccm 1000 1000 1000 1000 1000 1000 Loading density (g / ccm) 0.1 0.1 0.1 0.1 0.1 0.1 Pressure bar 427 444 470 457 654 810 Temperature K 1973 2116 2116 2116 2468 2666 Mole numbers of the combustion gases Mol / kg 21.1 22.6 23.9 23.4 27.5 28.8 Expl. Heat J / g 3369 3092 2998 2913 3852 4566

    Tabelle III zeigt eine Übersicht der beim Abbrand entstehenden Reaktionsprodukte und ihrer Mengen. Reaktionsprodukte bei 298 K, Freeze-Out-Temp. 1.500 K Verbindung (Gew. %) 1 2 3 4 5 6 CO2 3,604 10,086 11,538 13,228 12,408 3,768 H2O 18,952 18,817 18,828 17,711 22,935 26,692 N2 27,219 27,219 27,217 26,735 33,383 37,596 CO 0,000 0,134 1,283 1,223 0,000 0,000 H2 0,000 0,017 0,139 0,109 0,000 0,000 NO 0,001 0,000 0,000 0,000 0,009 0,018 O2 0,001 0,000 0,000 0,000 0,248 0,826 HCN 0,000 0,000 0,000 0,000 0,000 0,000 NH3 0,000 0,000 0,003 0,002 0,000 0,000 KOH 0,086 0,000 0,003 0,003 0,053 0,101 K2CO3 21,014 0,000 0,000 0,000 0,150 31,997 FeO - - 12,597 12,597 - - Fe2O3 3,726 0,000 0,000 0,000 - 0,000 Fe3O4 25,396 19,331 0,000 0,000 - 0,000 K2SiO3 - 23,572 23,572 23,572 30,813 - SiO2 - 0,820 4,820 4,820 - - Table III shows an overview of the reaction products formed during the combustion and their amounts. Reaction products at 298 K, freeze-out temp. 1,500 K. Connection (wt%) 1 2nd 3rd 4th 5 6 CO 2 3,604 10,086 11.538 13,228 12.408 3,768 H 2 O 18.952 18.817 18.828 17.711 22,935 26,692 N 2 27,219 27,219 27.217 26.735 33,383 37,596 CO 0.000 0.134 1,283 1,223 0.000 0.000 H 2 0.000 0.017 0.139 0.109 0.000 0.000 NO 0.001 0.000 0.000 0.000 0.009 0.018 O 2 0.001 0.000 0.000 0.000 0.248 0.826 HCN 0.000 0.000 0.000 0.000 0.000 0.000 NH 3 0.000 0.000 0.003 0.002 0.000 0.000 KOH 0.086 0.000 0.003 0.003 0.053 0.101 K 2 CO 3 21.014 0.000 0.000 0.000 0.150 31.997 FeO - - 12,597 12,597 - - Fe 2 O 3 3,726 0.000 0.000 0.000 - 0.000 Fe 3 O 4 25,396 19.331 0.000 0.000 - 0.000 K 2 SiO 3 - 23,572 23,572 23,572 30.813 - SiO 2 - 0.820 4,820 4,820 - -

    Tabelle IV zeigt Untersuchungsergebnisse zur Zersetzungsempfindlichkeit, Stabilität, der Schlackenbildung und dem Abbrandverhalten der verschiedenen Gemische. Gemische 1 bis 5 zeigten gutes bis sehr gutes Abbrandverhalten, insbesondere in bezug auf eine konstante hohe Brenngeschwindigkeit. Für das Vergleichsgemisch 6, das weder Siliciumdioxid noch Eisen(III)oxid als Komponente (C) enthält, konnten nur unzureichende Schlackenbildung und unzureichendes Abbrandverhalten festgestellt werden. Untersuchungsergebnisse Gemisch 1 2 3 4 5 6 Zersetzungstemp. °C - 207 178 203 - Meßbedingungen : Aufheizgeschwindigkeit 2°C/min ab 15°C unter Zersetzungstemp. Stabilität : Holland-Test Probengewicht : 2,5g Prüftemperatur : 105°C Prüfdauer : 72h Gewichtsverlust (Gew. %) - - 0,28 0,40 0,13 - Schlackenbildung ++ ++ ++ ++ ++ - Abbrandverhalten + ++ ++ ++ + - Anm.: ++ Sehr gut; + Gut; - Unzureichend Table IV shows test results on the sensitivity to decomposition, stability, slag formation and the combustion behavior of the various mixtures. Mixtures 1 to 5 showed good to very good burning behavior, especially with regard to a constant high burning rate. For the comparison mixture 6, which contains neither silicon dioxide nor iron (III) oxide as component (C), only inadequate slag formation and inadequate combustion behavior could be found. Investigation results mixture 1 2nd 3rd 4th 5 6 Decomposition temp. ° C - 207 178 203 - Measurement conditions: Heating rate 2 ° C / min from 15 ° C below decomposition temp. Stability: Holland test Sample weight: 2.5g Test temperature: 105 ° C Test duration: 72h Weight loss (% by weight) - - 0.28 0.40 0.13 - Slag formation ++ ++ ++ ++ ++ - Burning behavior + ++ ++ ++ + - Note: ++ Very good; + Good; - Inadequate

    Stabilitätsuntersuchungen zu Gemisch 1Stability studies on mixture 1

  • 1. Differentialthermoanalyse
    Gerät: HERAEUS - FUS-O-MAT
    Aufheizgeschwindigkeit 10°C/min, Einwaage 10 mg
    Ergebnis KNO3-Umwandlung: 129/130°C
       Beginn der exotherm. Reaktion: 168°C    1. Differential thermal analysis
    Device: HERAEUS - FUS-O-MAT
    Heating rate 10 ° C / min, weight 10 mg
    Result of KNO 3 conversion: 129/130 ° C
    Beginning of the exothermic. Response: 168 ° C
  • 2. Differentialthermogravimetrie
    Gerät: LINSEIS - Simultan DTA/TG
    Aufheizgeschwindigkeit 5°C/min, Einwaage 20 mg
    Ergebnis KNO3-Umwandlung: 127°C
       Beginn der exotherm. Reaktion: 135°C
       Verpuffung : 158°C    2. Differential thermogravimetry
    Device: LINSEIS - Simultaneous DTA / TG
    Heating rate 5 ° C / min, weight 20 mg
    Result of KNO 3 conversion: 127 ° C
    Beginning of the exothermic. Reaction: 135 ° C
    Deflagration: 158 ° C

    • Versuchsabbrand Gemisch 1Test burn-up mixture 1

    Ein Versuchsabbrand des Gemisches 1 wurde in einem normalen Gasgeneratorgehäuse aus Aluminium für einen 60 Liter-Airbag, versehen mit einer Bohrung zur Druckmessung, in einer 60 Liter-Kanne durchgeführt.
    Die Versuchstemperatur für Versuch 1 betrug -35°C, das Treibsatzgewicht 51,0g. Der Treibsatz bestand aus Tabletten mit 6 mm Durchmesser und einer Höhe von 2 mm.    A trial burn of the mixture 1 was carried out in a normal gas generator housing made of aluminum for a 60 liter airbag, provided with a bore for pressure measurement, in a 60 liter can.
    The test temperature for test 1 was -35 ° C., the propellant weight was 51.0 g. The propellant consisted of tablets with a diameter of 6 mm and a height of 2 mm.

    Figur 1 zeigt für Versuch 1 den Druck in der Brennkammer in Einheiten von 105 Pascal in Abhängigkeit von der Zeit nach der Zündung in Millisekunden.For test 1, FIG. 1 shows the pressure in the combustion chamber in units of 10 5 Pascals as a function of the time after ignition in milliseconds.

    Der Druckaufbau erfolgt innerhalb ca. 1,5 ms und der Druckabfall auf die Hälfte des Maximaldrucks erfolgt nach ca 27 ms. Der maximale Druck beträgt 1,88*107 Pa, er wird nach 12,3 ms erreicht.The pressure builds up within approx. 1.5 ms and the pressure drop to half the maximum pressure occurs after approx. 27 ms. The maximum pressure is 1.88 * 10 7 Pa, it is reached after 12.3 ms.

    Analyse der erzeugten toxischen Gasanteile in ppmAnalysis of the generated toxic gas fractions in ppm

    CO 300   NH3 >70   NOx 60CO 300 NH 3 > 70 NO x 60

    Versuchsabbrände Gemisch 2Test burns mixture 2

    Die Versuchsabbrände des Gemisches 2 wurde in einem Euro-Gasgeneratorgehäuse aus Aluminium für einen 35 Liter-Airbag, versehen mit einer Bohrung zur Druckmessung, in einer 60 Liter-Kanne durchgeführt. Die Versuchstemperatur betrug in Versuch 2 -35°C, in Versuch 3 + 20°C. Das Treibsatzgewicht betrug bei Versuch 2 41,0g, bei Versuch 3 30,0g. Der Treibsatz bestand aus Tabletten mit 6 mm Durchmesser und einer Höhe von 2 mm. The test burns of mixture 2 was in a Euro gas generator housing made of aluminum for a 35 liter airbag, provided with a hole for pressure measurement, carried out in a 60 liter jug. The test temperature in test 2 was -35 ° C, in test 3 + 20 ° C. The Propellant weight was 41.0 g in test 2 and 30.0 g in test 3. The Propellant consisted of tablets with a diameter of 6 mm and a height of 2 mm.

    Figur 2 zeigt für Versuch 2 den Druck in der Brennkammer in Einheiten von 105 Pascal in Abhängigkeit von der Zeit nach der Zündung in Millisekunden.For test 2, FIG. 2 shows the pressure in the combustion chamber in units of 10 5 Pascals as a function of the time after ignition in milliseconds.

    Der Druckaufbau erfolgt innerhalb ca. 1,5 ms und der Druckabfall auf die Hälfte des Maximaldrucks erfolgt nach ca 27 ms. Der maximale Druck betrug 1,45*107 Pa, er wurde nach 15,7 ms erreicht.The pressure builds up within approx. 1.5 ms and the pressure drop to half the maximum pressure occurs after approx. 27 ms. The maximum pressure was 1.45 * 10 7 Pa, it was reached after 15.7 ms.

    Figur 3 zeigt für Versuch 3 den Druck in der Brennkammer in Einheiten von 105 Pascal in Abhängigkeit von der Zeit nach der Zündung in Millisekunden.For experiment 3, FIG. 3 shows the pressure in the combustion chamber in units of 10 5 Pascal as a function of the time after ignition in milliseconds.

    Der Druckaufbau erfolgt innerhalb ca. 1,5 ms und der Druckabfall auf die Hälfte des Maximaldrucks erfolgt nach ca 27 ms. Der maximale Druck betrug 1,33*107 Pa, er wurde nach 7,5 ms erreicht.The pressure builds up within approx. 1.5 ms and the pressure drop to half the maximum pressure occurs after approx. 27 ms. The maximum pressure was 1.33 * 10 7 Pa, it was reached after 7.5 ms.

    Der erfindungsgemäße Gasgeneratortreibstoff besteht aus nichttoxischen, leicht herstellbaren und kostengünstigen Komponenten, deren Verarbeitung unproblematisch ist. Ihre thermische Stabilität bewirkt gute Lagerfähigkeit. Trotz niederer Verbrennungstemperatur ist die Anzündbarkeit der Gemische gut. Sie brennen schnell und liefern große Gasausbeute mit sehr geringen CO- und NO-Anteilen. Die erfindungsgemäßen Gemische sind daher zur Verwendung als Gaserzeugungsmittel in den verschiedenen Airbag-Systemen, als Löschmittel oder Treibmittel besonders geeignet. Zudem sind die Gasgeneratortreibstoffe gut recyclingfähig.The gas generator fuel according to the invention consists of non-toxic, light producible and inexpensive components, their processing is unproblematic. Their thermal stability ensures good shelf life. In spite of at low combustion temperatures, the ignitability of the mixtures is good. she burn quickly and deliver large gas yields with very low CO and NO contents. The mixtures according to the invention are therefore for use as Gas generating agent in the various airbag systems, as an extinguishing agent or blowing agent particularly suitable. The gas generator fuels are also good recyclable.

    Claims (12)

    1. A gas generator propellant, comprising
      (A) at least one carbonate, hydrogen carbonate or nitrate of guanidine, aminoguanidine, diaminoguanidine or triaminoguanidine in a quantity of about 20 to 55% by weight, relative to the total quantity of components (A) and (B),
      (B) at least one alkali-metal or alkaline-earth-metal nitrate or ammonium nitrate as oxidizing agent in a quantity of about 80 to 45% by weight, relative to the total quantity of components (A) and (B), and
      to moderate burn up and improve slag formation in a quantity of 5 to 45% by weight, relative to the total quantity of components (A) and (B),
      (C1) at least one carrier substance selected from silicon dioxide, alkali-metal silicates, alkaline-earth-metal silicates or aluminosilicates and/or
      (C2) at least one oxygen-supplying carrier substance selected from iron(III) oxide, cobalt oxides, manganese dioxide and copper(II) oxide.
    2. A gas generator propellant according to Claim 1, wherein component (A) is present in a quantity of 50 to 55% by weight, component (B) in a quantity of 50 to 45% by weight and components (C1) and/or (C2) , relative to the total quantity of components (A) and (B), in a quantity of 8 to 20% by weight.
    3. A gas generator propellant according to Claim 1 or 2, wherein component (A) is triaminoguanidine nitrate.
    4. A gas generator propellant according to any one of Claims 1 to 3, wherein component (B) is potassium nitrate.
    5. A gas generator propellant according to any one of Claims 1 to 4, wherein component (C1) is highly dispersed silicic acid.
    6. A gas generator propellant according to any one of Claims 1 to 5, wherein component (A) is composed of 99 to 50% by weight of triaminoguanidine nitrate and 1 to 50% by weight of nitroguanidine, relative to the total quantity of component (A).
    7. A gas generator propellant according to any one of Claims 1 to 6, wherein component (C2) is iron(III) oxide.
    8. A gas generator propellant according to Claim 7, wherein the iron(III) oxide is present in a quantity of 20 to 40% by weight, preferably 25 to 35% by weight, relative to the total quantity of components (A) and (B).
    9. A gas generator propellant according to any one of Claims 1 to 8, additionally comprising (D) a binder which is soluble in water at room temperature.
    10. A gas generator propellant according to Claim 9, wherein the binder is a cellulose ether such as carboxymethylcellulose, methylcellulose ether and preferably methylhydroxyethylcellulose or a polymer of one or more polymerizable olefinic unsaturated monomers.
    11. A gas generator propellant according to Claim 9 or 10, wherein the binder is present in a quantity of 0.1 to 5% by weight, preferably 1.5 to 2.5% by weight, relative to the total quantity of components (A) and (B).
    12. Use of the gas generator propellant according to any one of Claims 1 to 11 as a gas generating agent in airbags, as extinguishing agent or as propellant.
    EP94928758A 1993-10-06 1994-10-06 Gas developing agent Expired - Lifetime EP0722429B1 (en)

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    DE4334099 1993-10-06
    DE4334099 1993-10-06
    PCT/DE1994/001184 WO1995009825A1 (en) 1993-10-06 1994-10-06 Gas developing agent

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    HU9600744D0 (en) 1996-05-28
    BR9407761A (en) 1997-03-04
    WO1995009825A1 (en) 1995-04-13
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    CZ88796A3 (en) 1996-08-14
    PL175606B1 (en) 1999-01-29
    EP0722429A1 (en) 1996-07-24
    JPH09503195A (en) 1997-03-31
    PL313943A1 (en) 1996-08-05
    ATE178304T1 (en) 1999-04-15
    DE59408048D1 (en) 1999-05-06
    CA2172822A1 (en) 1995-04-13
    AU687895B2 (en) 1998-03-05
    SK45596A3 (en) 1997-01-08
    RU2117649C1 (en) 1998-08-20
    ES2130448T3 (en) 1999-07-01
    HUT76867A (en) 1997-12-29
    CN1132501A (en) 1996-10-02
    AU7806694A (en) 1995-05-01

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