EP1069096B1 - Non-azide gas generating composition - Google Patents
Non-azide gas generating composition Download PDFInfo
- Publication number
- EP1069096B1 EP1069096B1 EP00113004A EP00113004A EP1069096B1 EP 1069096 B1 EP1069096 B1 EP 1069096B1 EP 00113004 A EP00113004 A EP 00113004A EP 00113004 A EP00113004 A EP 00113004A EP 1069096 B1 EP1069096 B1 EP 1069096B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- acid
- nitrate
- composition
- set forth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
- C06B23/02—Compositions characterised by non-explosive or non-thermic constituents for neutralising poisonous gases from explosives produced during blasting
-
- 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 present invention relates to an azide-free gas-generating Composition consisting essentially of at least one organic Fuel, at least one inorganic oxidizer and iron oxide consists.
- the composition is particularly suitable for use in Gas generators for vehicle occupant restraint systems.
- Generic gas generating compositions are for example DE 94 16 112 U1 known.
- This document shows a solid gas generator fuel with at least one organic fuel, at least one inorganic oxidizer and at least one carrier substance and / or at least an oxygen-providing carrier, wherein the oxygen carrier Vehicle can be iron (III) oxide.
- the oxygen carrier Vehicle can be iron (III) oxide.
- Gas generating compositions of this type are also known from DE-C2-4411654.
- the gas-generating mixture described therein consists of 20 to 50 wt .-% of a nitrogen-rich organic compound having a nitrogen content of at least 40 wt .-%, 20 to 70 wt .-% of an inorganic oxidizer, 0 to 40 wt .-% of a transition metal oxide and 0.1 to 20 wt .-% zeolite.
- Iron oxide with an average particle size of less than 1 ⁇ m and a specific surface area of more than 8 m 2 / g according to BET is mentioned in particular as transition metal oxide.
- the zeolite addition is intended to bring about a reduction of the carbon monoxide and nitrogen oxide content in the gas mixture resulting from the burning off of the gas-generating composition.
- an azide-free gas generating mixture for use in gas generators for vehicle occupant restraint systems which consists essentially of at least one organic fuel, at least one inorganic oxidizer and iron oxide and which is characterized in that the iron oxide is brown, ferromagnetic ⁇ -Fe 2 O 3 , and the organic fuel is selected from the group consisting of the nitrogen-rich tetrazole, triazole and guanidine compounds and mixtures thereof, or from the group consisting of the nitrogen-containing heterocyclic organic acids and mixtures thereof.
- Iron oxide exists in various modifications; For example, a distinction is made between red ⁇ -Fe 2 O 3 (hematite), brown ⁇ -Fe 2 O 3 (maghemite), black Fe 3 O 4 (magnetite), yellow ⁇ -FeOOH (goethite) and yellow ⁇ -FeOOH (lepidocrocite). which can be both natural and synthetic.
- the preferred iron oxide according to the invention is synthetically produced, brown, ferromagnetic iron oxide ( ⁇ -Fe 2 O 3 , maghemite).
- the iron oxide particularly preferably has an average particle size of ⁇ 1 ⁇ m and a specific surface area of ⁇ 10 m 2 / g.
- the core idea of the invention is the use of brown ⁇ -iron oxide instead of the commonly used red iron oxide ( ⁇ -Fe 2 O 3 , hematite) or other iron oxides.
- ⁇ -iron oxide as a special modification of the available iron oxides, a significant reduction of the noxious gas content, in particular the proportion of nitrogen oxides, can be achieved.
- the principle underlying the present invention of the exchange of red iron oxide for brown ⁇ -iron oxide is particularly useful for compositions containing iron oxide as an active ingredient anyway.
- the invention is not limited to such gas-generating compositions, but mutatis mutandis applicable to all acid-free gas-generating mixtures.
- Fe 3 O 4 is disadvantageous because of its lower oxidation equivalence, since larger amounts of iron oxide are needed to oxidize equal amounts of fuel. This is undesirable because of the associated deterioration in gas yield.
- the use of FeOOH is not preferred because of the high proportion of bound water, since this water evaporates on burning of the gas-generating mixture and the burning rate is thereby reduced too much.
- Experiments have also shown that when using Fe 3 O 4 or FeOOH, the reduction of the nitrogen oxide in the gas mixture does not occur to the same extent as in the use of ⁇ -Fe 2 O 3 .
- the proportion of ⁇ -Fe 2 O 3 in the gas-generating composition of the present invention is preferably 2 to 50% by weight, more preferably about 10 to 40% by weight.
- Tetrazole Triazole or guanidine compounds and mixtures thereof used.
- these compounds are 5-aminotetrazole, 1H-tetrazole, Bistetrazole, azotetrazole, triazolone, nitrotriazolone, Guanidine carbonate, guanidine nitrate, guanidine perchlorate, aminoguanidine nitrate, Guanidine perchlorate, diaminoguanidine nitrate, triaminoguanidine nitrate, Nitroguanidine and its salts, derivatives or mixtures thereof.
- the organic fuel may further be made from nitrogen-containing heterocyclic organic acids and mixtures thereof be selected from the existing group.
- nitrogenous heterocyclic organic acids are cyanuric acid, Isocyanuric acid, cyamelide, uracol, uracil, uramine, uracin, alloxan, Alloxanoic acid, alloxantine, xanthine, allantoin, barbituric acid, orotic acid, Dilituric acid, triazolone, violuric acid, succinimide, dialuric acid, Isodialuric acid, hydantoin, pseudohydantoin, imidazolone, pyrazolone, Parabanic acid, furazan, ammeline, creatinine, maleic hydrazide, Uric acid, pseudo-uric acid, guanazine, guanazole, melamine, their salts, Derivatives or mixtures thereof.
- the inorganic gas contained in the gas generating composition Oxidator is preferably from the of the alkali and / or alkaline earth metal nitrates; chlorates, perchlorates and peroxides, and Ammonium nitrate or perchlorate, copper oxide or basic copper nitrate existing group selected. It can also be mixtures of the aforementioned oxidizers are used.
- the gas generating composition can still the commonly used processing aids, such as Freeze aids, pressing aids and / or lubricants.
- the processing aids are preferred in a proportion of up to 5 wt .-%, based on the total composition used.
- An inventively particularly preferred gas-generating composition consists essentially of 15 to 55 wt .-% 5-aminotetrazole, 25 to 65 wt .-% potassium nitrate and 20 to 60 wt .-% ⁇ -Fe 2 O 3 .
- potassium nitrate instead of potassium nitrate as an inorganic oxidizer, sodium nitrate can also be used.
- composition according to the invention consists essentially of 30 to 50 wt .-% guanidine nitrate. 15 to 35% by weight of basic copper nitrate, 10 to 25% by weight of copper oxide, 1 to 10% by weight of ammonium perchlorate, 1 to 10% by weight of sodium nitrate and 2 to 20% by weight of ⁇ -Fe 2 O 3 ,
- test results show that only the replacement of the red ⁇ -iron oxide by brown ⁇ -iron oxide, a reduction of the nitrogen oxide content effected in the released gas mixture.
- the carbon monoxide content remains almost unaffected.
- a comparable effect occurs when a conventional gas generating composition, brown ⁇ -iron oxide is added.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Air Bags (AREA)
Description
Die vorliegende Erfindung betrifft eine azidfreie gaserzeugende Zusammensetzung, die im wesentlichen aus wenigstens einem organischen Brennstoff, wenigstens einem anorganischen Oxidator und Eisenoxid besteht. Die Zusammensetzung eignet sich insbesondere zur Verwendung in Gasgeneratoren für Fahrzeuginsassen-Rückhaltesysteme.The present invention relates to an azide-free gas-generating Composition consisting essentially of at least one organic Fuel, at least one inorganic oxidizer and iron oxide consists. The composition is particularly suitable for use in Gas generators for vehicle occupant restraint systems.
Gattungsbildende gaserzeugende Zusammensetzungen sind beispielsweise aus der DE 94 16 112 U1 bekannt. Dieses Dokument zeigt einen festen Gasgeneratortreibstoff mit mindestens einem organischen Brennstoff, mindestens einem anorganischen Oxidator und mindestens einer Trägersubstanz und/oder mindestens einer sauerstoffliefernden Trägersubstanz, wobei die sauerstoffliefemde Trägersubstanz Eisen(III)oxid sein kann. Mit diesem Gemisch soll sich das Abbrandverhalten gezielt einstellen lassen, eine beim Abbrand gut zurückhaltbare Schlacke bilden und eine Minimierung der beim Abbrand entstehenden toxischen Gase erreicht werden.Generic gas generating compositions are for example DE 94 16 112 U1 known. This document shows a solid gas generator fuel with at least one organic fuel, at least one inorganic oxidizer and at least one carrier substance and / or at least an oxygen-providing carrier, wherein the oxygen carrier Vehicle can be iron (III) oxide. With this mixture should be the Can set burning behavior targeted, a good at burning burnable Form slag and minimize the resulting during combustion toxic Gases are reached.
Gaserzeugende Zusammensetzungen dieser Art sind auch aus der DE-C2-44 11 654 bekannt. Das darin beschriebene gaserzeugende Gemisch besteht aus 20 bis 50 Gew.-% einer stickstoffreichen organischen Verbindung mit einem Stickstoffgehalt von mindestens 40 Gew.-%, 20 bis 70 Gew.-% eines anorganischen Oxidators, 0 bis 40 Gew.-% eines Übergangsmetalloxids sowie 0,1 bis 20 Gew.-% Zeolith. Als Übergangsmetalloxid ist insbesondere Eisenoxid mit einer mittleren Teilchengröße von weniger als 1 µm und einer spezifischen Oberfläche von mehr als 8 m2/g nach BET genannt. Der Zeolithzusatz soll eine Reduktion des Kohlenmonoxid- und Stickoxidanteils in dem durch den Abbrand der gaserzeugenden Zusammensetzung entstehenden Gasgemisch bewirken.Gas generating compositions of this type are also known from DE-C2-4411654. The gas-generating mixture described therein consists of 20 to 50 wt .-% of a nitrogen-rich organic compound having a nitrogen content of at least 40 wt .-%, 20 to 70 wt .-% of an inorganic oxidizer, 0 to 40 wt .-% of a transition metal oxide and 0.1 to 20 wt .-% zeolite. Iron oxide with an average particle size of less than 1 μm and a specific surface area of more than 8 m 2 / g according to BET is mentioned in particular as transition metal oxide. The zeolite addition is intended to bring about a reduction of the carbon monoxide and nitrogen oxide content in the gas mixture resulting from the burning off of the gas-generating composition.
Das gleiche Ziel wird in der US-PS 5,139,588 verfolgt, die eine gaserzeugende Zusammensetzung auf der Grundlage von Azolverbindungen, wie zum Beispiel Triazol, Aminotetrazol, Tetrazol, Bitetrazol und Metallsalzen dieser Verbindungen beschreibt. Zur Verminderung des Schadgasanteils wird hier der Zusatz eines Alkalimetallsalzes einer anorganischen oder organischen Säure vorgeschlagen, welches aus der aus den Carbonaten, Triazolen, Tetrazolen sowie Salzen von 5 Aminotetrazol, Bitetrazol und 3-Nitro-1,2,4-triazol-5-on bestehenden Gruppe ausgewählt ist.The same goal is pursued in US Pat. No. 5,139,588, which has a Gas generating composition based on azole compounds, such as triazole, aminotetrazole, tetrazole, bitetrazole and Metal salts of these compounds describes. To reduce the Schadgasanteils here is the addition of an alkali metal salt inorganic or organic acid proposed, which consists of the the carbonates, triazoles, tetrazoles and salts of 5-aminotetrazole, Bitetrazole and 3-nitro-1,2,4-triazol-5-one existing group is selected.
In der WO-A-97/29927 wird im Zusammenhang mit der Verringerung des Anteils von Schadgasen allgemein eine Verwendung von Katalysatoren vorgeschlagen, die eine Umwandlung von Kohlenmonoxid und Stickoxiden in Kohlendioxid und Stickstoff begünstigen. Als bevorzugte Katalysatoren werden Alkalimetallsalze, Erdalkalimetallsalze und Übergangsmetallsalze von Tetrazolen, Bistetrazolen und Triazolen genannt. Ebenso wird die Verwendung von Übergangsmetalloxiden in einem Anteil von 0,1 bis 10 Gew.-% empfohlen.In WO-A-97/29927, in connection with the reduction of the Proportion of noxious gases in general a use of catalysts proposed that a conversion of carbon monoxide and nitrogen oxides in Favor carbon dioxide and nitrogen. As preferred catalysts Alkali metal salts, alkaline earth metal salts and transition metal salts of tetrazoles, Bistetrazoles and triazoles are called. Likewise, the use of Transition metal oxides in a proportion of 0.1 to 10 wt .-% recommended.
Aufgrund des Einsatzzwecks der gaserzeugenden Zusammensetzungen in Gasgeneratoren für Fahrzeuginsassen-Rückhaltesysteme ist eine Verringerung des Anteils toxischer Gase in dem durch den Abbrand der gaserzeugenden Zusammensetzungen entstehenden Gasgemisch erforderlich, um eine Gefährung der Fahrzeuginsassen zu vermeiden. Die im Stand der Technik in diesem Zusammenhang vorgeschlagenen Maßnahmen erfordern aber meist den Zusatz weiterer Komponenten und führen somit zu einem Anstieg der Herstellungskosten. Ferner können diese weiteren Komponenten auch das Abbrandverhalten des gaserzeugenden Gemisches in unerwünschter Weise beeinflussen.Due to the purpose of the gas generating compositions in Gas generators for vehicle occupant restraint systems is a reduction of Proportion of toxic gases in which by the combustion of the gas-producing Compositions resulting gas mixture required to create a hazard to avoid the vehicle occupants. The in the prior art in this Context proposed measures usually require the addition other components and thus lead to an increase in Production costs. Furthermore, these other components can also Burning behavior of the gas-generating mixture in an undesirable manner influence.
Es besteht daher weiterhin Bedarf an günstig herzustellenden gaserzeugenden Gemischen, die in Gasgeneratoren für Fahrzeuginsassen- Rückhaltesysteme verwendet werden können, und die einen niedrigen Anteil von toxischen Gasen im aus den Zusammensetzungen freigesetzten Gasgemisch aufweisen.There is therefore still a need for low-cost gas-producing Mixtures used in gas generators for vehicle occupant restraint systems can be used, and a low proportion of toxic gases in the released from the compositions gas mixture.
Gemäß der vorliegenden Erfindung wird hierzu ein azidfreies gaserzeugendes Gemisch zur Verwendung in Gasgeneratoren für Fahrzeuginsassen-Rückhaltesysteme bereitgestellt, welches im wesentlichen aus wenigstens einem organischen Brennstoff, wenigstens einem anorganischen Oxidator und Eisenoxid besteht, und welches dadurch gekennzeichnet ist, daß das Eisenoxid braunes, ferromagnetisches γ-Fe2O3 ist, und der organische Brennstoff aus der aus den stickstoffreichen Tetrazol-, Triazol- und Guanidinverbindungen sowie deren Mischungen bestehenden Gruppe oder aus der aus den stickstoffhaltigen heterocyclischen organischen Säuren sowie deren Mischungen bestehenden --Gruppe ausgewählt ist.According to the present invention, there is provided an azide-free gas generating mixture for use in gas generators for vehicle occupant restraint systems which consists essentially of at least one organic fuel, at least one inorganic oxidizer and iron oxide and which is characterized in that the iron oxide is brown, ferromagnetic γ -Fe 2 O 3 , and the organic fuel is selected from the group consisting of the nitrogen-rich tetrazole, triazole and guanidine compounds and mixtures thereof, or from the group consisting of the nitrogen-containing heterocyclic organic acids and mixtures thereof.
Eisenoxid existiert in den verschiedensten Modifikationen; man unterscheidet beispielsweise zwischen rotem α-Fe2O3 (Hämatit), braunem γ-Fe2O3 (Maghämit), schwarzem Fe3O4 (Magnetit), gelbem α-FeOOH (Goethit) und gelbem γ-FeOOH (Lepidokrokit), die sowohl natürlich vorkommen als auch synthetisch hergestellt werden können. Das erfindungsgemäß bevorzugte Eisenoxid ist synthetisch hergestelltes, braunes, ferromagnetisches Eisenoxid (γ-Fe2O3; Maghämit). Besonders bevorzugt weist das Eisenoxid eine mittlere Teilchengröße von ≤ 1 µm und eine spezifische Oberfläche von ≥ 10 m2/g auf.Iron oxide exists in various modifications; For example, a distinction is made between red α-Fe 2 O 3 (hematite), brown γ-Fe 2 O 3 (maghemite), black Fe 3 O 4 (magnetite), yellow α-FeOOH (goethite) and yellow γ-FeOOH (lepidocrocite). which can be both natural and synthetic. The preferred iron oxide according to the invention is synthetically produced, brown, ferromagnetic iron oxide (γ-Fe 2 O 3 , maghemite). The iron oxide particularly preferably has an average particle size of ≦ 1 μm and a specific surface area of ≥ 10 m 2 / g.
Der Kerngedanke der Erfindung ist die Verwendung von braunem γ-Eisenoxid anstelle des üblicherweise verwendeten roten Eisenoxids (α-Fe2O3, Hämatit) oder sonstiger Eisenoxide. Schon aufgrund der Auswahl von γ-Eisenoxid als einer speziellen Modifikation der zur Verfügung stehenden Eisenoxide kann eine erhebliche Reduzierung des Schadgasanteils, insbesondere des Anteils an Stickoxiden, erreicht werden. Das der vorliegenden Erfindung zugrundeliegende Prinzip des Austausches von rotem Eisenoxid gegen braunes γ-Eisenoxid ist insbesondere für Zusammensetzungen verwendbar, die ohnehin Eisenoxid als wirksamen Bestandteil enthalten. Die Erfindung ist jedoch nicht auf derartige gaserzeugende Zusammensetzungen beschränkt, sondern sinngemäß auf alle azidfreien gaserzeugenden Gemische anwendbar.The core idea of the invention is the use of brown γ-iron oxide instead of the commonly used red iron oxide (α-Fe 2 O 3 , hematite) or other iron oxides. Already due to the choice of γ-iron oxide as a special modification of the available iron oxides, a significant reduction of the noxious gas content, in particular the proportion of nitrogen oxides, can be achieved. The principle underlying the present invention of the exchange of red iron oxide for brown γ-iron oxide is particularly useful for compositions containing iron oxide as an active ingredient anyway. However, the invention is not limited to such gas-generating compositions, but mutatis mutandis applicable to all acid-free gas-generating mixtures.
Eine theoretische Erklärung für die höhere Reaktivität des γ-Fe2O3 im Vergleich zu dem üblicherweise verwendeten α-Fe2O3 könnte in der spinellartigen Kristallstruktur von γ-Fe2O3 gegenüber der Korund-Struktur von α-Fe2O3 und der damit verbundenen, um 5,7 kJ/mol geringeren Bildungswärme von γ-Fe2O3 zu sehen sein. Reaktionen mit γ-Fe2O3 sind daher um den genannten Betrag energetisch günstiger. Die geringere Härte von γ-Fe2O3 begünstigt zudem dessen Verarbeitung.A theoretical explanation for the higher reactivity of γ-Fe 2 O 3 compared to the commonly used α-Fe 2 O 3 could be found in the spinel-like crystal structure of γ-Fe 2 O 3 over the corundum structure of α-Fe 2 O 3 and the associated 5.7 kJ / mol lower formation heat of γ-Fe 2 O 3 . Reactions with γ-Fe 2 O 3 are therefore energetically more favorable by the stated amount. The lower hardness of γ-Fe 2 O 3 also favors its processing.
Eine Verwendung von Fe3O4 ist wegen seiner geringeren Oxidations-äquivalenz nachteilhaft, da zur Oxidation gleicher Mengen an Brennstoff größere Mengen Eisenoxid benötigt werden. Dies ist wegen der damit verbundenen Verschlechterung der Gasausbeute nicht erwünscht. Der Einsatz von FeOOH ist wegen des hohen Anteils an gebundenem Wasser nicht bevorzugt, da dieses Wasser beim Abbrand des gaserzeugenden Gemisches verdampft und die Abbrandgeschwindigkeit hierdurch zu stark herabgesetzt wird. Versuche haben zudem ergeben, daß bei Verwendung von Fe3O4 oder FeOOH die Verringerung des Stickoxidinteils im Gasgemisch nicht in gleichem Maße auftritt wie bei der Verwendung von γ-Fe2O3.Use of Fe 3 O 4 is disadvantageous because of its lower oxidation equivalence, since larger amounts of iron oxide are needed to oxidize equal amounts of fuel. This is undesirable because of the associated deterioration in gas yield. The use of FeOOH is not preferred because of the high proportion of bound water, since this water evaporates on burning of the gas-generating mixture and the burning rate is thereby reduced too much. Experiments have also shown that when using Fe 3 O 4 or FeOOH, the reduction of the nitrogen oxide in the gas mixture does not occur to the same extent as in the use of γ-Fe 2 O 3 .
Der Anteil des γ-Fe2O3 in der erfindungsgemäßen gaserzeugenden Zusammensetzung beträgt vorzugsweise 2 bis 50 Gew.-%, besonders bevorzugt etwa 10 bis 40 Gew.-%.The proportion of γ-Fe 2 O 3 in the gas-generating composition of the present invention is preferably 2 to 50% by weight, more preferably about 10 to 40% by weight.
Als organischer Brennstoff werden stickstoffreiche Tetrazol-, Triazol- oder Guanidin-Verbindungen sowie deren Mischungen eingesetzt. Beispiele für diese Verbindungen sind 5-Aminotetrazol, 1H-Tetrazol, Bistetrazol, Azotetrazol, Triazolon, Nitrotriazolon, Guanidincarbonat, Guanidinnitrat, Guanidinperchlorat, Aminoguanidinnitrat, Guanidinperchlorat, Diaminoguanidinnitrat, Triaminoguanidinnitrat, Nitroguanidin sowie deren Salze, Derivate oder deren Mischungen.As organic fuel are nitrogen-rich Tetrazole, triazole or guanidine compounds and mixtures thereof used. Examples of these compounds are 5-aminotetrazole, 1H-tetrazole, Bistetrazole, azotetrazole, triazolone, nitrotriazolone, Guanidine carbonate, guanidine nitrate, guanidine perchlorate, aminoguanidine nitrate, Guanidine perchlorate, diaminoguanidine nitrate, triaminoguanidine nitrate, Nitroguanidine and its salts, derivatives or mixtures thereof.
Der organische Brennstoff kann ferner aus der aus stickstoffhaltigen heterocyclischen organischen Säuren sowie deren Mischungen bestehenden Gruppe ausgewählt sein. Beispiele für diese stickstoffhaltigen heterocyclischen organischen Säuren sind Cyanursäure, Isocyanursäure, Cyamelid, Urazol, Uracil, Uramin, Urazin, Alloxan, Alloxansäure, Alloxantin, Xanthin, Allantoin, Barbitursäure, Orotsäure, Dilitursäure, Triazolon, Violursäure, Succinimid, Dialursäure, Isodialursäure, Hydantoin, Pseudohydantoin, Imidazolon, Pyrazolon, Parabansäure, Furazan, Ammelin, Kreatinin, Maleinsäurehydrazid, Harnsäure, Pseudoharnsäure, Guanazin, Guanazol, Melamin, deren Salze, Derivate oder deren Mischungen. The organic fuel may further be made from nitrogen-containing heterocyclic organic acids and mixtures thereof be selected from the existing group. Examples of these nitrogenous heterocyclic organic acids are cyanuric acid, Isocyanuric acid, cyamelide, uracol, uracil, uramine, uracin, alloxan, Alloxanoic acid, alloxantine, xanthine, allantoin, barbituric acid, orotic acid, Dilituric acid, triazolone, violuric acid, succinimide, dialuric acid, Isodialuric acid, hydantoin, pseudohydantoin, imidazolone, pyrazolone, Parabanic acid, furazan, ammeline, creatinine, maleic hydrazide, Uric acid, pseudo-uric acid, guanazine, guanazole, melamine, their salts, Derivatives or mixtures thereof.
Der in der gaserzeugenden Zusammensetzung enthaltene anorganische Oxidator ist vorzugsweise aus der aus den Alkali- und/oder Erdalkalimetallnitraten; -chloraten, -perchloraten und -peroxiden, sowie Ammoniumnitrat oder -perchlorat, Kupferoxid oder basischem Kupfernitrat bestehenden Gruppe ausgewählt. Es können auch Mischungen der vorgenannten Oxidatoren eingesetzt werden.The inorganic gas contained in the gas generating composition Oxidator is preferably from the of the alkali and / or alkaline earth metal nitrates; chlorates, perchlorates and peroxides, and Ammonium nitrate or perchlorate, copper oxide or basic copper nitrate existing group selected. It can also be mixtures of the aforementioned oxidizers are used.
Schließlich kann die gaserzeugende Zusammensetzung noch die üblicherweise verwendeten Verarbeitungshilfen, wie zum Beispiel Rieselhilfen, Preßhilfen und/oder Gleitmittel, enthalten. Die Verarbeitungshilfen werden bevorzugt in einem Anteil von bis zu 5 Gew.-%, bezogen auf die Gesamtzusammensetzung, eingesetzt.Finally, the gas generating composition can still the commonly used processing aids, such as Freeze aids, pressing aids and / or lubricants. The processing aids are preferred in a proportion of up to 5 wt .-%, based on the total composition used.
Eine erfindungsgemäß besonders bevorzugte gaserzeugende Zusammensetzung besteht im wesentlichen aus 15 bis 55 Gew.-% 5-Aminotetrazol, 25 bis 65 Gew.-% Kaliumnitrat und 20 bis 60 Gew.-% γ-Fe2O3. Anstelle von Kaliumnitrat als anorganischem Oxidator kann auch Natriumnitrat verwendet werden.An inventively particularly preferred gas-generating composition consists essentially of 15 to 55 wt .-% 5-aminotetrazole, 25 to 65 wt .-% potassium nitrate and 20 to 60 wt .-% γ-Fe 2 O 3 . Instead of potassium nitrate as an inorganic oxidizer, sodium nitrate can also be used.
Eine weitere bevorzugte erfindungsgemäße Zusammensetzung besteht im wesentlichen aus 30 bis 50 Gew.-% Guanidinnitrat. 15 bis 35 Gew.-% basischem Kupfernitrat, 10 bis 25 Gew.-% Kupferoxid, 1 bis 10 Gew.-% Ammoniumperchlorat, 1 bis 10 Gew.-% Natriumnitrat und 2 bis 20 Gew.-% γ-Fe2O3.Another preferred composition according to the invention consists essentially of 30 to 50 wt .-% guanidine nitrate. 15 to 35% by weight of basic copper nitrate, 10 to 25% by weight of copper oxide, 1 to 10% by weight of ammonium perchlorate, 1 to 10% by weight of sodium nitrate and 2 to 20% by weight of γ-Fe 2 O 3 ,
Weitere Vorteile der Erfindung ergeben sich aus der nachfolgenden Beschreibung einiger Ausführungsbeispiele, die jedoch nicht in einem einschränkenden Sinne zu verstehen sind. Further advantages of the invention will become apparent from the following Description of some embodiments, but not in one restrictive sense to understand.
280 g 5-Amminotetrazol, 392 g Kaliumnitrat, 328 g braunes γ-Eisenoxid (Hersteller: Bayer AG, Deutschland) und 5 g pyrogene Kieselsäure wurden in einer Kugelmühle insgesamt 2,5 Stunden gemischt, miteinander vermahlen und anschließend direkt auf einer Rundläuferpresse zu Tabletten mit einem Durchmesser von 6 mm und einer Dicke von 1,8 mm verpreßt. 58 g der so hergestellten Tabletten wurden in einem scrienmäßigen Gasgenerator zur Zündung gebracht und die Zusammensetzung des entstandenen Gasgemisches in einer 2,5 m3-Kammer gemessen.280 g of 5-aminotetrazole, 392 g of potassium nitrate, 328 g of brown γ-iron oxide (manufacturer: Bayer AG, Germany) and 5 g of fumed silica were mixed in a ball mill for a total of 2.5 hours, ground together and then directly into tablets on a rotary press pressed with a diameter of 6 mm and a thickness of 1.8 mm. 58 g of the tablets thus produced were made to ignite in a Scrienmäßig gas generator and measured the composition of the resulting gas mixture in a 2.5 m 3 chamber.
280 g 5-Aminotetrazol, 392 g Kaliumnitrat, 328 g rotes α-Eisenoxid (Hersteller: Firma Harcros, USA) und 5 g pyrogene Kieselsäure wurden in einer Kugelmühle insgesamt 2,5 Stunden gemischt, miteinander vermahlen und anschließend direkt auf einer Rundläuferpresse zu Tabletten mit einem Durchmesser von 6 mm und einer Dicke von 1,8 mm verpreßt. 58 g der so hergestellten Tabletten wurden in einem serienmäßigen Gasgenerator zur Zündung gebracht und die Zusammensetzung des entstandenen Gasgemisches in einer 2,5 m3-Kammer gemessen.280 g of 5-aminotetrazole, 392 g of potassium nitrate, 328 g of red α-iron oxide (Manufacturer: Harcros, USA) and 5 g of fumed silica were used in a ball mill for a total of 2.5 hours mixed, ground together and then with tablets directly on a rotary press a diameter of 6 mm and a thickness of 1.8 mm pressed. 58 g of the tablets thus prepared were in a standard Gas generator brought to ignition and the composition of the resulting gas mixture measured in a 2.5 m3 chamber.
1171,8 g gemahlenes Guanidinnitrat, 325,3 g feinteiliges Kupferoxid, 629,5 g basisches Kupfernitrat, 64,5 g Ammoniumperchlorat, 47,3 g Natriumnitrat, 12,5 g Calciumstearat und 249,3 g γ-Fe2O3 wurden zusammen in eine Kugelmühle eingewogen, 2 Stunden gemischt und miteinander vermahlen. Das resultierende feine Pulver wurde anschließend auf einer Rundläuferpresse zu Tabletten mit einem Durchmesser von 6 mm und einer Dicke von 1,3 mm verpreßt. 58 g der so hergestellten Tabletten wurden in einem serienmäßigen Gasgenerator zur Zündung gebracht und die Zusammensetzung des entstandenen Gasgemisches in einer 2,5 m3-Kammer gemessen. 1171.8 g of ground guanidine nitrate, 325.3 g of finely divided copper oxide, 629.5 g of basic copper nitrate, 64.5 g of ammonium perchlorate, 47.3 g of sodium nitrate, 12.5 g of calcium stearate and 249.3 g of γ-Fe 2 O 3 weighed together in a ball mill, mixed for 2 hours and ground together. The resulting fine powder was then pressed on a rotary press into tablets having a diameter of 6 mm and a thickness of 1.3 mm. 58 g of the tablets thus produced were made to ignite in a standard gas generator and the composition of the resulting gas mixture was measured in a 2.5 m 3 chamber.
1232,5 g gemahlenes Guanidinnitrat, 577,5 g Teinteiliges Kupferoxid, 577,5 g basisches Kupfernitrat, 65 g Ammoniumperchlorat, 47,5 g Natriumnitrat und 12,5 g Calciumstearat wurden zusammen in eine Kugelmühle eingewogen, 2 Stunden gemischt und miteinander vermahlen. Das resultierende feine Pulver wurde anschließend auf einer Rundläuferpresse zu Tabletten mit einem Durchmesser von 6 mm und einer Dicke von 1,3 mm verpreßt und wie in Beispiel 2 getestet.1232.5 g of ground guanidine nitrate, 577.5 g of Teinteiliges Copper oxide, 577.5 g basic copper nitrate, 65 g ammonium perchlorate, 47.5 g of sodium nitrate and 12.5 g of calcium stearate were combined in one Weighed ball mill, mixed for 2 hours and ground together. The resulting fine powder was then placed on a Rotary press to tablets with a diameter of 6 mm and a Thickness of 1.3 mm pressed and tested as in Example 2.
Die aus den obigen Versuchen erhaltenen Schadgaskonzentrationen
sind in der nachfolgenden Tabelle zusammengestellt:
Die Versuchsergebnisse zeigen, daß allein der Ersatz des roten α-Eisenoxid durch braunes γ-Eisenoxid eine Reduzierung des Stickoxidanteils im freigesetzten Gasgemisch bewirkt. Der Kohlenmonoxidanteil bleibt nahezu unbeeinflußt. Eine vergleichbare Wirkung tritt ein, wenn einer üblichen gaserzeugenden Zusammensetzung braunes γ-Eisenoxid beigemischt wird.The test results show that only the replacement of the red α-iron oxide by brown γ-iron oxide, a reduction of the nitrogen oxide content effected in the released gas mixture. The carbon monoxide content remains almost unaffected. A comparable effect occurs when a conventional gas generating composition, brown γ-iron oxide is added.
Claims (10)
- An azide-free gas generating composition for use in gas generators for vehicle occupant restraint systems, consisting essentially of at least one organic fuel, at least one inorganic oxidant and iron oxide, characterized in that the iron oxide is brown, ferromagnetic γ-Fe2O3 and the organic fuel is selected from the group consisting of high-nitrogenous tetrazole, triazole and guanidine compounds as well as mixtures thereof or from the group consisting of nitrogenous heterocyclic organic acids as well as mixtures thereof.
- The composition as set forth in claim 1, characterized in that the γ-Fe2O3 has a mean particle size of ≤ 1µm and a specific surface of ≥ 10 m2/g.
- The composition as set forth in claim 1 or 2, characterized in that the inorganic oxidant is selected from the group consisting of alkaline and/or alkaline earth metal nitrates, chlorates, perchlorates and peroxides, ammonium nitrate or perchlorate as well as copper oxide or basic copper nitrate, and mixtures thereof.
- The composition as set forth in any of claims 1 to 3, characterized in that the tetrazole, triazole and guanidine compounds are selected from the group consisting of 5-aminotetrazole, 1H-tetrazole, bistetrazole, azotetrazole, triazolone, nitrotriazolone, guanidine carbonate, guanidine nitrate, guanidine perchlorate, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, nitroguanidine as well as their salts or derivatives, and mixtures thereof.
- The composition as set forth in any of claims 1 to 3, characterized in that the nitrogenous heterocyclic organic acids are selected from the group consisting of cyanuric acid, isocyanuric acid, cyamelide, urazole, uracil, uramine, urazine, alloxan, alloxanic acid, alloxantin, xanthine, allantoin, barbituric acid, orotic acid, dilituric acid, triazolone, violuric acid, succinimide, dialuric acid, isodialuric acid, hydantoin, pseudohydantoin, imidazolone, pyrazolone, parabanic acid, furazan, ammeline, creatinine, maleic hydrazide, uric acid, pseudouric acid, guanazine, guanazole, melamine, as well as their salts or derivatives, and mixtures thereof.
- The composition as set forth in any of claims 1 to 5, characterized in that the mixture additionally contains up to 5 % by weight of processing aids.
- The composition as set forth in claim 1, consisting essentially of 15 to 55 % by weight 5-aminotetrazole, 25 to 65 % by weight potassium nitrate and 20 to 60 % by weight γ-Fe2O3.
- The composition as set forth in claim 1, consisting essentially of 15 to 55 % by weight 5-aminotetrazole, 25 to 65 % by weight sodium nitrate and 20 to 60 % by weight γ-Fe2O3.
- The composition as set forth in claim 1, consisting essentially of 30 to 50 % by weight guanidine nitrate, 15 to 35 % by weight basic copper nitrate, 10 to 25 % by weight copper oxide, 1 to 10 % by weight ammonium perchlorate, 1 to 10 % by weight sodium nitrate and 2 to 20 % by weight γ-Fe2O3.
- Use of γ-Fe2O3 for producing an azide-free gas generating composition as set forth in any of the preceding claims 1 to 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19932466A DE19932466A1 (en) | 1999-07-12 | 1999-07-12 | Azide free gas generating composition |
| DE19932466 | 1999-07-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1069096A1 EP1069096A1 (en) | 2001-01-17 |
| EP1069096B1 true EP1069096B1 (en) | 2005-05-11 |
Family
ID=7914451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00113004A Expired - Lifetime EP1069096B1 (en) | 1999-07-12 | 2000-06-20 | Non-azide gas generating composition |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP1069096B1 (en) |
| DE (2) | DE19932466A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4500399B2 (en) * | 2000-02-04 | 2010-07-14 | ダイセル化学工業株式会社 | Gas generant composition containing triazine derivative |
| DE10064285C1 (en) * | 2000-12-22 | 2002-10-17 | Nigu Chemie Gmbh | Gas generator fuel composition and its use |
| DE10230402B4 (en) * | 2002-07-05 | 2007-01-11 | Trw Airbag Systems Gmbh & Co. Kg | Process for the preparation of a gas generating composition |
| US20040094250A1 (en) * | 2002-11-14 | 2004-05-20 | Estes-Cox Corporation | Composite propellant compositions |
| US20050016646A1 (en) * | 2003-07-25 | 2005-01-27 | Barnes Michael W. | Chlorine-containing gas generant compositions including a copper-containing chlorine scavenger |
| US20060289096A1 (en) * | 2003-07-25 | 2006-12-28 | Mendenhall Ivan V | Extrudable gas generant |
| JP4767487B2 (en) * | 2003-10-20 | 2011-09-07 | ダイセル化学工業株式会社 | Gas generant composition |
| FR2871457B1 (en) * | 2004-06-10 | 2006-08-11 | Giat Ind Sa | PYROTECHNIC COMPOSITION HAVING IMPROVED MECHANICAL STRENGTH |
| CN100455553C (en) * | 2004-10-08 | 2009-01-28 | 彼得里-蒂恩充气系统两合公司 | Thermally initiatable ignition mixture |
| DE102004062168A1 (en) * | 2004-10-08 | 2006-04-13 | Petri-Dn Gmbh Inflator Systems | Mixture of substances as a thermally initiatable ignition mixture |
| FR2950624B1 (en) * | 2009-09-25 | 2013-05-10 | Snpe Materiaux Energetiques | PYROTECHNIC COMPOUND GAS GENERATOR |
| WO2017205257A1 (en) | 2016-05-23 | 2017-11-30 | Tk Holdings Inc. | Gas generating compositions and methods of making and using thereof |
| CN106810410B (en) * | 2016-12-30 | 2019-10-29 | 北京理工大学 | A kind of pyrotechnic gas propellant composition and preparation method thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3074830A (en) * | 1960-01-05 | 1963-01-22 | Cecil A Rassier | Combustion mixtures containing guanidine nitrate |
| US3214308A (en) * | 1962-12-13 | 1965-10-26 | Thiokol Chemical Corp | Thermally stable propellant powders containing powdered polymeric materials and perchlorates |
| US3617586A (en) * | 1963-12-30 | 1971-11-02 | John M Lenoir | Burning rate accelerating method |
| JPS526388A (en) * | 1975-07-07 | 1977-01-18 | Matsushita Electric Ind Co Ltd | Production process of catalyst for purification of waste gas of combus tion |
| US4214438A (en) * | 1978-02-03 | 1980-07-29 | Allied Chemical Corporation | Pyrotechnic composition and method of inflating an inflatable device |
| EP0543026A4 (en) * | 1991-05-28 | 1995-03-29 | Daicel Chem | Gas generating agent |
| US5382050A (en) * | 1993-04-08 | 1995-01-17 | Trw Inc. | Gas generator for vehicle occupant restraint |
| RU2117649C1 (en) * | 1993-10-06 | 1998-08-20 | Нигу Хеми ГмбХ | Power for gas producer |
| US5817972A (en) * | 1995-11-13 | 1998-10-06 | Trw Inc. | Iron oxide as a coolant and residue former in an organic propellant |
| JP3247929B2 (en) * | 1995-11-14 | 2002-01-21 | ダイセル化学工業株式会社 | Gas generating composition |
-
1999
- 1999-07-12 DE DE19932466A patent/DE19932466A1/en not_active Withdrawn
-
2000
- 2000-06-20 DE DE50010265T patent/DE50010265D1/en not_active Expired - Lifetime
- 2000-06-20 EP EP00113004A patent/EP1069096B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP1069096A1 (en) | 2001-01-17 |
| DE50010265D1 (en) | 2005-06-16 |
| DE19932466A1 (en) | 2001-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0949225B1 (en) | Non-azide gas generating composition | |
| EP1069096B1 (en) | Non-azide gas generating composition | |
| DE69402043T2 (en) | Process aids for gas generating compositions | |
| EP0722429B1 (en) | Gas developing agent | |
| EP0905108B1 (en) | Particle-free gas generating mixture | |
| DE69016371T2 (en) | Gas generating compositions containing nitrotriazalone. | |
| DE69001893T2 (en) | Composition and method for inflating a safety air bag. | |
| EP1006096B1 (en) | Non-azide gas generating composition | |
| EP0691317B1 (en) | Non-azide gas generant formulations | |
| EP1345872B1 (en) | Gas generator fuel composition | |
| DE4411654C2 (en) | Gas generating mixture | |
| DE29722912U1 (en) | Azide free gas generating composition | |
| DE19907198A1 (en) | Gas generating composition for vehicle occupant safety system inflation device | |
| DE102007020549A1 (en) | Composition useful in gas generator devices for automotive restraint systems comprises DL-tartaric acid as a first fuel, second fuel e.g. triazoles, and potassium chlorate as a first oxidizer | |
| WO1998017607A1 (en) | Azide-free, gas-generating solid mixture | |
| DE19840993B4 (en) | Use of a gas-generating mixture as ignition mixture in a gas generator | |
| EP1162183B1 (en) | Ignition mixture for use in gas generators | |
| DE112007001117T5 (en) | Gas generating compositions | |
| DE19812372C2 (en) | Gas generator fuels | |
| DE19925442A1 (en) | Gas generating composition for car gas bag system contains organic fuel, ammonium nitrate stabilized with alkali or alkaline earth metal salt and ammonium halide, sulfate or sulfamate as coolant | |
| DE112011101072T5 (en) | Gas generating compositions | |
| EP1553071B1 (en) | Method of inflating an airbag and airbag module for use in this method | |
| EP1051373B1 (en) | Acid-free, gas-generating composition | |
| DE19531130A1 (en) | Granulated or pelleted gas generating substance, suitable for use in airbags | |
| DE19617538C1 (en) | Gas-generating, acid-free mixture of substances |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EUG | Se: european patent has lapsed | ||
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR SE |
|
| AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
| 17P | Request for examination filed |
Effective date: 20010712 |
|
| AKX | Designation fees paid |
Free format text: DE FR SE |
|
| 17Q | First examination report despatched |
Effective date: 20020913 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: TRW AIRBAG SYSTEMS GMBH |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR SE |
|
| REF | Corresponds to: |
Ref document number: 50010265 Country of ref document: DE Date of ref document: 20050616 Kind code of ref document: P |
|
| REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| ET | Fr: translation filed | ||
| 26N | No opposition filed |
Effective date: 20060214 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20060602 Year of fee payment: 7 |
|
| EUG | Se: european patent has lapsed | ||
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070621 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 17 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 18 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 19 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20190625 Year of fee payment: 20 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20190630 Year of fee payment: 20 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 50010265 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 50010265 Country of ref document: DE Representative=s name: PRINZ & PARTNER MBB PATENTANWAELTE RECHTSANWAE, DE Ref country code: DE Ref legal event code: R081 Ref document number: 50010265 Country of ref document: DE Owner name: ZF AIRBAG GERMANY GMBH, DE Free format text: FORMER OWNER: TRW AIRBAG SYSTEMS GMBH, 84544 ASCHAU, DE |