WO2008001005A2 - Pyrotechnic compositions initiable by heat, and their use - Google Patents

Pyrotechnic compositions initiable by heat, and their use Download PDF

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Publication number
WO2008001005A2
WO2008001005A2 PCT/FR2007/051527 FR2007051527W WO2008001005A2 WO 2008001005 A2 WO2008001005 A2 WO 2008001005A2 FR 2007051527 W FR2007051527 W FR 2007051527W WO 2008001005 A2 WO2008001005 A2 WO 2008001005A2
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pyrotechnic
compositions
composition according
gudn
onta
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PCT/FR2007/051527
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French (fr)
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WO2008001005A3 (en
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Frédéric MARLIN
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Snpe Materiaux Energetiques
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Priority to DE112007001437T priority Critical patent/DE112007001437T5/en
Publication of WO2008001005A2 publication Critical patent/WO2008001005A2/en
Publication of WO2008001005A3 publication Critical patent/WO2008001005A3/en

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    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06CDETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C9/00Chemical contact igniters; Chemical lighters
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00Compositions containing a nitrated organic compound
    • C06B25/34Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B33/00Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide

Definitions

  • the present invention relates to novel pyrotechnic compositions, particularly adapted to intervene in passive safety systems, as well as the use of said new pyrotechnic compositions as initiation charges.
  • Molybdenum is systematically associated with these compositions to lower the decomposition temperature and to increase the liberated energy.
  • the creation of co-melted phases by mixing various alkali nitrate or nitrate of metals or nitrate of organic compounds and / or alkali chlorate and perchlorate is a well-known physical phenomenon. It is also well known to those skilled in the art that increasing the number of phases induces a potential decrease in melting temperatures. In addition, in the pyrotechnic field, it is well known that a phase change is often the triggering element of a chemical reaction. On the other hand, it should be noted that the presence of a melting point initiating decomposition may be a problem for some applications. It may indeed be difficult to maintain the composition after melting for example in a housing. In addition, a fusion is an endothermic event that tends to delay the exothermic start of the composition. This delay can be a disadvantage for the protection of the systems during fast phenomena.
  • compositions similar to those described in the US patents mentioned above Said compositions are characterized by the morphology of the oxidant / reductant mixture they contain and by the presence of a binder, at a low level, to ensure the cohesion of the metal reducer in contact with the oxidants.
  • compositions based on nitroguanidine, antimony sulphide and silver nitrate having self-initiation temperatures of between 127 and 150 ° C.
  • the thermal fusible compositions are made with a mixture of AZODN and co-melt oxidants of potassium silver nitrate.
  • the compositions may also contain an additive reducing agent with a high oxygen content, a metal oxide as a decomposition catalyst, a binder for shaping and a stabilizer for capturing the nitrogen oxides possibly emitted by the decomposition during aging.
  • the compositions described have initiation temperatures of between 147 and 166 ° C. at atmospheric pressure.
  • Patent application WO 2006/026774 describes compositions containing carboxylic acids and potassium chlorate.
  • thermo-initiation compatible with the needs of the application
  • thermo-initiation a maximum temperature of stability as close as possible to the temperature of thermo-initiation
  • Said novel compositions contain GUDN (guanyl urea dinitramide) of I 1 ONTA (3-nitro-l, 2,4-triazol-5-one) and NG (guanidine nitrate). They contain, more precisely, expressed in percentages by mass:
  • compositions have the advantage of having a low initiation temperature, less than 15O 0 C, or even lower than 145 ° C, and a high temperature stability temperature: said compositions are still stable at 107 ° C.
  • compositions do not show a phase change before reaction.
  • phase change makes it possible to ensure the mechanical integrity of the product before its operation and not to induce a delay in the operation due to the endothermicity of the melting.
  • Their self-initiation temperature is not influenced by the physical state (powder, granule or lozenge).
  • Their self-initiation temperature is not influenced by the mass used when this mass exceeds a few milligrams. This lack of influence of the mass on the operation is related to the shape of the exothermic peak of decomposition which is very narrow.
  • Guanidine nitrate (NG) and guanyl urea dinitramide (GUDN) are materials that flow well under stress, which makes it possible to obtain, from these raw materials, pellets having an acceptable mechanical strength for most applications. targeted, without having to add binder.
  • the presence of such a binder is likely to disturb the operation and / or the thermal stability of these compositions. It is understood that the compositions of the invention are advantageously free of binder.
  • thermo-initiatable pyrotechnic compositions which are particularly interesting in they have a small difference in temperature between their maximum temperature of thermal stability and their minimum temperature of thermo-initiation.
  • Such pyrotechnic compositions are suitable for performing safety functions, such as the ignition of a third composition, the deconfinement of a closed volume or any other function in connection with a system potentially having a dangerous behavior for its environment, in case of abnormal heating.
  • the pyrotechnic compositions of the invention consist essentially of the three constituent elements identified above, occurring in the proportions specified above.
  • essentially constituted it is meant that said three constituent elements represent at least 90%, or even at least 95% by weight, of said compositions.
  • compositions essentially consisting of said three constituent elements, are particularly suitable for flame-free gas generation applications.
  • the pyrotechnic compositions of the invention comprise, in addition to the three constituent elements identified above, at least one oxidizer.
  • Said at least one oxidant is advantageously chosen from alkaline nitrates, chlorates and perchlorates, ammonium perchlorate and strontium nitrate. It is very useful advantageously in an alkaline nitrate or perchlorate which does not disturb the thermal stability of the composition.
  • the level of oxidant (s) is adjusted as necessary up to generally a maximum rate of 40% by weight of the composition.
  • Said oxidant (s) ratio is advantageously between 20 to 40% by weight of the composition.
  • compositions of the invention containing at least one such oxidant, generally comprise, expressed in percentages by weight:
  • the invention relates to compositions consisting essentially (at least 90% or even at least 95% by weight) of the four types of ingredients listed above.
  • the pyrotechnic compositions of the invention which comprise at least one oxidant, are perfectly suitable in applications requiring the production of only nontoxic gases (CO 2 , H 2 O, N 2 ).
  • the pyrotechnic compositions of the invention advantageously contain at least one metal reducing agent.
  • a metal reducer is advantageously chosen from boron, magnesium, aluminum, titanium and zirconium. It is generally added up to 10% by weight of the composition. It intervenes advantageously at a rate of between 5 and 10% by weight of the composition.
  • compositions of the invention may also be in the form of granules, obtained in a known Persian manner, after a compaction step - granulation of the powder mixture, carried out by the dry route or by the wet route.
  • the median diameter of the granules is generally between 200 and 600 microns.
  • the pyrotechnic compositions of the invention decompose with rapid emission of gas, with a narrow and very marked exothermic peak.
  • the new pyrotechnic compositions of the invention, described above, are perfectly suitable as pyrotechnic initiating charge (in combustion) in a pyrotechnic device generating gas.
  • DSC Differential Scanning Calorimetry or Differential Enthalpic Analysis
  • thermoinitiation The drop in self-initiation temperature observed on the mixture of raw materials two by two is further increased on the ternary mixtures. No phase change is detectable before the exothermic peak.
  • the operation obtained with respect to thermoinitiation is close to the mixing behavior of materials with respect to the melting point (formation of eutectics).
  • the increase in the number of different materials leads to a lowering of the thermo-initiation in a manner similar to the lowering of the melting temperature obtained on ternary mixtures with respect to binary mixtures.
  • the composition ONTA / GUDN / NG: 33.3 / 33.3 / 33.3 (Ex. 2) is the composition which has the lowest temperature of initiation: 144 ° C., for masses of 2 mg.
  • the mixture ONTA / GUDN / NG: 50/40/10 (Ex. 1) is however retained as preferred mixture because it is the one that offers the best compromise between the temperature of thermoinitiation and the released energy.
  • composition in a sealed environment and the closed box is more representative of the actual integration
  • the formulations may have decomposition rates catalyzed by the partial pressure of the released gases (auto-catalytic phenomenon).
  • a composition can be considered stable in an aging test if its weight loss during this test is low (generally less than 1%) and the product retains its main function.
  • thermoinitiation temperature in terms of thermoinitiation temperature, thermal stability, gas yield, decomposition temperature, output energy and implementation, the three basic ingredients of the composition for obtaining the function thermo-initiation can be used at variable rates.
  • the level of GUDN is advantageously between 20 and 70%, the ONTA level between 20 and 70%, and the guanidine nitrate content between 5 and 60% (% by weight).
  • the composition according to Example 1 is a base composition of low temperature thermo-decomposition having good stability in aging at high temperature.
  • various constituents at least one oxidant, at least one reducing agent, at least one oxidizing agent and at least one reducing agent (see above), etc. may be added depending on the intended application.

Abstract

The present invention relates to pyrotechnic compositions comprising, expressed as percentages by mass; 10% to 80% of guanylurea dinitramide (GUDN), 10% to 80% of 3-nitro-1,2,4-triazol-5-one (ONTA), 3% to 60% of guanidine nitrate (NG). It provides more particularly compositions consisting essentially, expressed as percentages by mass, of: 20% to 70% of GUDN, 20% to 70% of ONTA, 5% to 60% of NG. Pyrotechnic compositions of this kind are highly effective thermally initiable pyrotechnic compositions.

Description

Compositions pyrotechniques thermo-initiables, utilisation. Thermo-initiating pyrotechnic compositions, use.
La présente invention concerne de nouvelles compositions pyrotechniques, particulièrement adaptées pour intervenir dans les systèmes de sécurité passifs, ainsi que l'utilisation desdites nouvelles compositions pyrotechniques comme charges d'initiation.The present invention relates to novel pyrotechnic compositions, particularly adapted to intervene in passive safety systems, as well as the use of said new pyrotechnic compositions as initiation charges.
Dans de tels systèmes, des compositions pyrotechniques interviennent pour restituer une information de type pyrotechnique (c'est- à-dire génération de gaz, allumage, poussée...) quand le système hôte est soumis à un échauffement anormal (contexte d'un incendie, d'un court- circuit, d'une friction excessive). Ladite information est destinée à limiter les effets potentiels du système hôte (explosion, projections...) soumis à un tel échauffement anormal.In such systems, pyrotechnic compositions intervene to restore information of the pyrotechnic type (that is to say gas generation, ignition, thrust ...) when the host system is subjected to an abnormal heating (context of a fire, short circuit, excessive friction). Said information is intended to limit the potential effects of the host system (explosion, projections ...) subjected to such abnormal heating.
Les applications principales envisagées pour les compositions pyrotechniques de l'invention sont :The main applications envisaged for the pyrotechnic compositions of the invention are:
- le déconfinement de piles ou de batteries électriques,- the deconfinement of batteries or electric batteries,
- l'initiation de compositions génératrices de gaz pour systèmes de sécurité type airbags.the initiation of gas generating compositions for airbag type safety systems.
De surcroît, lesdites compositions conviennent pour initier des systèmes d'injection d'additif de protection pour la maintenance préventive ou d'urgence et pour déclencher des actionneurs de dernier secours ou de sécurité.In addition, said compositions are suitable for initiating protective additive injection systems for preventive or emergency maintenance and for triggering last-aid or safety actuators.
Durant les 10 dernières années, les compositions dites fusibles thermiques ont principalement été étudiées dans le cadre de la sécurité automobile pour les applications airbags. Dans ce domaine, de nombreuses compositions ont été décrites avec des températures de thermo-décomposition comprises entre 80 et plus de 2000C.During the last 10 years, the so-called thermal fuse compositions have mainly been studied in the context of automotive safety for airbag applications. In this field, numerous compositions have been described with thermo-decomposition temperatures of between 80 and more than 200 ° C.
Les brevets US 6,221,187 - US 6,101,947 - US 5,959,242 - US 5,739,460 décrivent des compositions qui présentent un point d'initiation piloté par la présence d'un co-fondu (eutectique ou péritectique). La nature des oxydants et des réducteurs organiques employés influe sur la température d'apparition de ce co-fondu et de manière induite sur la température de thermo-initiation. Les principaux ingrédients employés sont le nitrate de guanidine, la nitroguanidine, le nitrate d'ammonium, le nitrate d'argent, le tetraméthyl ammonium nitrate, le 5-aminotétrazole, le chlorate et le perchlorate de potassium et l'acide barbiturique. Le molybdène est systématiquement associé à ces compositions pour abaisser la température de décomposition et pour augmenter l'énergie libérée. La création de phases co-fondues par mélange de divers nitrate d'alcalin ou de nitrate de métaux ou de nitrate de composés organiques et/ou de chlorate et perchlorate d'alcalin est un phénomène physique bien connu. Il est aussi bien connu pour l'homme de l'art que l'accroissement du nombre de phases induit une baisse potentielle des températures de fusion. En outre, dans le domaine pyrotechnique, il est bien connu qu'un changement de phase est souvent l'élément déclencheur d'une réaction chimique. D'autre part, il convient de noter que la présence d'un point de fusion initiant la décomposition peut être un problème pour certaines applications. Il peut, en effet, être difficile de maintenir la composition après fusion par exemple dans un logement. De plus, une fusion est un événement endothermique qui a tendance à retarder le démarrage exothermique de la composition. Ce retard peut être un inconvénient pour la protection des systèmes lors de phénomènes rapides.US Patents 6,221,187 - US 6,101,947 - US 5,959,242 - US 5,739,460 describe compositions which have an initiation point driven by the presence of a co-melted (eutectic or peritectic). The nature of the oxidants and organic reductants employed affects the onset temperature of this co-melted and induced on the temperature of thermo-initiation. The main ingredients used are guanidine nitrate, nitroguanidine, ammonium nitrate, silver nitrate, tetramethyl ammonium nitrate, 5-aminotetrazole, chlorate and potassium perchlorate and barbituric acid. Molybdenum is systematically associated with these compositions to lower the decomposition temperature and to increase the liberated energy. The creation of co-melted phases by mixing various alkali nitrate or nitrate of metals or nitrate of organic compounds and / or alkali chlorate and perchlorate is a well-known physical phenomenon. It is also well known to those skilled in the art that increasing the number of phases induces a potential decrease in melting temperatures. In addition, in the pyrotechnic field, it is well known that a phase change is often the triggering element of a chemical reaction. On the other hand, it should be noted that the presence of a melting point initiating decomposition may be a problem for some applications. It may indeed be difficult to maintain the composition after melting for example in a housing. In addition, a fusion is an endothermic event that tends to delay the exothermic start of the composition. This delay can be a disadvantage for the protection of the systems during fast phenomena.
Le brevet US 6,605,167 décrit des compositions proches de celles décrites dans les brevets US mentionnés ci-dessus. Lesdites compositions se caractérisent par la morphologie du mélange oxydant/réducteur qu'elles renferment et par la présence d'un liant, à faible taux, pour assurer la cohésion du réducteur métallique au contact des oxydants.US Patent 6,605,167 describes compositions similar to those described in the US patents mentioned above. Said compositions are characterized by the morphology of the oxidant / reductant mixture they contain and by the presence of a binder, at a low level, to ensure the cohesion of the metal reducer in contact with the oxidants.
La demande WO 03/083373 décrit des compositions à base de nitroguanidine, de sulfure d'antimoine et de nitrate d'argent, présentant des températures d'auto-initiation comprises entre 127 et 1500C.The application WO 03/083373 describes compositions based on nitroguanidine, antimony sulphide and silver nitrate, having self-initiation temperatures of between 127 and 150 ° C.
Le brevet US 5,460,671 décrit des compositions à base d'hydrate de carbone et de chlorate. Des essais de vieillissement 400 h à 1070C sont décrits. Les compositions à base de chlorate et d'hydrate de carbone sont toutefois réputées pour ne pas être stables à 1070C en milieu confiné surtout sous forme de pastilles, c'est-à-dire quand les contacts entre les ingrédients sont intimes. La présence de chlorate induit en outre un risque de formation de chlorate d'ammonium en cas de contact avec une matière contenant un ion ammonium (nitrate ou perchlorate d'ammonium). La demande de brevet US 2003/0015266 décrit des compositions contenant de l'azobisformamidine-di-nitrate (AZODN). Les compositions fusibles thermiques sont réalisées avec un mélange d'AZODN et d'oxydants co-fondu de nitrate d'argent de potassium. Les compositions peuvent aussi contenir un réducteur additif à haute teneur en oxygène, un oxyde métallique comme catalyseur de décomposition, un liant pour la mise en forme et un stabilisateur pour capter les oxydes d'azote éventuellement émis par la décomposition lors du vieillissement. Les compositions décrites présentent des températures d'initiation comprises entre 147 et 166 0C à la pression atmosphérique.US Patent 5,460,671 discloses carbohydrate and chlorate compositions. Aging tests 400 h at 107 ° C. are described. The chlorate and carbohydrate compositions are, however, reputed not to be stable at 107 ° C. in a confined medium, especially in the form of pellets, that is to say when the contacts between the ingredients are intimate. The presence of chlorate also induces a risk of formation of ammonium chlorate in case of contact with a material containing an ammonium ion (nitrate or ammonium perchlorate). US patent application 2003/0015266 describes compositions containing azobisformamidine-di-nitrate (AZODN). The thermal fusible compositions are made with a mixture of AZODN and co-melt oxidants of potassium silver nitrate. The compositions may also contain an additive reducing agent with a high oxygen content, a metal oxide as a decomposition catalyst, a binder for shaping and a stabilizer for capturing the nitrogen oxides possibly emitted by the decomposition during aging. The compositions described have initiation temperatures of between 147 and 166 ° C. at atmospheric pressure.
Le brevet US 5,866,842 décrit des compositions à base de nitrate d'ammonium stabilisé par du nitrate de potassium, d'ONTA (3-nitro-l,2,4-triazol-5-one), de bore et de iodate d'ammonium. Ces compositions ont des températures d'initiation comprises entre 1300C et 1660C.US Pat. No. 5,866,842 discloses ammonium nitrate compositions stabilized with potassium nitrate, ONTA (3-nitro-1,2,4-triazol-5-one), boron and ammonium iodate. . These compositions have initiation temperatures of between 130 ° C. and 166 ° C.
La demande de brevet WO 2006/026774 décrit des compositions contenant des acides carboxyliques et du chlorate de potassium.Patent application WO 2006/026774 describes compositions containing carboxylic acids and potassium chlorate.
La demande de brevet US 2001/0042577 décrit des compositions à base d'ONTA, de nitrate de guanidine et d'un oxydant complémentaire, nitrate d'alcalin ou perchlorate d'alcalin, ayant des températures d'auto-initiation supérieures à 15O0C.US Patent Application 2001/0042577 discloses compositions based on ONTA, guanidine nitrate and a complementary oxidant, alkaline nitrate or alkali perchlorate, having self-initiation temperatures greater than 150 ° C. vs.
Les exigences principales à satisfaire pour des compositions pyrotechniques thermo-initiables de sécurité sont généralement les suivantes :The main requirements to be satisfied for thermo-initiatory pyrotechnic safety compositions are generally the following:
- disposer d'une température de thermo-initiation compatible avec les besoins de l'application ;- have a temperature of thermo-initiation compatible with the needs of the application;
- présenter une température maximale de stabilité la plus proche possible de la température de thermo-initiation ;- present a maximum temperature of stability as close as possible to the temperature of thermo-initiation;
- avoir une température de thermo-initiation qui soit la moins influencée possible par la masse employée et la vitesse de montée en température ;- Have a temperature-initiation temperature that is the least influenced possible by the mass used and the rate of rise in temperature;
- conserver des caractéristiques fonctionnelles inchangées après vieillissement ;- maintain unchanged functional characteristics after aging;
- libérer une information de sortie compatible avec la fonction recherchée (génération de gaz, allumage d'une tierce composition, ..). Dans le cadre de la présente invention, on propose de nouvelles compositions pyrotechniques particulièrement performantes en référence aux exigences rappelées ci-dessus.- Release an output information compatible with the desired function (gas generation, ignition of a third composition, ..). In the context of the present invention, there are proposed new pyrotechnic compositions particularly effective in reference to the requirements mentioned above.
Lesdites nouvelles compositions contiennent du GUDN (guanyl urée dinitramide), de I1ONTA (3-nitro-l,2,4-triazol-5-one) et du NG (nitrate de guanidine). Elles contiennent, plus précisément, exprimé en pourcentages en masse :Said novel compositions contain GUDN (guanyl urea dinitramide) of I 1 ONTA (3-nitro-l, 2,4-triazol-5-one) and NG (guanidine nitrate). They contain, more precisely, expressed in percentages by mass:
- de 10 à 80 % de guanyl urée dinitramide (GUDN),from 10 to 80% of guanyl urea dinitramide (GUDN),
- de 10 à 80 % de 3-nitro-l,2,4-triazol-5-one (ONTA),from 10 to 80% of 3-nitro-1,2,4-triazol-5-one (ONTA),
- de 3 à 60 % de nitrate de guanidine (NG).- from 3 to 60% of guanidine nitrate (NG).
De telles compositions présentent l'avantage d'avoir une température d'initiation basse, inférieure à 15O0C, voire inférieure à 145°C, et une température de stabilité thermique haute : lesdites compositions sont encore stables à 1070C.Such compositions have the advantage of having a low initiation temperature, less than 15O 0 C, or even lower than 145 ° C, and a high temperature stability temperature: said compositions are still stable at 107 ° C.
En outre, lesdites compositions ne présentent pas de changement de phase avant réaction. Une telle absence de changement de phase permet d'assurer l'intégrité mécanique du produit avant son fonctionnement et de ne pas induire de retard dans le fonctionnement du fait de l'endothermicité de la fusion. Leur température d'auto-initiatîon n'est pas influencée par l'état physique (poudre, granulé ou pastille). Leur température d'auto-initiation n'est pas influencée par la masse mise en œuvre dès lors que cette masse dépasse quelques milligrammes. Cette absence d'influence de la masse sur le fonctionnement est en relation avec la forme du pic exothermique de décomposition qui est très étroit.In addition, said compositions do not show a phase change before reaction. Such an absence of phase change makes it possible to ensure the mechanical integrity of the product before its operation and not to induce a delay in the operation due to the endothermicity of the melting. Their self-initiation temperature is not influenced by the physical state (powder, granule or lozenge). Their self-initiation temperature is not influenced by the mass used when this mass exceeds a few milligrams. This lack of influence of the mass on the operation is related to the shape of the exothermic peak of decomposition which is very narrow.
Le nitrate de guanidine (NG) et la guanyl urée dinitramide (GUDN) sont des matériaux qui fluent bien sous contrainte, ce qui permet d'obtenir, à partir de ces matières premières, des pastilles présentant une tenue mécanique acceptable pour la plupart des applications visées, sans avoir à ajouter de liant. La présence d'un tel liant est susceptible de perturber le fonctionnement et/ou la stabilité thermique desdîtes compositions. On a compris que les compositions de l'invention sont avantageusement exemptes de liant.Guanidine nitrate (NG) and guanyl urea dinitramide (GUDN) are materials that flow well under stress, which makes it possible to obtain, from these raw materials, pellets having an acceptable mechanical strength for most applications. targeted, without having to add binder. The presence of such a binder is likely to disturb the operation and / or the thermal stability of these compositions. It is understood that the compositions of the invention are advantageously free of binder.
Les compositions pyrotechniques de l'invention s'auto-initient, en cas d'accroissement anormal de la température. Il s'agit de compositions pyrotechniques thermo-initiables, particulièrement intéressantes en ce qu'elles présentent un faible écart de température entre leur température maximale de stabilité thermique et leur température minimale de thermo-initiation.The pyrotechnic compositions of the invention self-initiate, in case of abnormal increase of the temperature. These are thermo-initiatable pyrotechnic compositions, which are particularly interesting in they have a small difference in temperature between their maximum temperature of thermal stability and their minimum temperature of thermo-initiation.
De telles compositions pyrotechniques conviennent pour remplir des fonctions de sécurité, telles l'allumage d'une tierce composition, le déconfinement d'un volume clos ou toute autre fonction en relation avec un système ayant potentiellement un comportement dangereux pour son environnement, en cas d'échauffement anormal.Such pyrotechnic compositions are suitable for performing safety functions, such as the ignition of a third composition, the deconfinement of a closed volume or any other function in connection with a system potentially having a dangerous behavior for its environment, in case of abnormal heating.
Les compositions de l'invention comprennent donc du GUDN, de PONTA et du NG. Ces trois composés sont des réducteurs à fort taux d'azote, dont l'oxygène balance (O. B) se situe vers -25 %. L'oxygène balance est, exprimé en pourcentage (%) du produit considéré, la quantité d'oxygène qu'il faut ajouter pour que les réactions de combustion conduisent à la formation de CO2, H2O et N2.The compositions of the invention thus comprise GUDN, PONTA and NG. These three compounds are reducing agents with a high nitrogen content, whose oxygen balance (O. B) is around -25%. The oxygen balance is expressed as a percentage (%) of the product concerned, the amount of oxygen to be added to the combustion reactions lead to the formation of CO2, H2O and N2.
• Selon une première variante, les compositions pyrotechniques de l'invention sont essentiellement constituées des trois éléments constitutifs identifiés ci-dessus, intervenant en les proportions précisées ci-dessus. Par essentiellement constituées, on entend que lesdits trois éléments constitutifs représentent au moins 90 %, voire au moins 95 % en masse, desdites compositions.According to a first variant, the pyrotechnic compositions of the invention consist essentially of the three constituent elements identified above, occurring in the proportions specified above. By essentially constituted, it is meant that said three constituent elements represent at least 90%, or even at least 95% by weight, of said compositions.
De telles compositions, essentiellement constituées desdits trois éléments constitutifs, conviennent particulièrement à des applications de génération de gaz sans flamme.Such compositions, essentially consisting of said three constituent elements, are particularly suitable for flame-free gas generation applications.
De telles compositions présentent avantageusement la composition pondérale ci-après :Such compositions advantageously have the following weight composition:
- 20 à 70 % de GUDN- 20 to 70% of GUDN
- 20 à 70 % d'ONTA, et- 20 to 70% of ONTA, and
- 5 à 60 % de NG.- 5 to 60% of NG.
• Selon une seconde variante, les compositions pyrotechniques de l'invention comprennent, outre les trois éléments constitutifs identifiés ci-dessus, au moins un oxydant. Ledit au moins un oxydant est avantageusement choisi parmi les nitrates, chlorates et perchlorates alcalins, le perchlorate d'ammonium et le nitrate de strontium. Il consiste très avanta- geusement en un nitrate ou perchlorate alcalin qui ne perturbe pas la stabilité thermique de la composition.According to a second variant, the pyrotechnic compositions of the invention comprise, in addition to the three constituent elements identified above, at least one oxidizer. Said at least one oxidant is advantageously chosen from alkaline nitrates, chlorates and perchlorates, ammonium perchlorate and strontium nitrate. It is very useful advantageously in an alkaline nitrate or perchlorate which does not disturb the thermal stability of the composition.
Le taux d'oxydant(s) est ajusté au besoin jusqu'à généralement un taux maximal de 40 % en masse de la composition. Ledit taux d'oxydant(s) est avantageusement compris entre 20 à 40 % en masse de la composition.The level of oxidant (s) is adjusted as necessary up to generally a maximum rate of 40% by weight of the composition. Said oxidant (s) ratio is advantageously between 20 to 40% by weight of the composition.
Les compositions de l'invention, renfermant au moins un tel oxydant, comprennent généralement, exprimé en pourcentages en masse :The compositions of the invention, containing at least one such oxidant, generally comprise, expressed in percentages by weight:
- de 12 à 56 % de GUDN,- from 12 to 56% of GUDN,
- de 12 à 56 % d'ONTA,- from 12 to 56% of ONTA,
- de 3 à 48 % de NG, et- from 3 to 48% of NG, and
- de 20 à 40 % d'au moins un oxydant.from 20 to 40% of at least one oxidant.
Dans le cadre de cette seconde variante, l'invention concerne des compositions constituées essentiellement (à au moins 90 %, voire à au moins 95 %, en masse) des quatre types d'ingrédients listés ci-dessus.In the context of this second variant, the invention relates to compositions consisting essentially (at least 90% or even at least 95% by weight) of the four types of ingredients listed above.
Les compositions pyrotechniques de l'invention, qui comprennent au moins un oxydant, conviennent parfaitement dans des applications nécessitant l'obtention de gaz non toxiques uniquement (CO2, H2O, N2).The pyrotechnic compositions of the invention, which comprise at least one oxidant, are perfectly suitable in applications requiring the production of only nontoxic gases (CO 2 , H 2 O, N 2 ).
On peut également, de manière générale, diminuer la toxicité des gaz générés, en fonctionnant en pression, c'est-à-dire dans un espace confiné.It is also possible, in general, to reduce the toxicity of the gases generated by operating under pressure, that is to say in a confined space.
Pour les applications nécessitant une forte enthalpie de réaction et/ou la présence de particules chaudes (fonction allumage), les compositions pyrotechniques de l'invention renferment avantageusement au moins un réducteur métallique. Un tel réducteur métallique est avantageusement choisi parmi le bore, le magnésium, l'aluminium, le titane et le zirconium. Il est généralement ajouté jusqu'à 10 % en masse de la composition. Il intervient avantageusement à un taux compris entre 5 et 10 % en masse de la composition.For applications requiring a high enthalpy of reaction and / or the presence of hot particles (ignition function), the pyrotechnic compositions of the invention advantageously contain at least one metal reducing agent. Such a metal reducer is advantageously chosen from boron, magnesium, aluminum, titanium and zirconium. It is generally added up to 10% by weight of the composition. It intervenes advantageously at a rate of between 5 and 10% by weight of the composition.
L'ajout d'au moins un réducteur est avantageusement fait de manière conjointe avec celui d'au moins un oxydant. Les compositions de l'invention, renfermant au moins un oxydant et au moins un réducteur, comprennent généralement, exprimé en pourcentages en masse :The addition of at least one reducing agent is advantageously made in conjunction with that of at least one oxidizer. The compositions of the invention, containing at least one oxidant and at least one reducing agent, generally comprise, expressed in percentages by weight:
- de 10 à 35 % de GUDN,- from 10 to 35% of GUDN,
- de 10 à 35 % d'ONTA,- from 10 to 35% of ONTA,
- de 3 à 30 % de NG,- from 3 to 30% of NG,
- de 20 à 40 % d'au moins un oxydant, etfrom 20 to 40% of at least one oxidant, and
- de 5 à 10 % d'au moins un réducteur métallique.from 5 to 10% of at least one metallic reducing agent.
Dans le cadre de sa seconde variante, l'invention concerne tout particulièrement des compositions pyrotechniques essentiellement constituées (à au moins 90 %, voire à au moins 95 %, en masse) des cinq types d'ingrédients listés ci-dessus.In the context of its second variant, the invention relates particularly pyrotechnic compositions consisting essentially (at least 90% or at least 95% by weight) of the five types of ingredients listed above.
Pour les applications nécessitant une stabilité thermique de longue durée en milieu confiné, à haute température (au-dessus de 1000C), un stabilisateur peut intervenir dans les compositions pyrotechniques de l'invention. Un tel stabilisateur a pour fonction d'absorber les oxydes d'azote potentiellement libérés lors du vieillissement. Un tel stabilisateur (au moins un) est employé à un taux généralement inférieur à 5 % en masse. Un tel stabilisateur renferme généralement, dans sa formule chimique, au moins une fonction aminé greffée sur un cycle aromatique. Il peut notamment consister en de la diphénylamine, de la N-nitrodiphénylamine, de la N-méthyl-4-nitroaniline ou de l'éthylcentralite. Certaines aminés aromatiques sont classées "CMR" ("Cancérigène, Mutagène, Tératogène"). On veillera donc à limiter, voire éviter, leur utilisation.For applications requiring long-term thermal stability in a confined environment, at high temperature (above 100 ° C.), a stabilizer can be used in the pyrotechnic compositions of the invention. Such a stabilizer has the function of absorbing the nitrogen oxides potentially released during aging. Such a stabilizer (at least one) is used at a rate generally less than 5% by weight. Such a stabilizer generally contains, in its chemical formula, at least one amine function grafted onto an aromatic ring. It can consist in particular of diphenylamine, N-nitrodiphenylamine, N-methyl-4-nitroaniline or ethylcentralite. Some aromatic amines are classified as "CMR"("Carcinogenic, Mutagenic, Teratogenic"). We will take care to limit or even avoid their use.
Au sein des compositions pyrotechniques de l'invention, les éléments constitutifs - notamment GUDN, ONTA et NG - interviennent à l'état de poudres, présentant avantageusement des granulométries médianes inférieures ou égales à 50 microns.Within the pyrotechnic compositions of the invention, the constituent elements - in particular GUDN, ONTA and NG - intervene in the form of powders, advantageously having median particle sizes less than or equal to 50 microns.
Les compositions de l'invention peuvent être obtenues par simple mélange de leurs éléments constitutifs (poudres), à l'état de poudre. Le mélange peut être mis en œuvre, aussi bien à l'échelle du laboratoire (dans un mortier, par exemple) qu'à l'échelle industrielle (dans un mélangeur à soc de charrue, par exemple). Les mélanges de poudres peuvent être conditionnés, par exemple dans des gélules.The compositions of the invention may be obtained by simple mixing of their constituent elements (powders), in the form of powder. The mixing can be carried out both at the laboratory scale (in a mortar, for example) and on an industrial scale (in a plow mixer, for example). The powder mixtures can be packaged, for example in capsules.
Les compositions de l'invention peuvent aussi se présenter sous la forme de granulés, obtenus de façon connue perse, après une étape de compactage - granulation du mélange des poudres, mise en œuvre par voie sèche ou par voie humide. Le diamètre médian des granulés est généralement compris entre 200 et 600 μm.The compositions of the invention may also be in the form of granules, obtained in a known Persian manner, after a compaction step - granulation of the powder mixture, carried out by the dry route or by the wet route. The median diameter of the granules is generally between 200 and 600 microns.
Les compositions de l'invention peuvent aussi se présenter sous la forme de pastilles, obtenues de façon connue per se, par compression de granulés. Généralement, de telles pastilles présentent les dimensions ci-après : un diamètre compris entre 3 à 10 mm et une épaisseur entre 1 et 5 mm.The compositions of the invention may also be in the form of pellets, obtained in a known manner per se, by compression of granules. Generally, such pellets have the following dimensions: a diameter of between 3 to 10 mm and a thickness between 1 and 5 mm.
Ainsi, les compositions de l'invention peuvent-elles notamment exister sous la forme de poudres, de gélules renfermant de la poudre, de granulés et de pastilles.Thus, the compositions of the invention can in particular exist in the form of powders, capsules containing powder, granules and pellets.
Les compositions pyrotechniques de l'invention se décomposent avec émission rapide de gaz, avec un pic exothermique étroit et très marqué.The pyrotechnic compositions of the invention decompose with rapid emission of gas, with a narrow and very marked exothermic peak.
Les nouvelles compositions pyrotechniques de l'invention, décrites ci-dessus, conviennent parfaitement comme charge pyrotechnique d'initiation (en combustion) dans un dispositif pyrotechnique générateur de gaz.The new pyrotechnic compositions of the invention, described above, are perfectly suitable as pyrotechnic initiating charge (in combustion) in a pyrotechnic device generating gas.
La présente invention a également pour objet cette utilisation desdites nouvelles compositions. En d'autres termes, elle a également pour objet un dispositif pyrotechnique générateur de gaz, renfermant un chargement pyrotechnique et une charge pyrotechnique d'initiation en combustion dudit chargement ; ladite charge pyrotechnique d'initiation présentant, de façon classique, une température d'auto-inflammation inférieure à celle dudit chargement pyrotechnique, et comprenant, de façon caractéristique, une composition pyrotechnique de l'invention, telle que décrite ci-dessus.The present invention also relates to this use of said new compositions. In other words, it also relates to a pyrotechnic device generating a gas, containing a pyrotechnic charge and a pyrotechnic charge for initiation of combustion of said charge; said pyrotechnic initiation charge having, in a conventional manner, a self-ignition temperature lower than that of said pyrotechnic charge, and typically comprising a pyrotechnic composition of the invention, as described above.
On se propose maintenant d'illustrer l'invention par les exemples ci-après. Pour les tests décrits dans les tableaux qui suivent, les définitions et paramètres ci-après sont à prendre en compte.It is now proposed to illustrate the invention by the examples below. For the tests described in the tables that follow, the following definitions and parameters should be taken into account.
DSC : "Differential Scanning Calorimetry" ou Analyse Enthalpique DifférentielleDSC: Differential Scanning Calorimetry or Differential Enthalpic Analysis
T onset : température de démarrage du pic de décomposition, qu'il soit exothermique ou endothermiqueT onset: start temperature of the decomposition peak, whether exothermic or endothermic
Creuset de DSC en aluminium (creuset basse pression)Aluminum DSC Crucible (low pressure crucible)
Vitesse de chauffe : 5°C/min pour tous les essaisHeating rate: 5 ° C / min for all tests
Gaz de balayage pour la DSC : AzoteScavenging gas for DSC: Nitrogen
TAI ; température d'auto-initiation mesurée pour une masse de 200 mg, pour une vitesse de chauffe de 5°C/mn. La composition est introduite dans un tube en verre qui baigne dans un bain de composé métallique à bas point de fusion.TAI; self-initiation temperature measured for a mass of 200 mg, for a heating rate of 5 ° C / min. The composition is introduced into a glass tube which bathes in a bath of low melting point metal compound.
ESV : épreuve de stabilité sous vide : le produit est mis sous vide et en température ; le volume de gaz émis est suivi pendant 200 heures. La stabilité est considérée comme répondant aux exigences opérationnelles si ledit volume de gaz émis est inférieur à 2 cm3/g.ESV: vacuum stability test: the product is evacuated and at temperature; the volume of gas emitted is monitored for 200 hours. The stability is considered as meeting the operational requirements if said volume of emitted gas is less than 2 cm 3 / g.
Dans ce qui suit, les pourcentages indiqués sont des pourcentages en masse.In what follows, the percentages indicated are percentages by mass.
A) On s'intéresse, dans un premier temps, aux éléments constitutifs seuls - GUDN, ONTA, NG - des compositions ternaires de l'invention (première variante).A) First of all, the constitutive elements alone - GUDN, ONTA, NG - are the ternary compositions of the invention (first variant).
Test en DSC des matières premières seules (masse environ 2 mg et creuset ouvert)DSC test of raw materials alone (mass approx. 2 mg and open crucible)
Figure imgf000010_0001
Seuls l'ONTA et le GUDN présentent des pics de décomposition exothermique. Le NG fond à 212°C avant de se décomposer de manière endothermique à partir de 3200C. Les énergies libérées par l'ONTA et le GUDN se situent vers 1440 J/g. Ces deux matières sont dans le mélange les matières qui participent à l'exothermicité de la réaction et donc à son bon déroulement.
Figure imgf000010_0001
Only ONTA and GUDN show peaks of exothermic decomposition. NG melts at 212 ° C before decomposing endothermically from 320 0 C. The energies released by ONTA and GUDN are around 1440 J / g. These two materials are in the mixture the materials that participate in the exothermicity of the reaction and therefore in its smooth running.
B) On s'intéresse, dans un deuxième temps, à des mélanges binaires (7 mélanges binaires) desdits éléments constitutifs.B) We are interested, in a second time, in binary mixtures (7 binary mixtures) of said constituent elements.
Test en DSC des mélanges binaires (masse environ 2 mg et creuset ouvert)DSC test of binary mixtures (mass about 2 mg and open crucible)
Figure imgf000011_0001
Figure imgf000011_0001
Tous les mélanges binaires présentent des pics de décomposition abaissés par rapport à ceux des matières premières d'origine seule. Sur le plan de l'abaissement des températures de réaction, les mélanges ONTA/NG et GUDN/NG sont ceux qui présentent la meilleure synergie en termes de baisse de température. Le mélange GUDN/NG est le seul qui présente une fusion avant réaction. All binary mixtures have lower decomposition peaks than raw materials alone. In terms of lowering the reaction temperatures, the ONTA / NG and GUDN / NG mixtures have the best synergy in terms of temperature drop. The GUDN / NG mixture is the only one that has a pre-reaction melting.
C) On s'intéresse enfin à des mélanges ternaires de l'invention.C) Finally, we are interested in ternary mixtures of the invention.
Test en DSC des mélanges ternaires (masse environ 2 mg et creuset ouvert)DSC test of ternary mixtures (mass about 2 mg and open crucible)
Figure imgf000012_0001
Figure imgf000012_0001
La baisse de température d'auto-initiation constatée sur le mélange des matières premières deux à deux est encore accru sur les mélanges ternaires. Aucun changement de phase n'est détectable avant le pic exothermique. Le fonctionnement obtenu vis-à-vis de la thermoinitiation est proche du comportement de mélange de matières vis-à-vis du point de fusion (formation d'eutectiques). L'accroissement du nombre de matières différentes conduit à un abaissement de la thermo-initiation de manière similaire à la baisse de la température de fusion obtenue sur des mélanges ternaires par rapport à des mélanges binaires.The drop in self-initiation temperature observed on the mixture of raw materials two by two is further increased on the ternary mixtures. No phase change is detectable before the exothermic peak. The operation obtained with respect to thermoinitiation is close to the mixing behavior of materials with respect to the melting point (formation of eutectics). The increase in the number of different materials leads to a lowering of the thermo-initiation in a manner similar to the lowering of the melting temperature obtained on ternary mixtures with respect to binary mixtures.
Exemples de compositions testées en DSC (masse environ 10 mg et creuset fermé)Examples of compositions tested with DSC (mass approximately 10 mg and closed crucible)
Figure imgf000012_0002
Figure imgf000012_0002
Les essais conduits en DSC sur des faibles masses et en creuset ouvert ont été pour certains refaits avec une masse légèrement plus élevée en creuset fermé en début de réaction. La température d'Onset de la réaction est systématiquement abaissée de 2 à environ 100C. Cet abaissement a probablement pour cause un effet de masse d'environ 2 et 10 mg.The tests carried out in DSC on small masses and in open crucible were for some redone with a slightly higher mass in closed crucible at the beginning of reaction. The Onset temperature of the reaction is systematically lowered from 2 to approximately 10 ° C. This lowering probably results in a mass effect of about 2 and 10 mg.
La composition ONTA/GUDN/NG : 33,3 / 33,3 / 33,3 (Ex. 2) est la composition qui présente la température de thermo-initiation la plus basse : 144°C, pour des masses de 2 mg. Le mélange ONTA/GUDN/NG : 50/40/10 (Ex. 1) est toutefois retenu comme mélange préféré car il est celui qui offre le meilleur compromis entre la température de thermoinitiation et l'énergie libérée.The composition ONTA / GUDN / NG: 33.3 / 33.3 / 33.3 (Ex. 2) is the composition which has the lowest temperature of initiation: 144 ° C., for masses of 2 mg. The mixture ONTA / GUDN / NG: 50/40/10 (Ex. 1) is however retained as preferred mixture because it is the one that offers the best compromise between the temperature of thermoinitiation and the released energy.
Tableau des résultats obtenus sur le mélange préféréTable of results obtained on the preferred mixture
Figure imgf000013_0001
Figure imgf000013_0001
* Les pastilles préparées (par empreinte dans un moule par compression manuelle) et testées ont un diamètre de 10 mm pour une épaisseur comprise entre 2 et 2,5 mm. Les résultats obtenus sur la composition suivant l'Exemple 1 montrent que cette formulation présente une température d'auto-initiation basse, vers 1400C. Compte tenu de la précision du moyen de mesure (valeur de TAI donnée à +/- 5°C), nous pouvons constater que la fonction principale de la composition n'est pas perturbée par les vieillissements à 900C et à 1070C. La composition suivant l'Exemple 1 ne présente pas non plus de perte de masse significative à 9O0C en volume fermé et à 1070C à la pression atmosphérique.* The pellets prepared (by impression in a mold by manual compression) and tested have a diameter of 10 mm for a thickness of between 2 and 2.5 mm. The results obtained on the composition according to Example 1 show that this formulation has a low self-initiation temperature, around 140 ° C. Given the accuracy of the measuring means (TAI value given at +/- 5 ° C), we can see that the main function of the composition is not disturbed by aging at 90 ° C. and at 107 ° C. The composition according to Example 1 also does not show significant loss of mass at 90 ° C. 0 C closed volume and 107 0 C at atmospheric pressure.
Les vieillissements ont été conduits à la pression atmosphérique (c'est-à-dire en boite non fermée) et en boite étanche pour deux raisons :Aging was conducted at atmospheric pressure (that is to say, in an unclosed box) and in a sealed box for two reasons:
- dans la plupart des systèmes, la composition est dans un environnement étanche et la boite fermée est plus représentative de l'intégration réelle ;in most systems, the composition is in a sealed environment and the closed box is more representative of the actual integration;
- en fonction de la cinétique de décomposition, les formulations peuvent présenter des vitesses de décomposition catalysées par la pression partielle des gaz libérés (phénomène auto-catalytique).- Depending on the decomposition kinetics, the formulations may have decomposition rates catalyzed by the partial pressure of the released gases (auto-catalytic phenomenon).
Une composition peut être considérée comme stable lors d'un essai de vieillissement si sa perte de masse durant cet essai est faible (généralement inférieure à 1%) et si le produit conserve sa fonction principale.A composition can be considered stable in an aging test if its weight loss during this test is low (generally less than 1%) and the product retains its main function.
Suivant les besoins, en termes de température de thermoinitiation, de stabilité thermique, de rendement gazeux, de température de décomposition, d'énergie de sortie et de mise en œuvre, les trois ingrédients de base de la composition permettant l'obtention de la fonction thermo-initiation peuvent être employés à des taux variables. Comme indiqué ci-dessus, le taux de GUDN est avantageusement compris entre 20 et 70%, le taux d'ONTA entre 20 et 70%, et le taux de nitrate de guanidine entre 5 et 60% (% en masse).According to the needs, in terms of thermoinitiation temperature, thermal stability, gas yield, decomposition temperature, output energy and implementation, the three basic ingredients of the composition for obtaining the function thermo-initiation can be used at variable rates. As indicated above, the level of GUDN is advantageously between 20 and 70%, the ONTA level between 20 and 70%, and the guanidine nitrate content between 5 and 60% (% by weight).
La composition suivant l'Exemple 1 est une base de composition à faible température de thermo-décomposition présentant une bonne stabilité en vieillissement à haute température. A cette base, divers constituants (au moins un oxydant, au moins un réducteur, au moins un oxydant et au moins un réducteur (voir ci-dessus)...) peuvent être ajoutés suivant l'application envisagée. The composition according to Example 1 is a base composition of low temperature thermo-decomposition having good stability in aging at high temperature. On this basis, various constituents (at least one oxidant, at least one reducing agent, at least one oxidizing agent and at least one reducing agent (see above), etc.) may be added depending on the intended application.

Claims

REVENDICATIONS
1. Composition pyrotechnique comprenant, exprimé en pourcentages en masse :1. Pyrotechnic composition comprising, expressed in percentages by mass:
- de 10 à 80 % de guanyl urée dinitramide (GUDN),from 10 to 80% of guanyl urea dinitramide (GUDN),
- de 10 à 80 % de 3-nitro-l,2,4-triazol-5-one (ONTA),from 10 to 80% of 3-nitro-1,2,4-triazol-5-one (ONTA),
- de 3 à 60 % de nitrate de guanidine (NG).- from 3 to 60% of guanidine nitrate (NG).
2. Composition selon la revendication 1, caractérisée en ce qu'elle comprend en outre au moins un oxydant.2. Composition according to claim 1, characterized in that it further comprises at least one oxidizer.
3. Composition selon la revendication 2, caractérisée en ce que ledit au moins un oxydant est choisi parmi les nitrates, chlorates et perchlorates alcalins, le perchlorate d'ammonium et le nitrate de strontium.3. Composition according to claim 2, characterized in that said at least one oxidant is selected from alkaline nitrates, chlorates and perchlorates, ammonium perchlorate and strontium nitrate.
4. Composition selon la revendication 2 ou 3, caractérisée en ce qu'elle comprend, exprimé en pourcentages en masse :4. Composition according to claim 2 or 3, characterized in that it comprises, expressed in percentages by weight:
- de 12 à 56 % de GUDN,- from 12 to 56% of GUDN,
- de 12 à 56 % d'ONTA,- from 12 to 56% of ONTA,
- de 3 à 48 % de NG, et- from 3 to 48% of NG, and
- de 20 à 40 % d'au moins un oxydant.from 20 to 40% of at least one oxidant.
5. Composition selon l'une quelconque des revendications 1 à 4, caractérisée en ce qu'elle comprend en outre au moins un réducteur métallique.5. Composition according to any one of claims 1 to 4, characterized in that it further comprises at least one metal reducer.
6. Composition selon la revendication 5, caractérisée en ce que ledit au moins un réducteur métallique est choisi parmi le bore, le magnésium, l'aluminium, le titane et le zirconium.6. Composition according to claim 5, characterized in that said at least one metal reducer is selected from boron, magnesium, aluminum, titanium and zirconium.
7. Composition selon la revendication 5 ou 6, caractérisée en ce qu'elle comprend jusqu'à 10 % en masse d'au moins un réducteur.7. Composition according to claim 5 or 6, characterized in that it comprises up to 10% by weight of at least one reducing agent.
8. Composition selon l'une quelconque des revendications 5 à 7, caractérisée en ce qu'elle comprend, exprimée en pourcentages en masse :8. Composition according to any one of claims 5 to 7, characterized in that it comprises, expressed in percentages by weight:
- de 10 à 35 % de GUDN,- from 10 to 35% of GUDN,
- de 10 à 35 % d'ONTA,- from 10 to 35% of ONTA,
- de 3 à 30 % de NG,- from 3 to 30% of NG,
- de 20 à 40 % d'au moins un oxydant, etfrom 20 to 40% of at least one oxidant, and
- de 5 à 10 % d'au moins un réducteur métallique. from 5 to 10% of at least one metallic reducing agent.
9. Composition selon la revendication 1, caractérisée en ce qu'elle consiste essentiellement en, exprimé en pourcentages en masse ;9. Composition according to claim 1, characterized in that it consists essentially of, expressed in percentages by weight;
- 10 à 80 % de GUDN,- 10 to 80% of GUDN,
- 10 à 80 % d'ONTA, et- 10 to 80% of ONTA, and
- 3 à 60 % de NG ; en ce qu'elle consiste avantageusement essentiellement en, exprimé en pourcentages en masse :- 3 to 60% of NG; in that it advantageously consists essentially of, expressed in percentages by mass:
- 20 à 70 % de GUDN,- 20 to 70% of GUDN,
- 20 à 70 % d'ONTA, et- 20 to 70% of ONTA, and
- 5 à 60 % de NG.- 5 to 60% of NG.
10. Composition selon l'une quelconque des revendications 1 à 9, caractérisée en ce qu'elle se présente sous la forme d'une poudre, de gélules renfermant une telle poudre, de granulés ou de pastilles.10. Composition according to any one of claims 1 to 9, characterized in that it is in the form of a powder, capsules containing such a powder, granules or pellets.
11. Utilisation d'une composition, selon l'une quelconque des revendications précédentes, comme charge d'initiation en combustion d'un chargement pyrotechnique dans un dispositif pyrotechnique générateur de gaz.11. Use of a composition, according to any one of the preceding claims, as a charge of initiation into combustion of a pyrotechnic charge in a pyrotechnic device generating gas.
12. Dispositif pyrotechnique générateur de gaz, renfermant un chargement pyrotechnique et une charge pyrotechnique d'initiation en combustion dudit chargement, ladite charge pyrotechnique d'initiation présentant une température d'auto-inflammation inférieure à celle dudit chargement pyrotechnique, caractérisé en ce que ladite charge pyrotechnique d'initiation comprend une composition selon l'une quelconque des revendications 1 à 10. 12. pyrotechnic device generating a gas, containing a pyrotechnic charge and a pyrotechnic charge for initiation of combustion of said charge, said pyrotechnic initiation charge having a self-ignition temperature lower than that of said pyrotechnic charge, characterized in that said Pyrotechnic initiation charge comprises a composition according to any one of claims 1 to 10.
PCT/FR2007/051527 2006-06-27 2007-06-26 Pyrotechnic compositions initiable by heat, and their use WO2008001005A2 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2945288A1 (en) * 2009-05-05 2010-11-12 Snpe Materiaux Energetiques Solid pyrotechnic composition, useful to ignite electrical initiators/to implement and pressurize active structures, comprises metal reducing filler, oxidizing filler of e.g. ammonium perchlorate and nitrogenous reducing charge
US8425703B1 (en) 2010-03-24 2013-04-23 The United States of Amierica as Represented by the Secretary of the Navy Insensitive munitions primers

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3007659B1 (en) 2013-06-28 2017-03-24 Herakles METHOD FOR DELIVERING A PRESSURIZED LIQUID FROM THE COMBUSTION GASES OF AT LEAST ONE PYROTECHNIC LOAD
FR3037812B1 (en) 2015-06-29 2017-08-04 Herakles FIRE EXTINGUISHER
FR3077989B1 (en) 2018-02-20 2021-11-19 Arianegroup Sas FIRE EXTINGUISHER

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998055428A1 (en) * 1997-05-21 1998-12-10 Försvarets Forskningsanstalt New chemical compound, explosive containing the compound and use of the compound in gas generators
EP1216977A2 (en) * 2000-12-22 2002-06-26 Snpe Hydrocarbon binder containing pyrotechnic gas-generating compositions and method for continuous manufacturing
DE202004009621U1 (en) * 2004-06-18 2004-08-19 Trw Airbag Systems Gmbh Pyrotechnic composition
DE202004009449U1 (en) * 2004-06-15 2004-10-28 Trw Airbag Systems Gmbh Gas generating composition
WO2006103366A2 (en) * 2005-03-30 2006-10-05 Davey Bickford Self-initiating compositions, electrical initiators using said comparisons and gas generators comprising said initiators

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0706505B1 (en) 1994-04-04 2005-11-16 Automotive Systems Laboratory Inc. Gas generator autoignition with a chlorate composition
US6221187B1 (en) 1996-05-14 2001-04-24 Talley Defense Systems, Inc. Method of safely initiating combustion of a gas generant composition using an autoignition composition
US5959242A (en) 1996-05-14 1999-09-28 Talley Defense Systems, Inc. Autoignition composition
US6101947A (en) 1996-05-14 2000-08-15 Talley Defense Systems, Inc. Method of safety initiating combustion of a gas generant composition using autoignition composition
US5866842A (en) 1996-07-18 1999-02-02 Primex Technologies, Inc. Low temperature autoigniting propellant composition
US6605167B1 (en) 2000-09-01 2003-08-12 Trw Inc. Autoignition material for a vehicle occupant protection apparatus
US6645326B2 (en) 2002-03-25 2003-11-11 Breed Automotive Technology, Inc. Low temperature autoignition material
WO2006026774A2 (en) 2004-08-31 2006-03-09 Automotive Systems Laboratory, Inc. Autoignition compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998055428A1 (en) * 1997-05-21 1998-12-10 Försvarets Forskningsanstalt New chemical compound, explosive containing the compound and use of the compound in gas generators
EP1216977A2 (en) * 2000-12-22 2002-06-26 Snpe Hydrocarbon binder containing pyrotechnic gas-generating compositions and method for continuous manufacturing
DE202004009449U1 (en) * 2004-06-15 2004-10-28 Trw Airbag Systems Gmbh Gas generating composition
DE202004009621U1 (en) * 2004-06-18 2004-08-19 Trw Airbag Systems Gmbh Pyrotechnic composition
WO2006103366A2 (en) * 2005-03-30 2006-10-05 Davey Bickford Self-initiating compositions, electrical initiators using said comparisons and gas generators comprising said initiators

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2945288A1 (en) * 2009-05-05 2010-11-12 Snpe Materiaux Energetiques Solid pyrotechnic composition, useful to ignite electrical initiators/to implement and pressurize active structures, comprises metal reducing filler, oxidizing filler of e.g. ammonium perchlorate and nitrogenous reducing charge
US8425703B1 (en) 2010-03-24 2013-04-23 The United States of Amierica as Represented by the Secretary of the Navy Insensitive munitions primers

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WO2008001005A3 (en) 2008-02-28
FR2902783B1 (en) 2008-10-24
FR2902783A1 (en) 2007-12-28
DE112007001437T5 (en) 2009-05-14

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