EP1037864B1 - Pyrotechnic mixtures generating non-toxic gases based on ammonium perchlorate - Google Patents

Pyrotechnic mixtures generating non-toxic gases based on ammonium perchlorate Download PDF

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EP1037864B1
EP1037864B1 EP98959947A EP98959947A EP1037864B1 EP 1037864 B1 EP1037864 B1 EP 1037864B1 EP 98959947 A EP98959947 A EP 98959947A EP 98959947 A EP98959947 A EP 98959947A EP 1037864 B1 EP1037864 B1 EP 1037864B1
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Prior art keywords
composition according
ammonium perchlorate
composition
weight
nitrate
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EP98959947A
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German (de)
French (fr)
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EP1037864A1 (en
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Gilles Fonblanc
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Societe Nationale des Poudres et Explosifs
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Societe Nationale des Poudres et Explosifs
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
    • 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 the field technique of pyrotechnic gas generation usable in particular in protection systems occupants of a motor vehicle by means of cushions which are inflated by the combustion gases of a pyrotechnic charge. More specifically the invention relates to pyrotechnic compositions generating acceptable temperatures for automotive safety clean, so-called "cold" gases, rich in nitrogen and non-toxic.
  • pyrotechnic gas generators For different pyrotechnic needs and in particular to ensure correct inflation of the cushions protection, pyrotechnic gas generators must supply in extremely short time, around thirty milliseconds, clean gases that is to say free of solid particles liable to create hot spots that can damage the wall cushion, and non-toxic i.e. low nitrogen oxides, carbon oxides and chlorinated products.
  • a first family relates to compositions based on alkali or alkaline earth azide in the presence of a mineral oxidant such as potassium nitrate or a metal oxide.
  • These compositions which may optionally include a binder have major drawbacks. On the one hand they produce during their combustion a lot of dust which must be filtered by relatively large filtration systems, which increases both the weight and the price of the generator.
  • azides are very toxic products which also have the possibility of forming lead azides or other heavy metals which are primary explosives. These compositions are therefore difficult to keep in good conditions for several years in a motor vehicle.
  • a second family concerns compositions with nitrocellulose and nitroglycerin base. These compositions, still known as “double base powders" are very interesting because they burn very quickly and without producing dust. However, they have the disadvantage of not be completely stable over time, a phenomenon which, over the years, affects the effectiveness of these compositions in a motor vehicle.
  • a third family concerns the compositions said "composites” basically constituted by a organic binder and by an oxidizing mineral filler like in particular a mineral perchlorate. These compositions are a priori very interesting because they present good burning speed and excellent stability to aging.
  • compositions have also been proposed constituted by a silicone binder crosslinkable to room temperature, also known as linking "RTV” (Room Temperature Vulcanizable), and potassium perchlorate, the potassium atom playing the role of internal chlorine sensor.
  • RTV Room Temperature Vulcanizable
  • Such compositions are, for example, described in patents FR-A-2 190 776 and FR-B-2 213 254 or in their US correspondents US-A-3,986,908 and US-A-3,964,256.
  • these compositions have the disadvantage of generating gases very rich in oxygen that are not wanted by the manufacturers of automobile industry.
  • compositions based ammonium perchlorate and sodium nitrate mixed with nitro compounds such as azides or metallic nitrides have the disadvantages mentioned previously about compositions containing azides.
  • compositions which consist of a mixture of ammonium perchlorate and sodium nitrate combined with a nitrogenous compound of triazole or tetrazole.
  • Such compositions which are, for example, described in American patent US Pat. No. 4,909,549 generate clean gases, rich in nitrogen, but these gases are relatively toxic and must be diluted with air in order to be used in motor vehicle safety.
  • a person skilled in the art is thus always in search of pyrotechnic compositions which exhibit easy ignition, sustained combustion and which generate, at temperatures acceptable for motor vehicle safety, clean gases, rich in nitrogen and non-toxic.
  • the object of the present invention is precisely to provide such compositions.
  • the invention therefore relates to a gas-generating pyrotechnic composition
  • a gas-generating pyrotechnic composition comprising in particular a crosslinked reducing binder, additives and a main oxidizing charge comprising at least one mixture of ammonium perchlorate associated with a chlorine sensor chosen from the group consisting of nitrate of sodium, lithium carbonate and potassium carbonate, the weight ratio of ammonium perchlorate / chlorine sensor being less than 5.0, characterized in that the weight content of said binder represents at most 10% of the total weight of the composition , in that the weight content of said main oxidizing charge is between 50% and 75% of the total weight of the composition and in that said additives contain at least one copper compound chosen from the group consisting of the oxide cupric CuO and by basic copper nitrate Cu (NO 3 ) 2 , 3Cu (OH) 2 and contain at least one organic nitrogen compound chosen from the group consisting pa r nitroguanidine, guanidinium nitrate, oxamide, dicy
  • the said binder is chosen from the group consisting of crosslinkable resin-based binders silicone, by crosslinkable resin-based binders epoxy and polyacrylic rubbers to reactive terminations, such as terminations epoxy or hydroxyl.
  • the weight content of said binder will advantageously be between 6% and 10% of the weight total composition and weight content of the said main oxidizing charge will then advantageously between 70% and 75% of the total weight of composition.
  • the report ammonium perchlorate by weight / chlorine sensor sera less than 4.0 and preferably less than 1.5.
  • a preferred chlorine sensor is nitrate of sodium and in this case according to a second preferred mode of realization of the invention, the said oxidizing charge main will consist of particles of ammonium perchlorate and sodium nitrate co-precipitates. Such particles are for example obtained by atomization of a perchlorate solution ammonium and sodium nitrate and evaporation of the water contained in the droplets thus obtained. This atomization and this evaporation can be made using commonly used devices to obtain granules of coprecipitated salts.
  • the main oxidizing charge contains, next to the sodium nitrate, other chlorine sensors it is also possible to involve them in the co-precipitation.
  • the particles of coprecipitated ammonium perchlorate and sodium nitrate generally have a particle size of between 10 ⁇ m and 50 ⁇ m .
  • ammonium perchlorate / sensor weight ratio of chlorine is close to 0.95.
  • the metal cyanamides will be chosen from sodium, zinc and copper cyanamides.
  • Zinc cyanamide of formula ZnCN 2 is particularly preferred.
  • the so-called main oxidizing charge contains also potassium perchlorate.
  • weight content of said load of perchlorate of potassium will advantageously be substantially close to 1.7 times its weight content in ammonium perchlorate.
  • the compositions according to the invention have the advantage of lighting up. easily and burn at moderate temperatures, less than or equal to 2200 ° K, or even often less than or equal to 2000 ° K, while producing clean gases, rich in nitrogen and non-toxic which are well suited to inflate protective cushions for occupants of motor vehicles.
  • the binder in the non-crosslinked state, is already in the solid state, as is frequently the case with binders based on epoxy resin, the manufacture and shaping of the compositions according to the invention will be carried out. advantageously by pastillage.
  • the various solid constituents of the composition are ground separately at particle sizes between 10 and 50 micrometers and then are mixed in the dry phase.
  • the mixture thus produced is calibrated by passing over a hopper and dry compressed in the form of pellets or discs.
  • the polymerization of the crosslinkable binder is carried out by hot baking, generally for two and a half hours at 100 ° C or for thirty minutes at 120 ° C.
  • the manufacture and shaping of the compositions according to the invention will advantageously be made by extrusion at so-called "ambient", that is to say close to 20 ° C.
  • a temperature-regulated screw the binder, generally diluted in a solvent, for example trichlorethylene, methyl ethyl ketone or toluene.
  • the dough obtained is extruded to the chosen geometry, by example in the form of a tubular strand, a lobed crown multi-perforated or multi-perforated cylinder.
  • the binder is polymerized crosslinkable by baking.
  • compositions according to the invention are presented so basically like compositions composite pyrotechnics consisting essentially by a crosslinkable reducing binder, by a filler main oxidant based on ammonium perchlorate and at least one chlorine sensor and additives reactive.
  • the binder is a crosslinkable reducing binder whose weight content represents a maximum of 10% of the weight total of the composition.
  • the compositions according to the invention are therefore compositions with a low content by linking.
  • the weight content of binder will be between 6 and 10%.
  • Preferred binders are reducing binders based on epoxy resin, based on silicone resin, or based on rubbers polyacrylics with hydroxyl endings or epoxy terminations.
  • these various binders can be either in the liquid state or in the solid state as a polymerizable molding powder at low temperature.
  • the former will be preferred for compositions intended to be shaped by extrusion while the latter will be preferred for the compositions intended to be shaped by pastillage.
  • the weight content of the oxidizing charge main is between 50% and 75% of the total weight of the composition, preferably it will be understood between 70% and 75%.
  • This main oxidizing charge must contain a mixture of perchlorate of ammonium and a chlorine sensor chosen from sodium nitrate, lithium carbonate and potassium carbonate.
  • the chlorine sensor will often sodium nitrate.
  • the weight report ammonium perchlorate / chlorine sensor will be lower at 5.0 and advantageously less than 4.0. In a way to guarantee a very low level of nitrogen oxides and a combustion temperature below 2200 ° K, often close to 2000 ° K, the perchlorate weight ratio ammonium / chlorine sensor will preferably be less than 1.5 and often close to 0.95.
  • ammonium perchlorate particles coprecipitated with the chlorine sensor especially when the latter is sodium nitrate.
  • the main oxidizing charge may also, alongside ammonium perchlorate, contain potassium perchlorate which, thanks to the potassium ion, has an internal chlorine sensor.
  • the latter contain, alongside the main oxidizing charge, reactive additives which comprise on the one hand a copper compound chosen from the group consisting of cupric oxide CuO and basic copper nitrate Cu (NO 3 ) 2 , 3Cu (OH) 2 and on the other hand a nitrogenous organic compound chosen from the group consisting of nitroguanidine, guanidinium nitrate, oxamide, dicyandiamide and metallic cyanamides.
  • metallic cyanamides sodium, zinc and copper cyanamides are preferred, and more particularly zinc cyanamide ZnCN 2 .
  • additives additional.
  • silicone microbeads The constituents of the charge main oxidant as well as the various additives usable in the context of the invention are presented in solid form and will be finely ground, in general at particle sizes between 10 and 50 ⁇ m, before to be used for formulation and formatting compositions.
  • compositions were produced and put in the form of pellets with a diameter of 7 mm, the oxidizing charge of which is constituted by the mixture NH 4 ClO 4 + NaNO 3 .
  • the binder was ground to a particle size between 20 and 30 ⁇ m, the ammonium perchlorate to a particle size between 10 and 50 ⁇ m , the sodium nitrate and the nitrogenous organic compounds to a particle size close to 30 ⁇ m, and the copper compounds with a particle size of a few ⁇ m.
  • ammonium perchlorate and sodium nitrate are used in the form of co-precipitated particles, it is not necessary to carry out prior grinding, in fact these particles have a particle size between 10 and 50 ⁇ m , often close to 20 ⁇ m.
  • compositions 1 to 21 being particularly interesting by their temperatures of very moderate combustion and the fact that for these compositions there is a near equality between the values obtained for solid residues at the temperature of combustion and those obtained at 1000 ° K, which means that for these compositions all the residues solids is formed in the combustion chamber, before filtration.
  • Examples 11, 25, 37, 38 and 39 have used to fill gas generators for cushion 60 liters. These generators were placed in 60 liter containers and lit. We measured the actual combustion temperature of the loads as well than the carbon monoxide and oxide contents nitrogen from the gases inside the said containers using "DRAEGER" ® tubes.

Abstract

The invention concerns pyrotechnic mixtures generating non-toxic gases characterised in that they essentially consist of a cross-linkable reducing binder based on epoxy resin or silicone resin, an oxidising filler based on ammonium perchlorate and a chlorine scavenger such as sodium nitrate and energetic additives consisting of a cupric compound such as cupric oxide or basic copper nitrate and of a nitrogenated organic compound such as, for example, nitroguanidin or guanidine nitrate. The filler can also contain potassium perchlorate. Said compositions burn at moderate temperatures generating gases rich in nitrogen and poor in nitrogen oxides and carbon monoxide. They are most suitable as pyrotechnic load for gas generators designed to inflate protective air bags for motor vehicle passengers.

Description

La présente invention se rapporte au domaine technique de la génération pyrotechnique de gaz utilisables notamment dans les systèmes de protection des occupants d'un véhicule automobile au moyen de coussins qui sont gonflés par les gaz de combustion d'un chargement pyrotechnique. Plus précisément l'invention concerne des compositions pyrotechniques générant à des températures acceptables pour la sécurité automobile des gaz propres, dits "froids", riches en azote et non-toxiques.The present invention relates to the field technique of pyrotechnic gas generation usable in particular in protection systems occupants of a motor vehicle by means of cushions which are inflated by the combustion gases of a pyrotechnic charge. More specifically the invention relates to pyrotechnic compositions generating acceptable temperatures for automotive safety clean, so-called "cold" gases, rich in nitrogen and non-toxic.

Pour différents besoins pyrotechniques et notamment pour assurer un gonflement correct des coussins de protection, les générateurs pyrotechniques de gaz doivent fournir en des temps extrêmement courts, de l'ordre de trente millisecondes, des gaz propres c'est-à-dire exempts de particules solides susceptibles de constituer des points chauds pouvant endommager la paroi du coussin, et non toxiques c'est-à-dire à faible teneurs en oxydes d'azote, en oxydes de carbone et en produits chlorés.For different pyrotechnic needs and in particular to ensure correct inflation of the cushions protection, pyrotechnic gas generators must supply in extremely short time, around thirty milliseconds, clean gases that is to say free of solid particles liable to create hot spots that can damage the wall cushion, and non-toxic i.e. low nitrogen oxides, carbon oxides and chlorinated products.

Diverses familles de compositions pyrotechniques ont été développées dans ce but.
   Une première famille concerne les compositions à base d'azoture alcalin ou alcalino-terreux en présence d'un oxydant minéral comme le nitrate de potassium ou d'un oxyde métallique. Ces compositions qui peuvent le cas échéant comporter un liant présentent des inconvénients majeurs. D'une part elles produisent lors de leur combustion beaucoup de poussières qui doivent être filtrées par des systèmes de filtration relativement importants, ce qui augmente à la fois le poids et le prix du générateur. D'autre part les azotures sont des produits très toxiques qui présentent de surcroít la possibilité de former des azotures de plomb ou d'autres métaux lourds qui sont des explosifs primaires. Ces compositions sont donc difficiles à conserver dans de bonnes conditions pendant plusieurs années dans un véhicule automobile.Various families of pyrotechnic compositions have been developed for this purpose.
A first family relates to compositions based on alkali or alkaline earth azide in the presence of a mineral oxidant such as potassium nitrate or a metal oxide. These compositions which may optionally include a binder have major drawbacks. On the one hand they produce during their combustion a lot of dust which must be filtered by relatively large filtration systems, which increases both the weight and the price of the generator. On the other hand azides are very toxic products which also have the possibility of forming lead azides or other heavy metals which are primary explosives. These compositions are therefore difficult to keep in good conditions for several years in a motor vehicle.

Une seconde famille concerne les compositions à base de nitrocellulose et de nitroglycérine. Ces compositions, encore connues sous l'appellation de "poudres à double base", sont très intéressantes car elles brûlent très vite et sans produire de poussière. Mais elles présentent toutefois l'inconvénient de ne pas être totalement stables dans le temps, phénomène qui, au fil des ans, altère l'efficacité de ces compositions dans un véhicule automobile.A second family concerns compositions with nitrocellulose and nitroglycerin base. These compositions, still known as "double base powders" are very interesting because they burn very quickly and without producing dust. However, they have the disadvantage of not be completely stable over time, a phenomenon which, over the years, affects the effectiveness of these compositions in a motor vehicle.

Une troisième famille concerne les compositions dites "composites" constituées fondamentalement par un liant organique et par une charge minérale oxydante comme notamment un perchlorate minéral. Ces compositions sont à priori très intéressantes car elles présentent une bonne vitesse de combustion et une excellente stabilité au vieillissement.A third family concerns the compositions said "composites" basically constituted by a organic binder and by an oxidizing mineral filler like in particular a mineral perchlorate. These compositions are a priori very interesting because they present good burning speed and excellent stability to aging.

Il a ainsi été proposé par le brevet FR-A-2 137 619 ou par son correspondant US-A-3, 723, 205 des compositions dont le liant est un chlorure de polyvinyle et dont la charge oxydante est un perchlorate d'ammonium en présence de nitrate de sodium comme capteur interne de chlore. Néanmoins l'emploi d'un liant chloré en présence de charges énergétiques est d'une mise en oeuvre délicate, notamment au plan de la sécurité et de la non toxicité des gaz générés.It has thus been proposed by patent FR-A-2 137 619 or by its correspondent US-A-3, 723, 205 of the compositions whose binder is polyvinyl chloride and whose oxidizing charge is an ammonium perchlorate in presence of sodium nitrate as internal sensor of chlorine. However, the use of a chlorinated binder in the presence of energy charges is an implementation delicate, especially in terms of security and safety toxicity of the gases generated.

Il a aussi été proposé des compositions composites constituées par un liant silicone réticulable à température ambiante, encore connu sous l'appellation de liant "RTV" (Room Temperature Vulcanizable), et de perchlorate de potassium, l'atome de potassium jouant le rôle de capteur interne de chlore. De telles compositions sont, par exemple, décrites dans les brevets FR-A-2 190 776 et FR-B-2 213 254 ou dans leurs correspondants américains US-A-3,986,908 et US-A-3,964,256. Ces compositions présentent cependant l'inconvénient de générer des gaz très riches en oxygène qui ne sont pas recherchés par les constructeurs de l'industrie automobile.Composite compositions have also been proposed constituted by a silicone binder crosslinkable to room temperature, also known as linking "RTV" (Room Temperature Vulcanizable), and potassium perchlorate, the potassium atom playing the role of internal chlorine sensor. Such compositions are, for example, described in patents FR-A-2 190 776 and FR-B-2 213 254 or in their US correspondents US-A-3,986,908 and US-A-3,964,256. However, these compositions have the disadvantage of generating gases very rich in oxygen that are not wanted by the manufacturers of automobile industry.

Il a alors été proposé des compositions composites constituées par un liant silicone et par un mélange de perchlorate d'ammonium et de nitrate de sodium. De telles compositions qui sont pas exemple décrites dans le brevet français FR-A-2 728 562 ou dans son correspondant américain US-A-5 610 444, génèrent bien des gaz propres, riches en azote et non toxiques mais présentent l'inconvénient de brûler à des températures très élevées.Composite compositions were then proposed consisting of a silicone binder and a mixture of ammonium perchlorate and sodium nitrate. Of such compositions which are not example described in French patent FR-A-2,728,562 or in its US correspondent US-A-5 610 444, generate well clean gases, rich in nitrogen and non-toxic but have the disadvantage of burning at temperatures very high.

Il a également été proposé des compositions à base de perchlorate d'ammonium et de nitrate de sodium mélangés à des composés nitrés comme des azotures ou des nitrures métalliques. Ces compositions qui sont par exemple décrites dans le brevet américain US-A-3 814 694 présentent cependant les inconvénients mentionnés précédemment à propos des compositions contenant des azotures. It has also been proposed compositions based ammonium perchlorate and sodium nitrate mixed with nitro compounds such as azides or metallic nitrides. These compositions which are by example described in US patent US-A-3,814,694 have the disadvantages mentioned previously about compositions containing azides.

Il a enfin également été proposé des compositions constituées par un mélange de perchlorate d'ammonium et de nitrate de sodium associé à un composé azoté du triazole ou du tétrazole. De telles compositions qui sont par exemple décrites dans le brevet américain US-A-4 909 549 génèrent bien des gaz propres, riches en azote mais ces gaz sont relativement toxiques et doivent être dilués avec l'air pour pouvoir être utilisés en sécurité automobile.
   L'homme de métier est ainsi toujours à la recherche de compositions pyrotechniques qui présentent un allumage facile, une combustion entretenue et qui génèrent, à des températures acceptables pour la sécurité automobile, des gaz propres, riches en azote et non toxiques. L'objet de la présente invention est précisément de proposer de telles compositions.Finally, compositions have also been proposed which consist of a mixture of ammonium perchlorate and sodium nitrate combined with a nitrogenous compound of triazole or tetrazole. Such compositions which are, for example, described in American patent US Pat. No. 4,909,549 generate clean gases, rich in nitrogen, but these gases are relatively toxic and must be diluted with air in order to be used in motor vehicle safety.
A person skilled in the art is thus always in search of pyrotechnic compositions which exhibit easy ignition, sustained combustion and which generate, at temperatures acceptable for motor vehicle safety, clean gases, rich in nitrogen and non-toxic. The object of the present invention is precisely to provide such compositions.

L'invention concerne donc une composition pyrotechnique génératrice de gaz comprenant notamment un liant réducteur réticulé, des additifs et une charge oxydante principale comprenant au moins un mélange de perchlorate d'ammonium associé à un capteur de chlore choisi dans le groupe constitué par le nitrate de sodium, le carbonate de lithium et le carbonate de potassium, le rapport pondéral perchlorate d'ammonium/ capteur de chlore étant inférieur à 5,0 caractérisé en ce que la teneur pondérale du dit liant représente au maximum 10% du poids total de la composition, en ce que la teneur pondérale de la dite charge oxydante principale est comprise entre 50% et 75% du poids total de la composition et en ce que les dits additifs contiennent au moins un composé du cuivre choisi dans le groupe constitué par l'oxyde cuivrique CuO et par le nitrate basique de cuivre Cu(NO3)2,3Cu(OH)2 et contiennent au moins un composé organique azoté choisi dans le groupe constitué par la nitroguanidine, le nitrate de guanidinium, l'oxamide, le dicyandiamide de formule C2H4N4 et les cyanamides métalliques.The invention therefore relates to a gas-generating pyrotechnic composition comprising in particular a crosslinked reducing binder, additives and a main oxidizing charge comprising at least one mixture of ammonium perchlorate associated with a chlorine sensor chosen from the group consisting of nitrate of sodium, lithium carbonate and potassium carbonate, the weight ratio of ammonium perchlorate / chlorine sensor being less than 5.0, characterized in that the weight content of said binder represents at most 10% of the total weight of the composition , in that the weight content of said main oxidizing charge is between 50% and 75% of the total weight of the composition and in that said additives contain at least one copper compound chosen from the group consisting of the oxide cupric CuO and by basic copper nitrate Cu (NO 3 ) 2 , 3Cu (OH) 2 and contain at least one organic nitrogen compound chosen from the group consisting pa r nitroguanidine, guanidinium nitrate, oxamide, dicyandiamide of formula C 2 H 4 N 4 and metallic cyanamides.

Selon un premier mode préféré de réalisation de l'invention le dit liant est choisi dans le groupe constitué par les liants réticulables à base de résine silicone, par les liants réticulables à base de résine époxy et par les caoutchoucs polyacryliques à terminaisons réactives, comme notamment les terminaisons époxy ou hydroxyles. La teneur pondérale du dit liant sera avantageusement comprise entre 6% et 10% du poids total de la composition et la teneur pondérale de la dite charge oxydante principale sera alors avantageusement comprise entre 70% et 75% du poids total de la composition. Avantageusement encore le rapport pondérale perchlorate d'ammonium/capteur de chlore sera inférieur à 4,0 et préférentiellement inférieur à 1,5.According to a first preferred embodiment of the invention the said binder is chosen from the group consisting of crosslinkable resin-based binders silicone, by crosslinkable resin-based binders epoxy and polyacrylic rubbers to reactive terminations, such as terminations epoxy or hydroxyl. The weight content of said binder will advantageously be between 6% and 10% of the weight total composition and weight content of the said main oxidizing charge will then advantageously between 70% and 75% of the total weight of composition. Advantageously still the report ammonium perchlorate by weight / chlorine sensor sera less than 4.0 and preferably less than 1.5.

Un capteur de chlore préféré est le nitrate de sodium et dans ce cas selon un second mode préféré de réalisation de l'invention, la dite charge oxydante principale sera constituée par des particules de perchlorate d'ammonium et de nitrate de sodium coprécipités. De telles particules sont par exemple obtenues par atomisation d'une solution de perchlorate d'ammonium et de nitrate de sodium et évaporation de l'eau contenue dans les gouttelettes ainsi obtenues. Cette atomisation et cette évaporation peuvent être réalisés à l'aide des appareils habituellement utilisés pour obtenir des granulés de sels coprécipités. Lorsque la charge oxydante principale contient, à côté du nitrate de sodium, d'autres capteurs de chlore, il est également possible de faire participer ces derniers à la coprécipitation. A preferred chlorine sensor is nitrate of sodium and in this case according to a second preferred mode of realization of the invention, the said oxidizing charge main will consist of particles of ammonium perchlorate and sodium nitrate co-precipitates. Such particles are for example obtained by atomization of a perchlorate solution ammonium and sodium nitrate and evaporation of the water contained in the droplets thus obtained. This atomization and this evaporation can be made using commonly used devices to obtain granules of coprecipitated salts. When the main oxidizing charge contains, next to the sodium nitrate, other chlorine sensors it is also possible to involve them in the co-precipitation.

Les particules de perchlorate d'ammonium et de nitrate de sodium coprécipités ont en général une granulométrie comprise entre 10µm et 50µm.The particles of coprecipitated ammonium perchlorate and sodium nitrate generally have a particle size of between 10 μm and 50 μm .

Selon un quatrième mode préféré de réalisation de l'invention le rapport pondéral perchlorate d'ammonium/capteur de chlore est voisin de 0,95.According to a fourth preferred embodiment of the invention the ammonium perchlorate / sensor weight ratio of chlorine is close to 0.95.

Selon un cinquième mode préféré de réalisation de l'invention, les cyanamides métalliques seront choisis parmi les cyanamides de sodium, de zinc et de cuivre. Le cyanamide de zinc de formule ZnCN2 est particulièrement préféré.According to a fifth preferred embodiment of the invention, the metal cyanamides will be chosen from sodium, zinc and copper cyanamides. Zinc cyanamide of formula ZnCN 2 is particularly preferred.

Selon un sixième mode préféré de réalisation de l'invention la dite charge oxydante principale contient également du perchlorate de potassium. Dans ce cas la teneur pondérale de la dite charge en perchlorate de potassium sera avantageusement sensiblement voisine de 1,7 fois sa teneur pondérale en perchlorate d'ammonium.According to a sixth preferred embodiment of the invention the so-called main oxidizing charge contains also potassium perchlorate. In this case weight content of said load of perchlorate of potassium will advantageously be substantially close to 1.7 times its weight content in ammonium perchlorate.

Grâce à leur faible teneur en liant et grâce à la présence d'additifs réactifs à côté de la charge principale oxydante à base de perchlorate d'ammonium et de capteur de chlore, les compositions selon l'invention présentent l'avantage de s'allumer facilement et de brûler à des températures modérées, inférieures ou égales à 2200°K, voire souvent inférieure ou égales à 2000°K, tout en produisant des gaz propres, riches en azote et non toxiques qui conviennent bien pour gonfler des coussins de protection pour occupants de véhicules automobiles.
   Lorsque le liant, à l'état non réticulé, se trouve déjà à l'état solide, comme cela est fréquemment le cas avec les liants à base de résine époxy, la fabrication et la mise en forme des compositions selon l'invention se fera avantageusement par pastillage. Dans ce cas les différents constituants solides de la composition sont broyés séparément à des granulométries comprises entre 10 et 50 micromètres puis sont mélangés en phase sèche. Le mélange ainsi réalisé est calibré par passage sur une trémie et comprimé à sec sous forme de pastilles ou de disques. La polymérisation du liant réticulable est effectuée par cuisson à chaud, en général pendant deux heures et demie à 100°C ou pendant trente minutes à 120°C.Thanks to their low content of binder and thanks to the presence of reactive additives alongside the main oxidizing charge based on ammonium perchlorate and on chlorine sensor, the compositions according to the invention have the advantage of lighting up. easily and burn at moderate temperatures, less than or equal to 2200 ° K, or even often less than or equal to 2000 ° K, while producing clean gases, rich in nitrogen and non-toxic which are well suited to inflate protective cushions for occupants of motor vehicles.
When the binder, in the non-crosslinked state, is already in the solid state, as is frequently the case with binders based on epoxy resin, the manufacture and shaping of the compositions according to the invention will be carried out. advantageously by pastillage. In this case, the various solid constituents of the composition are ground separately at particle sizes between 10 and 50 micrometers and then are mixed in the dry phase. The mixture thus produced is calibrated by passing over a hopper and dry compressed in the form of pellets or discs. The polymerization of the crosslinkable binder is carried out by hot baking, generally for two and a half hours at 100 ° C or for thirty minutes at 120 ° C.

Lorsque le liant, à l'état non réticulé, se trouve encore à l'état liquide, comme cela est le cas avec les caoutchoucs polyacryliques à terminaisons réactives, avec les liants à base de résine silicone, mais aussi avec certains liants à base de résine époxy, la fabrication et la mise en forme des compositions selon l'invention se fera avantageusement par extrusion à tempérante dite "ambiante", c'est-à-dire voisine de 20°C. Pour ce faire on introduit dans une extrudeuse à vis régulée en température le liant, en général dilué dans un solvant, par exemple le trichloréthylène, la méthyléthylcétone ou le toluène. On ajoute alors les constituants solides broyés comme précédemment décrit et on extrude la pâte obtenue à la géométrie choisie, par exemple sous forme de brin tubulaire, de couronne lobée multiperforée ou de cylindre multiperforé. Après découpage à la longueur voulue et élimination du solvant par séchage on provoque la polymérisation du liant réticulable par cuisson.When the binder, in the non-crosslinked state, is still in a liquid state, as is the case with polyacrylic rubbers with reactive terminations, with silicone resin binders, but also with certain epoxy resin binders, the manufacture and shaping of the compositions according to the invention will advantageously be made by extrusion at so-called "ambient", that is to say close to 20 ° C. To do this, we introduce into a temperature-regulated screw the binder, generally diluted in a solvent, for example trichlorethylene, methyl ethyl ketone or toluene. We then add the solid constituents ground as previously described and the dough obtained is extruded to the chosen geometry, by example in the form of a tubular strand, a lobed crown multi-perforated or multi-perforated cylinder. After cutting to the desired length and removing the solvent by drying, the binder is polymerized crosslinkable by baking.

On donne ci-après une description détaillée d'une réalisation préférée de l'invention. A detailed description is given below of preferred embodiment of the invention.

Les compositions selon l'invention se présentent donc fondamentalement comme des compositions pyrotechniques composites constituées essentiellement par un liant réducteur réticulable, par une charge oxydante principale à base de perchlorate d'ammonium et d'au moins un capteur de chlore et par des additifs réactifs.The compositions according to the invention are presented so basically like compositions composite pyrotechnics consisting essentially by a crosslinkable reducing binder, by a filler main oxidant based on ammonium perchlorate and at least one chlorine sensor and additives reactive.

Le liant est un liant réducteur réticulable dont la teneur pondérale représente au maximum 10% du poids total de la composition. Les compositions selon l'invention sont donc des compositions à faible teneur en liant. Préférentiellement la teneur pondérale en liant sera comprise entre 6 et 10%. Les liants préférés sont les liants réducteurs à base de résine époxy, à base de résine silicone, ou à base de caoutchoucs polyacryliques à terminaisons hydroxyles ou à terminaisons époxy.The binder is a crosslinkable reducing binder whose weight content represents a maximum of 10% of the weight total of the composition. The compositions according to the invention are therefore compositions with a low content by linking. Preferably the weight content of binder will be between 6 and 10%. Preferred binders are reducing binders based on epoxy resin, based on silicone resin, or based on rubbers polyacrylics with hydroxyl endings or epoxy terminations.

Avant réticulation, ces différents liants peuvent se trouver soit à l'état liquide soit à l'état solide sous forme de poudre à mouler polymérisable à basse température. Les premiers seront préférés pour les compositions destinées à être mises en forme par extrusion tandis que les seconds seront préférés pour les compositions destinées à être mise en forme par pastillage.Before crosslinking, these various binders can be either in the liquid state or in the solid state as a polymerizable molding powder at low temperature. The former will be preferred for compositions intended to be shaped by extrusion while the latter will be preferred for the compositions intended to be shaped by pastillage.

La teneur pondérale de la charge oxydante principale est comprise entre 50% et 75% du poids total de la composition, préférentiellement elle sera comprise entre 70% et 75%. Cette charge oxydante principale contient obligatoirement un mélange de perchlorate d'ammonium et d'un capteur de chlore choisi parmi le nitrate de sodium, le carbonate de lithium et le carbonate de potassium. Le capteur de chlore sera souvent du nitrate de sodium. Le rapport pondéral perchlorate d'ammonium/capteur de chlore sera inférieur à 5,0 et avantageusement inférieur à 4,0. De manière à garantir un taux très faible en oxydes d'azote et une température de combustion inférieure à 2200°K, souvent voisine de 2000°K, le rapport pondéral perchlorate d'ammonium/capteur de chlore sera préférentiellement inférieur à 1,5 et souvent voisin de 0,95.The weight content of the oxidizing charge main is between 50% and 75% of the total weight of the composition, preferably it will be understood between 70% and 75%. This main oxidizing charge must contain a mixture of perchlorate of ammonium and a chlorine sensor chosen from sodium nitrate, lithium carbonate and potassium carbonate. The chlorine sensor will often sodium nitrate. The weight report ammonium perchlorate / chlorine sensor will be lower at 5.0 and advantageously less than 4.0. In a way to guarantee a very low level of nitrogen oxides and a combustion temperature below 2200 ° K, often close to 2000 ° K, the perchlorate weight ratio ammonium / chlorine sensor will preferably be less than 1.5 and often close to 0.95.

Afin de favoriser encore plus la fixation du chlore provenant du perchlorate d'ammonium, on pourra avantageusement utiliser des particules de perchlorate d'ammonium coprécipité avec le capteur de chlore, notamment lorsque ce dernier est du nitrate de sodium.
   Par ailleurs la charge oxydante principale pourra également, à côté du perchlorate d'ammonium, contenir du perchlorate de potassium qui possède, grâce à l'ion potassium, un capteur de chlore interneTo further promote the fixation of chlorine from ammonium perchlorate, it is advantageous to use ammonium perchlorate particles coprecipitated with the chlorine sensor, especially when the latter is sodium nitrate.
In addition, the main oxidizing charge may also, alongside ammonium perchlorate, contain potassium perchlorate which, thanks to the potassium ion, has an internal chlorine sensor.

Afin d'améliorer encore la qualité des gaz produits et de garantir un bon allumage et une bonne tenue en combustion des compositions selon l'invention, ces dernières contiennent, à côté de la charge oxydante principale, des additifs réactifs qui comprennent d'une part un composé du cuivre choisi dans le groupe constitué par l'oxyde cuivrique CuO et par le nitrate basique de cuivre Cu(NO3)2, 3Cu(OH)2 et d'autre part un composé organique azoté choisi dans le groupe constitué par la nitroguanidine, le nitrate de guanidinium, l'oxamide, le dicyandiamide et les cyanamides métalliques. Parmi les cyanamides métalliques sont préférés les cyanamides de sodium, de zinc et de cuivre et plus particulièrement le cyanamide de zinc ZnCN2. In order to further improve the quality of the gases produced and to guarantee good ignition and good combustion behavior of the compositions according to the invention, the latter contain, alongside the main oxidizing charge, reactive additives which comprise on the one hand a copper compound chosen from the group consisting of cupric oxide CuO and basic copper nitrate Cu (NO 3 ) 2 , 3Cu (OH) 2 and on the other hand a nitrogenous organic compound chosen from the group consisting of nitroguanidine, guanidinium nitrate, oxamide, dicyandiamide and metallic cyanamides. Among the metallic cyanamides, sodium, zinc and copper cyanamides are preferred, and more particularly zinc cyanamide ZnCN 2 .

Il est possible d'incorporer à la composition, à côté des dits additifs réactifs, des additifs supplémentaires. Pour les compositions destinées à être mises en forme par extrusion il est par exemple possible d'incorporer comme additif supplémentaire des microperles de silicone. Les constituants de la charge oxydante principale ainsi que les divers additifs utilisables dans le cadre de l'invention se présentent sous forme solide et seront broyés finement, en général à des granulométries comprises entre 10 et 50 µm, avant d'être utilisés pour la formulation et la mise en forme des compositions.It is possible to incorporate into the composition, side of said reactive additives, additives additional. For compositions intended to be shaped by extrusion it is for example possible to incorporate as an additional additive silicone microbeads. The constituents of the charge main oxidant as well as the various additives usable in the context of the invention are presented in solid form and will be finely ground, in general at particle sizes between 10 and 50 µm, before to be used for formulation and formatting compositions.

Les exemples qui suivent illustrent certaines possibilités de mise en oeuvre de l'invention sans limiter la portée.The following examples illustrate some possibilities of implementing the invention without limit the scope.

Exemples 1 à 31Examples 1 to 31

On a fabriqué et mis sous forme de pastilles de diamètre 7mm les compositions suivantes dont la charge oxydante est constituée par le mélange NH4ClO4+NaNO3. Le liant a été broyé à une granulométrie comprise entre 20 et 30 µm, le perchlorate d'ammonium à une granulométrie comprise entre 10 et 50 µm, le nitrate de sodium et les composés organiques azotés à une granulométrie voisine de 30 µm, et les composés du cuivre à une granulométrie de quelques µm.The following compositions were produced and put in the form of pellets with a diameter of 7 mm, the oxidizing charge of which is constituted by the mixture NH 4 ClO 4 + NaNO 3 . The binder was ground to a particle size between 20 and 30 μm, the ammonium perchlorate to a particle size between 10 and 50 μm , the sodium nitrate and the nitrogenous organic compounds to a particle size close to 30 μm, and the copper compounds with a particle size of a few µm.

Lorsque le perchlorate d'ammonium et le nitrate de sodium sont utilisés sous forme de particules coprécipitées, il n'est pas nécessaire de procéder à un broyage préalable, en effet ces particules ont une granulométrie comprise entre 10 et 50 µm, souvent voisine de 20µm. When ammonium perchlorate and sodium nitrate are used in the form of co-precipitated particles, it is not necessary to carry out prior grinding, in fact these particles have a particle size between 10 and 50 μm , often close to 20 µ m.

Le tableau n°1 qui suit résume les teneurs pondérales des différentes compositions en pourcents.The table n ° 1 which follows summarizes the contents by weight of the various percent compositions.

Les abréviations utilisées ont les significations suivantes :

PA/NS =
rapport pondéral perchlorate d'ammonium/nitrate de sodium,
NGu =
nitroguanidine,
NG =
nitrate de guanidinium,
Oxam =
oxamide,
NBCu =
nitrate basique de cuivre,
Rdt =
rendement gazeux (en moles pour 100g de composition).
Sil. =
silicone   CH = NH4ClO4+NaNO3
Epo. =
époxy   Ex = exemple
Ex. Liant CH PA/NS CuO .NBCu .NG. NGu. Oxam. Rdt. Sil. epo. 1 - 4 75 0,95 13 - - 8 - 2,3 2 - 6 75 0,95 - 11 8 - - 2,5 3 - 5 75 0,95 12 - - 8 - 2,4 4 - 6 75 0,95 11 - 8 - - 2,4 5 6 - 75 0,95 11 - 8 - - 2,4 6 - 6 75 0,95 10 - 9 - - 2,5 7 - 6 75 0,95 - 11 - 8 - 2,6 8 - 7 75 0,95 - 11 7 - - 2,55 9 - 6 70 0,95 16 - - 8 - 2,3 10 - 7 70 0,95 16 - 7 - - 2,3 11 - 6 75 0,95 11 - - 8 - 2,4 12 - 7 75 0,95 11 - 7 - - 2,4 13 6 - 75 0,95 11 - - 8 - 2,4 14 - 6 75 0,95 8 - 11 - - 2,55 15 - 7 75 0,95 9 - 9 - 2,5 16 - 7 75 0,95 11 - - 7 - 2,4 17 8 - 77 0,95 10 - 5 - - 2,4 18 - 8 75 0,95 - 9 8 - - 2,61 19 8 - 75 0,95 12 - - 5 2,3 20 - 8 75 0,95 9 - 8 - - 2,6 21 - 7 70 0,95 11 - 12 - - 2,5 22 8 - 70 0,95 14 - 8 - - 2,3 23 8 - 75 0,95 9 - 8 - - 2,5 24 - 6 70 0,95 11 - - 13 - 2,5 25 - 8 75 0,95 9 - - 8 - 2,5 26 - 7 70 0,95 8 - 15 - - 2,7 27 8 - 77 0,95 5 - 10 - 2,6 28 8 - 75 0,95 9 - - 8 2,5 29 - 6 73 0,95 6 - - 15 2,5 30 8 - 70 0,95 14 - - 8 2,3 31 - 8 75 0,95 9 - - - 8 2,5 The abbreviations used have the following meanings:
PA / NS =
ammonium perchlorate / sodium nitrate weight ratio,
NGu =
nitroguanidine,
NG =
guanidinium nitrate,
Oxam =
oxamide,
NBCu =
basic copper nitrate,
Yield =
gas yield (in moles per 100 g of composition).
Sil. =
silicone CH = NH 4 ClO 4 + NaNO 3
Epo. =
epoxy Ex = example
Ex. Binder CH PA / NS CuO .NBCu .NG. NGu. Oxam. Rdt. Sil. epo. 1 - 4 75 0.95 13 - - 8 - 2.3 2 - 6 75 0.95 - 11 8 - - 2.5 3 - 5 75 0.95 12 - - 8 - 2.4 4 - 6 75 0.95 11 - 8 - - 2.4 5 6 - 75 0.95 11 - 8 - - 2.4 6 - 6 75 0.95 10 - 9 - - 2.5 7 - 6 75 0.95 - 11 - 8 - 2.6 8 - 7 75 0.95 - 11 7 - - 2.55 9 - 6 70 0.95 16 - - 8 - 2.3 10 - 7 70 0.95 16 - 7 - - 2.3 11 - 6 75 0.95 11 - - 8 - 2.4 12 - 7 75 0.95 11 - 7 - - 2.4 13 6 - 75 0.95 11 - - 8 - 2.4 14 - 6 75 0.95 8 - 11 - - 2.55 15 - 7 75 0.95 9 - 9 - 2.5 16 - 7 75 0.95 11 - - 7 - 2.4 17 8 - 77 0.95 10 - 5 - - 2.4 18 - 8 75 0.95 - 9 8 - - 2.61 19 8 - 75 0.95 12 - - 5 2.3 20 - 8 75 0.95 9 - 8 - - 2.6 21 - 7 70 0.95 11 - 12 - - 2.5 22 8 - 70 0.95 14 - 8 - - 2.3 23 8 - 75 0.95 9 - 8 - - 2.5 24 - 6 70 0.95 11 - - 13 - 2.5 25 - 8 75 0.95 9 - - 8 - 2.5 26 - 7 70 0.95 8 - 15 - - 2.7 27 8 - 77 0.95 5 - 10 - 2.6 28 8 - 75 0.95 9 - - 8 2.5 29 - 6 73 0.95 6 - - 15 2.5 30 8 - 70 0.95 14 - - 8 2.3 31 - 8 75 0.95 9 - - - 8 2.5

L'évaluation théorique des performances de ces compositions dans un générateur de gaz pour coussin de 60 litres figure dans le tableau n°2 qui suite.
Les abréviations utilisées ont le significations suivantes :

TcK=
température de combustion en degrés Kelvin.
COppm =
teneur des gaz en monoxyde de carbone exprimée en ppm (ramenée à un volume de 2,5m3).
NOxppm =
teneur globale des gaz en oxydes d'azote exprimée en ppm (ramenée à un volume de 2,5m3).
rés. Tc =
teneur globale des gaz en résidus solides, exprimée en pourcents, à la température de combustion.
rés. 1000°K =
teneur globale des gaz à 1000K° en résidus solides, exprimées en pourcents. (1000°K correspondent approximativement à la température en sortie de générateur).
Exemple TcK. COppm. NOxppm. résTc. rés 1000K 1 1570 0 11 39 39 2 1636 0 12 32 33 3 1640 0 13 37 38 4 1650 0 13 35 37 5 1660 0 13 36 38 6 1686 0 14 34 36 7 1693 0 17 32 33 8 1703 0 15 32 33 9 1720 0 16 38 40 10 1730 0 16 38 40 11 1735 0 17 35 37 12 1745 0 17 35 37 13 1750 0 18 36 38 14 1754 0 17 32 34 15 1809 0 20 32 35 16 1815 0 21 34 37 17 1830 0 20 37 39 18 1858 0 21 29 32 19 1880 0 23 37 41 20 1890 0 23 32 34 21 1890 0 22 32 35 22 1910 0 24 37 41 23 1920 0 29 34 37 24 1925 0,1 26 31 35 25 1960 0,1 27 30 34 26 1965 0,2 26 28 32 27 1970 0,1 27 30 35 28 1990 0,2 29 33 37 29 1990 0,2 31 25 30 30 1990 0,2 26 36 41 31 2000 0,3 26 30 35 The theoretical evaluation of the performance of these compositions in a gas generator for a 60-liter cushion is given in table 2 below.
The abbreviations used have the following meanings:
TcK =
combustion temperature in degrees Kelvin.
COppm =
carbon monoxide content of the gases expressed in ppm (reduced to a volume of 2.5m 3 ).
NOxppm =
overall content of nitrogen oxide gases expressed in ppm (reduced to a volume of 2.5m 3 ).
res. Tc =
overall content of gases in solid residues, expressed in percent, at the combustion temperature.
res. 1000 ° K =
overall gas content at 1000K ° in solid residues, expressed in percent. (1000 ° K corresponds approximately to the temperature at the generator outlet).
Example TcK. COppm. NOxppm. RESTc. 1000K res 1 1570 0 11 39 39 2 1636 0 12 32 33 3 1640 0 13 37 38 4 1650 0 13 35 37 5 1660 0 13 36 38 6 1686 0 14 34 36 7 1693 0 17 32 33 8 1703 0 15 32 33 9 1720 0 16 38 40 10 1730 0 16 38 40 11 1735 0 17 35 37 12 1745 0 17 35 37 13 1750 0 18 36 38 14 1754 0 17 32 34 15 1809 0 20 32 35 16 1815 0 21 34 37 17 1830 0 20 37 39 18 1858 0 21 29 32 19 1880 0 23 37 41 20 1890 0 23 32 34 21 1890 0 22 32 35 22 1910 0 24 37 41 23 1920 0 29 34 37 24 1925 0.1 26 31 35 25 1960 0.1 27 30 34 26 1965 0.2 26 28 32 27 1970 0.1 27 30 35 28 1990 0.2 29 33 37 29 1990 0.2 31 25 30 30 1990 0.2 26 36 41 31 2000 0.3 26 30 35

Il ressort des tableaux 1 et 2 que les diverses compositions essayées satisfont aux objectifs de l'invention, les compositions 1 à 21 étant particulièrement intéressantes par leurs températures de combustion très modérées et du fait que pour ces compositions il y a une quasi-égalité entre les valeurs obtenues pour les résidus solides à la température de combustion et celles obtenues à 1000°K, ce qui signifie que pour ces compositions l'intégralité des résidus solides est formée dans la chambre de combustion, avant filtration.It appears from Tables 1 and 2 that the various compositions tested meet the objectives of the invention, compositions 1 to 21 being particularly interesting by their temperatures of very moderate combustion and the fact that for these compositions there is a near equality between the values obtained for solid residues at the temperature of combustion and those obtained at 1000 ° K, which means that for these compositions all the residues solids is formed in the combustion chamber, before filtration.

Exemples 32 à 39Examples 32 to 39

Le tableau n°3 qui suit présente d'autres compositions selon l'invention avec leur évaluation théorique. Les abréviations utilisées sont les mêmes que précédemment la nouvelle abréviation "DCDA" représentant le dicyandiamide. Exemple 32 33 34 35 36 37 38 39 Liant épo 7 6 6 8 5 5 5 5 NH4ClO4 + NaNO3
70
75
75
38
38
65 44
+
10 22
-
 PA/NS 1,42 1,42 1,42 1,42 1,42 2,1 KClO4 - - - 37 37 - - 37 Li2CO3 6 - - - - 10 21 16 CuO 16 8 10 9 9 11 11 11 NG - 11 5 8 6 - - - DCDA - - - - 5 9 9 9 Oxam - - 4 - - - - Tck 1870 1896 1898 1978 1990 2002 1940 1960 Rdt 2,5 2,7 2,6 2,2 2,2 2,6 2,34 1,93 COppm 0 0 0 0,2 0,2 0,45 0,6 0,4 NOxppm 21 23 22 26 29 20 11 18 rés.Tc 32 26 27 31 31 25 30 37 rés.1000K 35 29 31 39 39 34 36 45 Table 3 which follows presents other compositions according to the invention with their theoretical evaluation. The abbreviations used are the same as previously the new abbreviation "DCDA" representing dicyandiamide. Example 32 33 34 35 36 37 38 39 Epo binder 7 6 6 8 5 5 5 5 NH4ClO4 + NaNO3
70
75
75
38
38
65 44
+
10 22
-
PA / NS 1.42 1.42 1.42 1.42 1.42 2.1 KClO 4 - - - 37 37 - - 37 Li 2 CO 3 6 - - - - 10 21 16 CuO 16 8 10 9 9 11 11 11 NG - 11 5 8 6 - - - DCDA - - - - 5 9 9 9 Oxam - - 4 - - - - Tck 1870 1896 1898 1978 1990 2002 1940 1960 Rdt 2.5 2.7 2.6 2.2 2.2 2.6 2.34 1.93 COppm 0 0 0 0.2 0.2 0.45 0.6 0.4 NOxppm 21 23 22 26 29 20 11 18 res. 32 26 27 31 31 25 30 37 1000K res 35 29 31 39 39 34 36 45

Résultats complémentairesAdditional results

Les pastilles des exemples 11, 25, 37, 38 et 39 ont servi à remplir des générateurs de gaz pour coussin de 60 litres. Ces générateurs ont été placés dans des containers de 60 litres et allumés. On a mesuré la température de combustion réelle des chargements ainsi que les teneurs en monoxyde de carbone et en oxydes d'azote des gaz à l'intérieur des dits containers à l'aide de tubes "DRAEGER"®.The tablets of Examples 11, 25, 37, 38 and 39 have used to fill gas generators for cushion 60 liters. These generators were placed in 60 liter containers and lit. We measured the actual combustion temperature of the loads as well than the carbon monoxide and oxide contents nitrogen from the gases inside the said containers using "DRAEGER" ® tubes.

Les résultats ont été les suivants :

  • chargement constitué à partir des pastilles de l'exemple 11 :
  • température de combustion : 1735°K
  • teneur en oxydes d'azote : 1500-2500ppm
  • teneur en monoxyde de carbone : 400 ppm.
  • chargement constitué à partir des pastilles de l'exemple 25 :
  • température de combustion : 1960°K
  • teneur en oxydes d'azote : 1500-2000 ppm
  • teneur en monoxyde de carbone : 1000 ppm.
  • chargement constitué à partir des pastilles de l'exemple 37 :
  • température de combustion : 2002°K
  • teneur en oxydes d'azote : 1500 ppm
  • teneur en monoxyde de carbone : 1500 ppm.
  • chargement constitué à partir des pastilles de l'exemple 38 :
  • température de combustion : 1940°K
  • teneur en oxydes d'azote : 700 ppm
  • teneur en monoxyde de carbone : >3000 ppm.
  • chargement constitué à partir des pastilles de l'exemple 39 :
  • température de combustion : 1960°K
  • teneur en oxydes d'azote : 900 ppm
  • teneur en monoxyde de carbone : 1200 ppm.
The results were as follows:
  • loading constituted from the pellets of Example 11:
  • combustion temperature: 1735 ° K
  • nitrogen oxides content: 1500-2500ppm
  • carbon monoxide content: 400 ppm.
  • loading constituted from the pellets of Example 25:
  • combustion temperature: 1960 ° K
  • nitrogen oxide content: 1500-2000 ppm
  • carbon monoxide content: 1000 ppm.
  • loading constituted from the pellets of Example 37:
  • combustion temperature: 2002 ° K
  • nitrogen oxide content: 1500 ppm
  • carbon monoxide content: 1500 ppm.
  • loading constituted from the pellets of Example 38:
  • combustion temperature: 1940 ° K
  • nitrogen oxide content: 700 ppm
  • carbon monoxide content:> 3000 ppm.
  • loading constituted from the pellets of Example 39:
  • combustion temperature: 1960 ° K
  • nitrogen oxide content: 900 ppm
  • carbon monoxide content: 1200 ppm.

Claims (12)

  1. Pyrotechnic composition generating gas comprising in particular a crosslinked reducing binder, additives and a main oxidizing charge comprising at least one mixture of ammonium perchlorate associated with a chlorine captor selected from the group consisting of sodium nitrate, lithium carbonate and potassium carbonate, the weight ratio of ammonium perchlorate/chlorine captor being less than 5.0, characterized in that the concentration by weight of the said binder represents at most 10 % of the total weight of the composition, in that the composition by weight of the said main oxidizing charge lies between 50 % and 75 % of the total weight of the composition, and in that the said additives contain at least one copper compound selected from the group consisting of cupric oxide CuO and basic copper nitrate Cu(NO3)2, 3Cu(OH)2, and contain at least one nitrogen-containing organic compound selected from the group consisting of nitroguanidine, guanidinium nitrate, oxamide, dicyandiamide and metallic cyanamides.
  2. Composition according to claim 1, characterized in that the said binder is selected from the group consisting of crosslinkable reducing binders based on silicone resin, by crosslinkable reducing binders based on epoxy resin, and by polyacrylic rubbers with reactive end groups.
  3. Composition according to claim 2, characterized in that the concentration by weight of the said binder lies between 6 % and 10 % of the total weight of the composition.
  4. Composition according to claim 3, characterized in that the concentration by weight of the said main oxidizing charge lies between 70 % and 75 % of the total weight of the composition.
  5. Composition according to claim 4, characterized in that the weight ratio of ammonium perchlorate/chlorine captor is less than 4.0.
  6. Composition according to claim 1, characterized in that the weight ratio of ammonium perchlorate/chlorine captor is less than 1.5.
  7. Composition according to claim 1, characterized in that the said main oxidizing charge comprises coprecipitated ammonium perchlorate and sodium nitrate.
  8. Composition according to claim 7, characterized in that the particles of coprecipitated ammonium perchlorate and sodium nitrate have a particle size of between 10 µm and 50 µm.
  9. Composition according to claim 6, characterized in that the weight ratio of ammonium perchlorate/chlorine captor is close to 0.95.
  10. Composition according to claim 1, characterized in that the said metallic cyanamides consist of sodium, zinc and copper cyanamides.
  11. Composition according to claim 10, characterized in that the said metallic cyanamide is zinc cyanamide ZnCN2.
  12. Composition according to any one of claims 1 to 11, characterized in that the said main oxidizing charge also contains potassium perchlorate.
EP98959947A 1997-12-12 1998-12-10 Pyrotechnic mixtures generating non-toxic gases based on ammonium perchlorate Expired - Lifetime EP1037864B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9715745 1997-12-12
FR9715745A FR2772370B1 (en) 1997-12-12 1997-12-12 PYROTECHNIC COMPOSITIONS GENERATING NON-TOXIC GASES BASED ON AMMONIUM PERCHLORATE
PCT/FR1998/002684 WO1999031029A1 (en) 1997-12-12 1998-12-10 Pyrotechnic mixtures generating non-toxic gases based on ammonium perchlorate

Publications (2)

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EP1037864A1 EP1037864A1 (en) 2000-09-27
EP1037864B1 true EP1037864B1 (en) 2001-10-17

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EP98959947A Expired - Lifetime EP1037864B1 (en) 1997-12-12 1998-12-10 Pyrotechnic mixtures generating non-toxic gases based on ammonium perchlorate

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US (1) US6533878B1 (en)
EP (1) EP1037864B1 (en)
JP (1) JP3814754B2 (en)
KR (1) KR100375647B1 (en)
AT (1) ATE207049T1 (en)
AU (1) AU747904B2 (en)
DE (1) DE69802112T2 (en)
FR (1) FR2772370B1 (en)
WO (1) WO1999031029A1 (en)

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Also Published As

Publication number Publication date
FR2772370A1 (en) 1999-06-18
JP2002508297A (en) 2002-03-19
AU1566899A (en) 1999-07-05
WO1999031029A1 (en) 1999-06-24
KR20010032845A (en) 2001-04-25
DE69802112D1 (en) 2001-11-22
US6533878B1 (en) 2003-03-18
EP1037864A1 (en) 2000-09-27
DE69802112T2 (en) 2002-06-27
AU747904B2 (en) 2002-05-30
FR2772370B1 (en) 2000-01-07
ATE207049T1 (en) 2001-11-15
KR100375647B1 (en) 2003-03-15
JP3814754B2 (en) 2006-08-30

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