EP1037864B1 - Compositions pyrotechniques generatrices de gaz non toxiques a base de perchlorate d'ammonium - Google Patents
Compositions pyrotechniques generatrices de gaz non toxiques a base de perchlorate d'ammonium Download PDFInfo
- Publication number
- 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
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- nitrate
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Classifications
-
- 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.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Toxicology (AREA)
- Air Bags (AREA)
- Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
Description
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.
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.
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.
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 interne
- 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 |
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 |
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 |
- 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.
Claims (12)
- 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 caractérisée 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 et les cyanamides métalliques.
- Composition selon la revendication 1 caractérisée en ce que le dit liant est choisi dans le groupe constitué par les liants réducteurs réticulables à base de résine silicone, par les liants réducteurs réticulables à base de résine époxy et par les caoutchoucs polyacryliques à terminaisons réactives.
- Composition selon la revendication 2 caractérisée en ce que la teneur pondérale du dit liant est comprise entre 6% et 10% du poids total de la composition.
- Composition selon la revendication 3 caractérisée en ce que la teneur pondérale de la dite charge oxydante principale est comprise entre 70% et 75% du poids total de la composition.
- Composition selon la revendication 4 caractérisée en ce que le rapport pondéral perchlorate d'ammonium/capteur de chlore est inférieur à 4,0.
- Composition selon la revendication 1 caractérisé en ce que le rapport pondéral perchlorate d'ammonium/capteur de chlore est inférieur à 1,5.
- Composition selon la revendication 1 caractérisée en ce que la dite charge oxydante principale comprend du perchlorate d'ammonium et du nitrate de sodium coprécipités.
- Composition selon la revendication 7 caractérisé en ce que les particules de perchlorate d'ammonium et de nitrate de sodium coprécipités ont une granulométrie comprise entre 10 µm et 50 µm.
- Composition selon la revendication 6 caractérisée en ce que le rapport pondéral perchlorate d'ammonium/capteur de chlore est voisin de 0,95.
- Composition selon la revendication 1 caractérisée en ce que les dites cyanamides métalliques sont constitués par les cyanamides de sodium, de zinc et de cuivre.
- Composition selon la revendication 10 caractérisé en ce que le dit cyanamide métallique est le cyanamide de zinc ZnCN2.
- Composition selon l'une quelconque des revendications 1 à 11 caractérisée en ce que la dite charge oxydante principale contient également du perchlorate de potassium.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9715745A FR2772370B1 (fr) | 1997-12-12 | 1997-12-12 | Compositions pyrotechniques generatrices de gaz non toxiques a base de perchlorate d'ammonium |
FR9715745 | 1997-12-12 | ||
PCT/FR1998/002684 WO1999031029A1 (fr) | 1997-12-12 | 1998-12-10 | Compositions pyrotechniques generatrices de gaz non toxiques a base de perchlorate d'ammonium |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1037864A1 EP1037864A1 (fr) | 2000-09-27 |
EP1037864B1 true EP1037864B1 (fr) | 2001-10-17 |
Family
ID=9514511
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98959947A Expired - Lifetime EP1037864B1 (fr) | 1997-12-12 | 1998-12-10 | Compositions pyrotechniques generatrices de gaz non toxiques a base de perchlorate d'ammonium |
Country Status (9)
Country | Link |
---|---|
US (1) | US6533878B1 (fr) |
EP (1) | EP1037864B1 (fr) |
JP (1) | JP3814754B2 (fr) |
KR (1) | KR100375647B1 (fr) |
AT (1) | ATE207049T1 (fr) |
AU (1) | AU747904B2 (fr) |
DE (1) | DE69802112T2 (fr) |
FR (1) | FR2772370B1 (fr) |
WO (1) | WO1999031029A1 (fr) |
Families Citing this family (28)
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JP4318777B2 (ja) * | 1998-02-25 | 2009-08-26 | 日本化薬株式会社 | ガス発生剤組成物 |
DE69942892D1 (de) * | 1998-02-25 | 2010-12-09 | Nippon Kayaku Kk | Gaserzeugende zusammensetzung |
DE29821544U1 (de) * | 1998-12-02 | 1999-02-18 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azidfreie, gaserzeugende Zusammensetzung |
US7094296B1 (en) * | 1999-09-16 | 2006-08-22 | Automotive Systems Laboratory, Inc. | Gas generants containing silicone fuels |
JP4800469B2 (ja) * | 1999-10-08 | 2011-10-26 | ダイセル化学工業株式会社 | ガス発生剤組成物 |
CN100465097C (zh) * | 1999-09-27 | 2009-03-04 | 大赛璐化学工业株式会社 | 碱式金属硝酸盐、其制造方法和产气组合物 |
JP4493790B2 (ja) * | 1999-10-08 | 2010-06-30 | ダイセル化学工業株式会社 | 自動発火機能を有するガス発生器 |
JP2001315611A (ja) * | 2000-02-28 | 2001-11-13 | Daicel Chem Ind Ltd | エアバッグ用ガス発生器のクーラント/フィルター |
DE10009819A1 (de) * | 2000-03-01 | 2001-09-06 | Trw Airbag Sys Gmbh & Co Kg | Verfahren zur Herstellung von Treibstoff-Formlingen |
DE20010154U1 (de) | 2000-06-07 | 2000-09-07 | Trw Airbag Sys Gmbh & Co Kg | Anzündmischung zur Verwendung in Gasgeneratoren |
EP1186786B1 (fr) * | 2000-08-04 | 2005-06-08 | Automotive Systems Laboratory Inc. | Actionneur pyrotechnique |
FR2818636B1 (fr) * | 2000-12-22 | 2003-02-28 | Poudres & Explosifs Ste Nale | Compositions pyrotechniques generatrices de gaz a liant hydrocarbone et procede de fabrication en continu |
US6589375B2 (en) * | 2001-03-02 | 2003-07-08 | Talley Defense Systems, Inc. | Low solids gas generant having a low flame temperature |
FR2831123B1 (fr) * | 2001-10-19 | 2004-07-30 | Livbag Snc | Dispositif generateur de gaz hybride utilise en securite automobile pour gonfler un coussin de protection lateral |
JP3972628B2 (ja) * | 2001-10-23 | 2007-09-05 | 日本油脂株式会社 | ガス発生剤組成物及びガス発生器 |
US6964716B2 (en) | 2002-09-12 | 2005-11-15 | Daicel Chemical Industries, Ltd. | Gas generating composition |
CN100405000C (zh) * | 2003-05-20 | 2008-07-23 | 余本友 | 一种无烟焰火 |
FR2857359B1 (fr) * | 2003-07-10 | 2006-12-01 | Snpe Materiaux Energetiques | Composition pyrotechnique generatrice de gaz destinee a la securite automobile et brulant a des temperatures de combustion inferieures a 2200 k |
US8101033B2 (en) | 2004-07-26 | 2012-01-24 | Autoliv Asp, Inc. | Alkali metal perchlorate-containing gas generants |
US20050016646A1 (en) | 2003-07-25 | 2005-01-27 | Barnes Michael W. | Chlorine-containing gas generant compositions including a copper-containing chlorine scavenger |
DE102004001625B4 (de) * | 2004-01-12 | 2014-02-13 | Trw Airbag Systems Gmbh | Verfahren zum Aufblasen eines Gassacks und Gassackmodul zur Verwendung in dem Verfahren |
CN1331827C (zh) * | 2004-12-16 | 2007-08-15 | 中国航天科技集团公司第四研究院第四十二研究所 | 非叠氮气体发生剂及制造工艺 |
US8133335B2 (en) * | 2006-02-09 | 2012-03-13 | Mathieu Racette | Black powder substitutes for small caliber firearms |
FR2915746B1 (fr) * | 2007-05-02 | 2009-08-21 | Snpe Materiaux Energetiques Sa | Compose pyrotechnique generateur de gaz; procede d'obtention |
FR3007659B1 (fr) | 2013-06-28 | 2017-03-24 | Herakles | Procede de delivrance d'un liquide pressurise par les gaz de combustion d'au moins un chargement pyrotechnique |
FR3037812B1 (fr) | 2015-06-29 | 2017-08-04 | Herakles | Extincteur d'incendie |
FR3077989B1 (fr) | 2018-02-20 | 2021-11-19 | Arianegroup Sas | Extincteur d'incendie |
CN109160868A (zh) * | 2018-10-31 | 2019-01-08 | 湖北航天化学技术研究所 | 一种气囊用气体发生剂 |
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US4165247A (en) * | 1966-02-09 | 1979-08-21 | The United States Of America As Represented By The Secretary Of The Navy | Polyurethane solid propellant binder |
US3723205A (en) | 1971-05-07 | 1973-03-27 | Susquehanna Corp | Gas generating composition with polyvinyl chloride binder |
US3814694A (en) | 1971-08-09 | 1974-06-04 | Aerojet General Co | Non-toxic gas generation |
FR2190776B1 (fr) | 1972-07-05 | 1976-10-29 | Poudres & Explosifs Ste Nale | |
FR2213254B1 (fr) | 1972-10-17 | 1977-08-05 | Poudres & Explosifs Ste Nale | |
DE2820969C1 (de) * | 1978-05-12 | 1991-12-05 | Bayern Chemie Gmbh Flugchemie | Composit-Festtreibstoff mit stabilem Abbrand |
US4909549A (en) | 1988-12-02 | 1990-03-20 | Automotive Systems Laboratory, Inc. | Composition and process for inflating a safety crash bag |
US5783769A (en) * | 1989-03-17 | 1998-07-21 | Hercules Incorporated | Solid propellant with non-crystalline polyether/energetic plasticizer binder |
CZ291570B6 (cs) * | 1991-06-21 | 2003-04-16 | Dynamit Nobel Aktiengesellschaft | Hnací prostředek pro plynové generátory a způsob jeho výroby a jeho použití |
US5486248A (en) * | 1994-05-31 | 1996-01-23 | Morton International, Inc. | Extrudable gas generant for hybrid air bag inflation system |
DE4442037C1 (de) | 1994-11-25 | 1995-12-21 | Fraunhofer Ges Forschung | Gaserzeugende Mischung |
FR2728562B1 (fr) | 1994-12-22 | 1997-01-24 | Poudres & Explosifs Ste Nale | Procede de fabrication en continu de chargements pyrotechniques a liant silicone et compositions susceptibles d'etre mises en oeuvre par ce procede |
US5780768A (en) * | 1995-03-10 | 1998-07-14 | Talley Defense Systems, Inc. | Gas generating compositions |
US5854442A (en) * | 1995-03-31 | 1998-12-29 | Atlantic Research Corporation | Gas generator compositions |
US5608183A (en) * | 1996-03-15 | 1997-03-04 | Morton International, Inc. | Gas generant compositions containing amine nitrates plus basic copper (II) nitrate and/or cobalt(III) triammine trinitrate |
US6039820A (en) * | 1997-07-24 | 2000-03-21 | Cordant Technologies Inc. | Metal complexes for use as gas generants |
AU6908596A (en) | 1996-08-30 | 1998-03-19 | Talley Defense Systems, Inc. | Gas generating compositions |
US5841065A (en) * | 1997-04-15 | 1998-11-24 | Autoliv Asp, Inc. | Gas generants containing zeolites |
US5861571A (en) * | 1997-04-18 | 1999-01-19 | Atlantic Research Corporation | Gas-generative composition consisting essentially of ammonium perchlorate plus a chlorine scavenger and an organic fuel |
US5882036A (en) * | 1997-09-10 | 1999-03-16 | Autoliv Asp, Inc. | Hybrid inflator with reduced solid emissions |
-
1997
- 1997-12-12 FR FR9715745A patent/FR2772370B1/fr not_active Expired - Fee Related
-
1998
- 1998-12-10 AT AT98959947T patent/ATE207049T1/de not_active IP Right Cessation
- 1998-12-10 WO PCT/FR1998/002684 patent/WO1999031029A1/fr active IP Right Grant
- 1998-12-10 EP EP98959947A patent/EP1037864B1/fr not_active Expired - Lifetime
- 1998-12-10 JP JP2000538962A patent/JP3814754B2/ja not_active Expired - Fee Related
- 1998-12-10 AU AU15668/99A patent/AU747904B2/en not_active Ceased
- 1998-12-10 KR KR10-2000-7006172A patent/KR100375647B1/ko not_active IP Right Cessation
- 1998-12-10 DE DE69802112T patent/DE69802112T2/de not_active Expired - Lifetime
- 1998-12-10 US US09/554,042 patent/US6533878B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
US6533878B1 (en) | 2003-03-18 |
KR100375647B1 (ko) | 2003-03-15 |
DE69802112D1 (de) | 2001-11-22 |
AU1566899A (en) | 1999-07-05 |
WO1999031029A1 (fr) | 1999-06-24 |
DE69802112T2 (de) | 2002-06-27 |
JP2002508297A (ja) | 2002-03-19 |
EP1037864A1 (fr) | 2000-09-27 |
KR20010032845A (ko) | 2001-04-25 |
JP3814754B2 (ja) | 2006-08-30 |
FR2772370B1 (fr) | 2000-01-07 |
FR2772370A1 (fr) | 1999-06-18 |
ATE207049T1 (de) | 2001-11-15 |
AU747904B2 (en) | 2002-05-30 |
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