EP0924177A1 - Pyrotechnic composition for generating of a clean gas with a low nitrogen oxide content and pellets thereof - Google Patents
Pyrotechnic composition for generating of a clean gas with a low nitrogen oxide content and pellets thereof Download PDFInfo
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- EP0924177A1 EP0924177A1 EP98403120A EP98403120A EP0924177A1 EP 0924177 A1 EP0924177 A1 EP 0924177A1 EP 98403120 A EP98403120 A EP 98403120A EP 98403120 A EP98403120 A EP 98403120A EP 0924177 A1 EP0924177 A1 EP 0924177A1
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- 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
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- the present invention relates to the field of pyrotechnic production of gases intended for open systems. More specifically, the invention relates new pyrotechnic compositions generating clean gases, rich in nitrogen but low in content nitrogen oxides and intended to operate fire extinguishers, for inflating structures protective covers or protective cushions for occupants of a motor vehicle.
- compositions based on sodium azide like, for example, those described in the patent US-A-4,929,290.
- the compositions based sodium azide have many disadvantages.
- azide-based compositions are very sensitive to humidity and do not keep well over time.
- sodium azide which can lead to explosives primary, by combination with metals to form for example lead azide, these compositions must be subject to precautions when manufacturing and disposal of waste.
- compositions as a propellant for rocket and missile engines are known and described in numerous patents such as, for example, the US-A-3,725,516 which describes propellants for rocket engines constituted by a fluorinated binder, a salt oxidant such as ammonium nitrate or perchlorate potassium and a metal in powder form.
- propellants are not usable in the applications covered by this invention for at least two reasons.
- compositions based on ammonium nitrate and / or potassium perchlorate in combination with tetrazole derivatives and compounds metallic like boron oxide, vanadium oxide or silicates Such compositions which are, for example, described in US-A-5,035,757 give many non-toxic nitrogen-rich gases but still produce many solid residues which make it necessary to have a important filtration.
- compositions expressly excluding the presence of metallic compounds and comprising essentially an oxygenated thermoplastic binder, a energy plasticizer such as polyazide glycidyl and a compound oxidizing charge for at least 85% of its weight by ammonium nitrate.
- the composition contains at least 8% by weight of binder not to mention the energy plasticizer and the skilled person is, at least for some applications, again faced with the problem of gas toxicity.
- compositions whose oxidizing charge is based on ammonium nitrate and which contain less than 6% by weight of an oxygenated organic binder and between 0.5% and 5% by weight of a light metal chosen from the group consisting of boron and aluminum.
- These compositions which are advantageously put in the form of pellets by compression, have a burning rate satisfactory, they do not produce by combustion of heavy solid residues and the gases generated have a content in extremely low carbon monoxide.
- the gases generated by these compositions have a content of nitrogen oxides still a little too high when they're intended to operate in open systems on outside.
- composition contains as nitrogen compound oxidant of ammonium perchlorate the latter will advantageously combined with sodium nitrate which will function, during combustion, as a sensor chlorine.
- the nitrate weight ratio of sodium / ammonium perchlorate will advantageously close to 0.95.
- compositions according to the invention will contain advantageously cupric oxide CuO, the content of which by weight relative to the total weight of the composition could be up to 10%.
- compositions according to the invention may also advantageously contain up to 5% by weight of lithium carbonate and up to 1% by weight of silica SiO 2 . If one wants compositions having a good combustion rate and producing gases very poor in nitrogen oxides, it will be ensured that these compositions contain cupric oxide as indicated above and that the said nitrogenous compound reagent of either nitroguanidine and / or guanidinium nitrate excluding oxamide.
- Such compositions are very suitable for constituting pyrotechnic charges intended to inflate protective cushions for occupants of a motor vehicle.
- the weight content y of said reactive nitrogen compound will preferably be between 5% and 10% of the total weight of the composition and more preferably close to 6%.
- compositions will be put in the form of tablets or tablet dragees, the oxygenated binder crosslinkable being preferably chosen from polymers or copolymers with epoxy units or units silicone. After tableting the pellets obtained are cooked for a few hours at a similar temperature 100 ° C to cause crosslinking of the binder.
- composition pellets are then intended to constitute bulk loads of pyrotechnic gas generators for systems open to the outside like fire extinguishers pyrotechnics, inflation devices external structures or protective cushions for occupants of a motor vehicle.
- compositions according to the invention are therefore basically composite pyrotechnic compositions based on ammonium nitrate and containing a binder and a light metal of the type described in French patent application 96.08050.
- the binder is a crosslinkable oxygenated binder preferably chosen from binders based on epoxy resin or silicone resin based. Content by weight of the said binder relative to the total weight of the composition will be between 1% and 6%.
- the main oxidant of the compositions according to the invention is ammonium nitrate the content of which by weight relative to the total weight of the composition can be understood according to a first characteristic of the invention between 29% and 93.5%, but will preferably between 60% and 75%.
- the ammonium nitrate will be nitrate of ammonium stabilized, for example with nitrate of potassium and amaranth as described in the application French patent 2,743,797. In this case, we will use advantageously a stabilized mixture containing 96.5% in weight of ammonium nitrate, 3% by weight of nitrate of potassium and 0.5% by weight of amaranth.
- the light metal is chosen exclusively from the boron and aluminum and its weight content compared the total weight of the composition is between 0.5% and 5%.
- the compositions according to the invention may also contain other oxidants. They can thus contain perchlorate of potassium, the weight content of the latter relative the total weight of the composition which may be included between 0% and 30%. This weight content will often between 10% and 20%. They can also contain an oxidizing nitrogen compound selected from the group consisting of ammonium perchlorate, nitrate of triaminoguanidine, hexogen, octogen and hexanitrohexaazaisowurtzitane. Weight content x of this oxidizing nitrogenous compound relative to the total weight of the composition satisfies the relation 0% ⁇ x ⁇ 15%.
- ammonium perchlorate When ammonium perchlorate is used as oxidizing nitrogen compound, it will advantageously be combination with sodium nitrate so that avoid the formation of hydrochloric acid in the gases combustion. In this case the nitrate weight ratio sodium / ammonium perchlorate will advantageously close to 0.95.
- the pyrotechnic compositions imperatively contain a reactive organic nitrogen compound chosen from the group consisting of nitroguanidine, guanidinium nitrate and oxamide.
- a reactive organic nitrogen compound chosen from the group consisting of nitroguanidine, guanidinium nitrate and oxamide.
- compositions according to the invention can also contain various additives such as, for example, cupric oxide CuO, lithium carbonate Li 2 CO 3 or silica SiO 2 .
- additives have various functions, the silica which will generally be used at contents less than or equal to 1% by weight has an anti-caking effect on the ammonium nitrate during formulation and shaping of the composition before crosslinking of the binder.
- the lithium carbonate which will generally be used at contents less than or equal to 5% by weight makes it possible to lower the combustion temperature of the compositions according to the invention while the cupric oxide which will generally be used at lower weight contents or equal to 10%, most often close to 6%, makes it possible to improve the ignition of the compositions according to the invention and to increase their combustion rates.
- Vehicle safety compositions will therefore preferably contain cupric oxide. Gases intended to inflate protective cushions for occupants of a motor vehicle must not only be very poor in nitrogen oxides but must also be very low in monoxide carbon CO. To meet this last requirement we avoid the use of oxamide as a nitrogen component reactive in safety compositions automotive and we will limit our, for these compositions, to the use of nitroguanidine or guanidinium nitrate as reactive nitrogen compound.
- the weight content of reactive nitrogen compound will, for these compositions, between 5% and 10% compared to the total weight of the composition, and more particularly close to 6%.
- compositions according to the invention are used form by tableting after a mixing phase performed in a mixer.
- the oxygenated binder is then added in the state liquid, not completely polymerized.
- a thermosetting binder it will be liquid resin mixed with its hardener.
- the hardener will be advantageously a polyamine which is not very reactive so as to have a "pot life" for the binder of about 24 hours.
- compositions according to the invention being to contain only very little binder compared to usual compositions for propellants or low powders "LOVA" type vulnerability, a difficulty not negligible formulation of compositions according to the invention consists in successfully permeating the whole solid constituents, and in particular nitrate ammonium, with this small amount of liquid binder.
- the liquid binder will advantageously be introduced into the mixer in diluted form in a solvent very volatile and inert towards constituents of the composition.
- a polyepoxy binder advantageously use trichloroethane as a diluent.
- the mixer is then started and left on turn, bowl covered, for about an hour. In these conditions we can permeate all of the solid constituents by the binder and all of the diluent was removed by evaporation during the mixing operation.
- composition which appears at this stage under the appearance of a slightly wet powder is brought to the desired shape by compression. In general it is put in the form of pellets.
- the polymerization of the binder takes place at a temperature close to 100 ° C and after 7 hours, in the case of a polyepoxy binder, the loads pyrotechnics obtained show good performance mechanical allowing their use in a generator gas pyrotechnics.
- compositions according to the invention contain a low level of binder which is not sufficient for fill all the gaps between the nitrate grains ammonium. Therefore putting into the form of pellets by compression leads to objects having a natural porosity corresponding to an increase in the area available for combustion, which is very favorable in terms of the rate of combustion of the composition.
- ammonium nitrate stabilized as described above promotes the conservation over time of the material's properties gas generator.
- Example 1 Example 2
- Example 3 Example 4
- Example 6 epoxy binder 6 6 6 6 6 6 6 6 6 NH 4 NO 3 stabilized 71 62 71 71 62 62 boron 3 1 1 1 1 1 1 KClO 4 20 10 10 - 10 12 NH 4 CLO 4 + NaNO 3 - - - 10 - - CuO - 6 6 6 6 6 6 Nitroguanidine - 15 6 6 - - Oxamide - - - - - 15 13
- Example 1 relates to a composition such that described in French patent application 96.08050 and is given for comparison.
- Tables 1 and 2 shows that all the compositions according to the invention (example 2 to 6) reduce the oxide content of the gases nitrogen compared to the reference (example 1), the most dramatic results being achieved with oxamide (examples 5 and 6). Nevertheless the compositions with oxamide provide gases too rich in carbon monoxide for automotive safety. Those are compositions rich in ammonium nitrate and using nitroguanidine (examples 3 and 4) which provide the most attractive gases for the automotive safety.
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Abstract
Description
La présente invention se rapporte au domaine de la production par voie pyrotechnique de gaz destinés à des systèmes ouverts. Plus précisément l'invention concerne de nouvelles compositions pyrotechniques génératrices de gaz propres, riches en azote mais à faible teneur en oxydes d'azote et destinés à faire fonctionner des extincteurs pour incendie, à gonfler des structures externes de protection ou des coussins de protection pour occupants d'un véhicule automobile.The present invention relates to the field of pyrotechnic production of gases intended for open systems. More specifically, the invention relates new pyrotechnic compositions generating clean gases, rich in nitrogen but low in content nitrogen oxides and intended to operate fire extinguishers, for inflating structures protective covers or protective cushions for occupants of a motor vehicle.
Pour produire par voie pyrotechnique des gaz riches en azote on s'intéresse depuis longtemps aux compositions pyrotechniques à base d'azoture de sodium, comme, par exemple, celles décrite dans le brevet US-A-4,929,290. Toutefois les compositions à base d'azoture de sodium présentent de nombreux inconvénients. Tout d'abord, par combustion, ces compositions génèrent de nombreuses poussières solides. Il est donc nécessaire, lorsque l'on utilise ce type de compositions, d'équiper le générateur de gaz d'un dispositif sophistiqué de filtration ce qui augmente le poids et le coût du générateur. Par ailleurs les compositions à base d'azoture sont très sensibles à l'humidité et se conservent mal dans le temps. Enfin, l'azoture de sodium pouvant conduire à des explosifs primaires, par combinaison avec des métaux pour former par exemple de l'azoture de plomb, ces compositions doivent faire l'objet de précautions lors de leur fabrication et lors de l'élimination des déchets.To produce rich gases by pyrotechnics in nitrogen we have long been interested in pyrotechnic compositions based on sodium azide, like, for example, those described in the patent US-A-4,929,290. However the compositions based sodium azide have many disadvantages. First, by combustion, these compositions generate a lot of solid dust. It is therefore necessary, when using this type of compositions, to equip the gas generator with a sophisticated filtration device which increases the weight and cost of the generator. In addition, azide-based compositions are very sensitive to humidity and do not keep well over time. Finally, sodium azide which can lead to explosives primary, by combination with metals to form for example lead azide, these compositions must be subject to precautions when manufacturing and disposal of waste.
Pour toutes ces raisons l'homme de métier a cherché à s'affranchir de l'azoture de sodium et s'est orienté vers des compositions solides générant de l'azote et constituées par un liant et une charge oxydante, compositions qui sont très stables dans le temps. For all these reasons the skilled person sought to get rid of sodium azide and oriented towards solid compositions generating nitrogen and consisting of a binder and an oxidizing charge, compositions which are very stable over time.
L'emploi de ce type de compositions comme propergol pour moteurs de fusées et de missiles est connu et décrit dans de nombreux brevets comme, par exemple, le brevet US-A-3,725,516 qui décrit des propergols pour moteurs de fusée constitués par un liant fluoré, un sel oxydant comme le nitrate d'ammonium ou le perchlorate de potassium et un métal sous forme pulvérulente.The use of this type of composition as a propellant for rocket and missile engines is known and described in numerous patents such as, for example, the US-A-3,725,516 which describes propellants for rocket engines constituted by a fluorinated binder, a salt oxidant such as ammonium nitrate or perchlorate potassium and a metal in powder form.
De tels propergols ne sont cependant pas utilisables dans les applications visées par la présente invention pour au moins deux raisons. D'une part ils contiennent un taux de liant très élevé, souvent compris entre 10 et 35%, et de ce fait produisent par combustion de grandes quantités de gaz très toxiques et d'autre part il font appel à des composés métalliques qui génèrent de grandes quantités de résidus solides.However, such propellants are not usable in the applications covered by this invention for at least two reasons. On the one hand they contain a very high level of binder, often understood between 10 and 35%, and therefore produce by combustion large quantities of very toxic gases and other apart they use metallic compounds which generate large amounts of solid residue.
Pour tenter de remédier à ces difficultés, l'homme de métier a alors proposé des compositions à base de nitrate d'ammonium et/ou de perchlorate de potassium en association avec des dérivés du tétrazole et de composés métalliques comme l'oxyde de bore, l'oxyde de vanadium ou des silicates. De telles compositions qui sont, par exemple, décrites dans le brevet US-A-5,035,757 donnent bien des gaz non toxiques riches en azote mais produisent toujours de nombreux résidus solides qui rendent nécessaire la présence d'un système de filtration important.To try to remedy these difficulties, man by trade then proposed compositions based on ammonium nitrate and / or potassium perchlorate in combination with tetrazole derivatives and compounds metallic like boron oxide, vanadium oxide or silicates. Such compositions which are, for example, described in US-A-5,035,757 give many non-toxic nitrogen-rich gases but still produce many solid residues which make it necessary to have a important filtration.
Il a également été proposé, par exemple par le brevet US-A-5,462,579, des compositions à base d'acétate de cellulose, de nitrate d'ammonium et de perchlorate de potassium. De telles compositions conduisent bien à des gaz riches en azote mais, compte-tenu de leur teneur en liant, ces gaz sont souvent toxiques car trop riches en monoxyde de carbone. Par ailleurs pour atteindre des vitesses de combustion satisfaisantes, l'homme de métier est, dans la pratique, obligé de rajouter des oxydes métalliques ou des poudres métalliques, comme indiqué dans ce brevet, et de ce fait se trouve de nouveau confronté à la nécessité de filtrer les gaz de combustion.It has also been proposed, for example by the US-A-5,462,579, acetate-based compositions cellulose, ammonium nitrate and perchlorate potassium. Such compositions do lead to nitrogen-rich gases but, given their content binder, these gases are often toxic because they are too rich in carbon monoxide. In addition to reach satisfactory combustion speeds, the skilled person is, in practice, obliged to add oxides metallic or metallic powders, as shown in this patent, and therefore is found again faced with the need to filter gases from combustion.
Il a été proposé par la demande de brevet FR-A-2 713 632 des compositions excluant expressément la présence de composés métalliques et comprenant essentiellement un liant thermoplastique oxygéné, un plastifiant énergétique comme le polyazoture de glycidyle et une charge oxydante composée pour au moins 85% de son poids par du nitrate d'ammonium.It was proposed by the patent application FR-A-2 713 632 of compositions expressly excluding the presence of metallic compounds and comprising essentially an oxygenated thermoplastic binder, a energy plasticizer such as polyazide glycidyl and a compound oxidizing charge for at least 85% of its weight by ammonium nitrate.
Pour que les chargements ainsi constitués présentent une tenue mécanique satisfaisante, aussi bien immédiatement après la fabrication qu'après un long vieillissement, il est cependant nécessaire, en pratique, que la composition contienne au moins 8% en poids de liant sans parler du plastifiant énergétique et l'homme de métier se trouve, au moins pour certaines applications, à nouveau confronté au problème de la toxicité des gaz.So that the loads thus constituted have satisfactory mechanical strength, as well immediately after manufacture only after a long aging, however, it is necessary practical, that the composition contains at least 8% by weight of binder not to mention the energy plasticizer and the skilled person is, at least for some applications, again faced with the problem of gas toxicity.
Il a alors été proposé par la demande de brevet FR 96.08050 des compositions dont la charge oxydante est à base de nitrate d'ammonium et qui contiennent moins de 6% en poids d'un liant organique oxygéné et entre 0,5% et 5% en poids d'un métal léger choisi dans le groupe constitué par le bore et l'aluminium. Ces compositions qui sont avantageusement mises sous forme de pastilles par compression, présentent une vitesse de combustion satisfaisante, elles ne produisent pas par combustion de résidus solides lourds et les gaz générés ont une teneur en monoxyde de carbone extrêmement faible. Néanmoins, les gaz générés par ces compositions ont une teneur en oxydes d'azote encore un peu trop élevée lorsqu'ils sont destinés à fonctionner dans des systèmes ouverts sur l'extérieur.It was then proposed by the patent application FR 96.08050 of compositions whose oxidizing charge is based on ammonium nitrate and which contain less than 6% by weight of an oxygenated organic binder and between 0.5% and 5% by weight of a light metal chosen from the group consisting of boron and aluminum. These compositions which are advantageously put in the form of pellets by compression, have a burning rate satisfactory, they do not produce by combustion of heavy solid residues and the gases generated have a content in extremely low carbon monoxide. However, the gases generated by these compositions have a content of nitrogen oxides still a little too high when they're intended to operate in open systems on outside.
Le but de la présente invention est précisément de réaliser des compositions du type de celles décrites dans la demande FR 96.08050 de manière à ce qu'elles satisfassent simultanément aux trois critères suivants nécessaires à leur utilisation en direction de systèmes ouverts :
- bonne vitesse de combustion,
- absence de résidus solides lourds,
- gaz présentant une très faible teneur en oxydes d'azote.
- good burning speed,
- absence of heavy solid residues,
- gases with a very low content of nitrogen oxides.
L'invention concerne donc une composition
pyrotechnique génératrice de gaz propres comprenant un
liant organique réticulable oxygéné, un métal léger
choisi dans le groupe constitué par le bore et
l'aluminium, du perchlorate de potassium, un composant
azoté oxydant choisi dans le groupe constitué par le
perchlorate d'ammonium, le nitrate de triaminoguanidine,
l'hexogène, l'octogène et l'hexanitrohexaazaisowurtzitane,
du nitrate d'ammonium en phase stabilisée,
caractérisée en ce que,
Dans la présente description le symbole ≤ signifie "inférieur ou égal à" et le symbole ≥ signifie "supérieur ou égale à ".In the present description the symbol ≤ means "less than or equal to" and the symbol ≥ means "greater than or equal to".
Plus particulièrement, les teneurs pondérales des principaux constituants par rapport au poids total de la composition sont les suivantes :
- de 1 à 9% pour le liant organique réticulable oxygéné,
- de 0,5 à 5% pour le métal léger,
- de 0 à 30% pour le perchlorate de potassium.
- from 1 to 9% for the crosslinkable oxygenated organic binder,
- from 0.5 to 5% for light metal,
- from 0 to 30% for potassium perchlorate.
Lorsque la composition contient comme composé azoté oxydant du perchlorate d'ammonium ce dernier sera avantageusement associé à du nitrate de sodium qui fonctionnera, en cours de combustion, comme un capteur de chlore. Dans ce cas le rapport pondéral nitrate de sodium/perchlorate d'ammonium sera avantageusement voisin de 0,95. When the composition contains as nitrogen compound oxidant of ammonium perchlorate the latter will advantageously combined with sodium nitrate which will function, during combustion, as a sensor chlorine. In this case the nitrate weight ratio of sodium / ammonium perchlorate will advantageously close to 0.95.
Afin d'améliorer leur vitesse de combustion les compositions selon l'invention contiendront avantageusement de l'oxyde cuivrique CuO dont la teneur pondérale par rapport au poids total de la composition pourra s'élever jusqu'à 10%.In order to improve their burning speed, compositions according to the invention will contain advantageously cupric oxide CuO, the content of which by weight relative to the total weight of the composition could be up to 10%.
Les compositions selon l'invention pourront également avantageusement contenir jusqu'à 5% en poids de carbonate de lithium et jusqu'à 1% en poids de silice SiO2. Si l'on veut des compositions présentant une bonne vitesse de combustion et produisant des gaz très pauvres en oxydes d'azote, on veillera à ce que ces compositions contiennent de l'oxyde cuivrique comme indiqué plus haut et à ce que le dit composé azoté réactif soit de la nitroguanidine et/ou du nitrate de guanidinium à l'exclusion de l'oxamide. De telles compositions conviennent bien pour constituer des chargements pyrotechniques destinés à gonfler des coussins de protection pour occupants de véhicule automobile. Dans ce cas la teneur pondérale y du dit composé azoté réactif sera préférentiellement comprise entre 5% et 10% du poids total de la composition et plus préférentiellement voisine de 6%.The compositions according to the invention may also advantageously contain up to 5% by weight of lithium carbonate and up to 1% by weight of silica SiO 2 . If one wants compositions having a good combustion rate and producing gases very poor in nitrogen oxides, it will be ensured that these compositions contain cupric oxide as indicated above and that the said nitrogenous compound reagent of either nitroguanidine and / or guanidinium nitrate excluding oxamide. Such compositions are very suitable for constituting pyrotechnic charges intended to inflate protective cushions for occupants of a motor vehicle. In this case, the weight content y of said reactive nitrogen compound will preferably be between 5% and 10% of the total weight of the composition and more preferably close to 6%.
Les compositions seront mises sous forme de comprimés ou de dragées par pastillage, le liant oxygéné réticulable étant préférentiellement choisi parmi les polymères ou les copolymères à motifs époxy ou à motifs silicone. Après pastillage les pastilles obtenues sont cuites pendant quelques heures à une température voisine de 100°C pour provoquer la réticulation du liant.The compositions will be put in the form of tablets or tablet dragees, the oxygenated binder crosslinkable being preferably chosen from polymers or copolymers with epoxy units or units silicone. After tableting the pellets obtained are cooked for a few hours at a similar temperature 100 ° C to cause crosslinking of the binder.
Les pastilles de compositions réticulées sont alors destinées à constituer des chargements en vrac de générateurs pyrotechniques de gaz pour des systèmes ouverts sur l'extérieur comme des extincteurs pyrotechniques, des dispositifs de gonflage de structures externes ou des coussins de protection pour occupants d'un véhicule automobile.The crosslinked composition pellets are then intended to constitute bulk loads of pyrotechnic gas generators for systems open to the outside like fire extinguishers pyrotechnics, inflation devices external structures or protective cushions for occupants of a motor vehicle.
On donne ci-après une description détaillée d'un mode préféré de réalisation de l'invention. Les compositions selon l'invention sont donc fondamentalement des compositions pyrotechniques composites à base de nitrate d'ammonium et contenant un liant et un métal léger du type de celles décrites dans la demande de brevet français 96.08050.A detailed description is given below of preferred embodiment of the invention. The compositions according to the invention are therefore basically composite pyrotechnic compositions based on ammonium nitrate and containing a binder and a light metal of the type described in French patent application 96.08050.
Le liant est un liant oxygéné réticulable préférentiellement choisi parmi les liants à base de résine époxy ou à base de résine silicone. La teneur pondérale du dit liant par rapport au poids total de la composition sera comprise entre 1% et 6%.The binder is a crosslinkable oxygenated binder preferably chosen from binders based on epoxy resin or silicone resin based. Content by weight of the said binder relative to the total weight of the composition will be between 1% and 6%.
L'oxydant principal des compositions selon l'invention est du nitrate d'ammonium dont la teneur pondérale par rapport au poids total de la composition peut être comprise selon une première caractéristique de l'invention entre 29% et 93,5%, mais sera préférentiellement comprise entre 60% et 75%. Avantageusement le nitrate d'ammonium sera du nitrate d'ammonium stabilisé, par exemple par du nitrate de potassium et de l'amarante comme décrit dans la demande de brevet français 2 743 797. On utilisera dans ce cas avantageusement un mélange stabilisé contenant 96,5% en poids de nitrate d'ammonium, 3% en poids de nitrate de potassium et 0,5% en poids d'amarante.The main oxidant of the compositions according to the invention is ammonium nitrate the content of which by weight relative to the total weight of the composition can be understood according to a first characteristic of the invention between 29% and 93.5%, but will preferably between 60% and 75%. Advantageously, the ammonium nitrate will be nitrate of ammonium stabilized, for example with nitrate of potassium and amaranth as described in the application French patent 2,743,797. In this case, we will use advantageously a stabilized mixture containing 96.5% in weight of ammonium nitrate, 3% by weight of nitrate of potassium and 0.5% by weight of amaranth.
Le métal léger est choisi exclusivement parmi le bore et l'aluminium et sa teneur pondérale par rapport au poids total de la composition est comprise entre 0,5% et 5%. The light metal is chosen exclusively from the boron and aluminum and its weight content compared the total weight of the composition is between 0.5% and 5%.
A côté du nitrate d'ammonium les compositions selon l'invention peuvent également contenir d'autres oxydants. Elles peuvent ainsi contenir du perchlorate de potassium, la teneur pondérale de ce dernier par rapport au poids total de la composition pouvant être comprise entre 0% et 30%. Cette teneur pondérale sera souvent comprise entre 10% et 20%. Elles peuvent également contenir un composé azoté oxydant choisi dans le groupe constitué par le perchlorate d'ammonium, le nitrate de triaminoguanidine, l'hexogène, l'octogène et l'hexanitrohexaazaisowurtzitane. La teneur pondérale x de ce composé azoté oxydant par rapport au poids total de la composition satisfait à la relation 0% ≤ x ≤ 15%. Lorsque du perchlorate d'ammonium sera utilisé comme composé azoté oxydant, il le sera avantageusement en association avec du nitrate de sodium de manière à éviter la formation d'acide chlorhydrique dans les gaz de combustion. Dans ce cas le rapport pondéral nitrate de sodium/perchlorate d'ammonium sera avantageusement voisin de 0,95.Next to ammonium nitrate, the compositions according to the invention may also contain other oxidants. They can thus contain perchlorate of potassium, the weight content of the latter relative the total weight of the composition which may be included between 0% and 30%. This weight content will often between 10% and 20%. They can also contain an oxidizing nitrogen compound selected from the group consisting of ammonium perchlorate, nitrate of triaminoguanidine, hexogen, octogen and hexanitrohexaazaisowurtzitane. Weight content x of this oxidizing nitrogenous compound relative to the total weight of the composition satisfies the relation 0% ≤ x ≤ 15%. When ammonium perchlorate is used as oxidizing nitrogen compound, it will advantageously be combination with sodium nitrate so that avoid the formation of hydrochloric acid in the gases combustion. In this case the nitrate weight ratio sodium / ammonium perchlorate will advantageously close to 0.95.
Selon une seconde caractéristique essentielle de
l'invention, les compositions pyrotechniques contiennent
impérativement un composé azoté organique réactif choisi
dans le groupe constitué par la nitroguanidine, le
nitrate de guanidinium et l'oxamide. La teneur pondérale
y de ce composé azoté réactif exprimée par rapport au
poids total de la composition satisfait à la double
relation :
Ces composés azotés réactifs contribuent tous à augmenter la teneur des gaz produits en azote et à abaisser la teneur de ces gaz en oxydes d'azote. These reactive nitrogen compounds all contribute to increase the nitrogen content of the gases produced and lower the nitrogen oxide content of these gases.
Les compositions selon l'invention peuvent également contenir des additifs divers comme par exemple de l'oxyde cuivrique CuO, du carbonate de lithium Li2CO3 ou de la silice SiO2. Ces additifs ont des fonctions diverses, la silice qui sera en général utilisée à des teneurs inférieures ou égales à 1% en poids a un effet anti-mottant sur le nitrate d'ammonium en cours de formulation et de mise en forme de la composition avant réticulation du liant. Le carbonate de lithium qui sera en général utilisé à des teneurs inférieures ou égales à 5% en poids permet d'abaisser la température de combustion des compositions selon l'invention tandis que l'oxyde cuivrique qui sera en général utilisé à des teneurs pondérales inférieures ou égales à 10%, le plus souvent voisines de 6%, permet d'améliorer l'allumage des compositions selon l'invention et d'en augmenter les vitesses de combustion.The compositions according to the invention can also contain various additives such as, for example, cupric oxide CuO, lithium carbonate Li 2 CO 3 or silica SiO 2 . These additives have various functions, the silica which will generally be used at contents less than or equal to 1% by weight has an anti-caking effect on the ammonium nitrate during formulation and shaping of the composition before crosslinking of the binder. The lithium carbonate which will generally be used at contents less than or equal to 5% by weight makes it possible to lower the combustion temperature of the compositions according to the invention while the cupric oxide which will generally be used at lower weight contents or equal to 10%, most often close to 6%, makes it possible to improve the ignition of the compositions according to the invention and to increase their combustion rates.
Les compositions destinées à la sécurité automobile contiendront donc de préférence de l'oxyde cuivrique. Les gaz destinés à gonfler des coussins de protection pour occupants d'un véhicule automobile doivent non seulement être très pauvres en oxydes d'azote mais doivent également être très pauvres en monoxyde de carbone CO. Pour satisfaire à cette dernière exigence on évitera l'emploi de l'oxamide comme composant azoté réactif dans les compositions destinées à la sécurité automobile et on se limitera, pour ces compositions, à l'emploi de nitroguanidine ou de nitrate de guanidinium comme composé azoté réactif. De manière préférée la teneur pondérale en composé azoté réactif sera, pour ces compositions, comprise entre 5% et 10% par rapport au poids total de la composition, et plus particulièrement voisine de 6%. Vehicle safety compositions will therefore preferably contain cupric oxide. Gases intended to inflate protective cushions for occupants of a motor vehicle must not only be very poor in nitrogen oxides but must also be very low in monoxide carbon CO. To meet this last requirement we avoid the use of oxamide as a nitrogen component reactive in safety compositions automotive and we will limit ourselves, for these compositions, to the use of nitroguanidine or guanidinium nitrate as reactive nitrogen compound. Preferably the weight content of reactive nitrogen compound will, for these compositions, between 5% and 10% compared to the total weight of the composition, and more particularly close to 6%.
Les compositions selon l'invention sont mises en forme par pastillage après une phase de mélange effectuée dans un malaxeur.The compositions according to the invention are used form by tableting after a mixing phase performed in a mixer.
Dans un malaxeur ouvert on introduit les charges solides pulvérulentes constituées par le nitrate d'ammonium, le bore ou l'aluminium, les composés azotés cités plus haut ainsi que, le cas échéant, le perchlorate de potassium et les additifs solides éventuels.In an open mixer we introduce the charges powdery solids consisting of nitrate ammonium, boron or aluminum, nitrogen compounds cited above as well as, where applicable, the potassium perchlorate and solid additives possible.
On ajoute ensuite le liant oxygéné à l'état liquide, non complètement polymérisé. Dans le cas d'un liant thermodurcissable il s'agira de la résine liquide mélangée à son durcisseur. Lorsque la résine employée est une résine polyépoxy, le durcisseur sera avantageusement une polyamine peu réactive de manière à disposer d'une "vie de pot" pour le liant d'environ 24 heures.The oxygenated binder is then added in the state liquid, not completely polymerized. In the case of a thermosetting binder it will be liquid resin mixed with its hardener. When the resin used is a polyepoxy resin, the hardener will be advantageously a polyamine which is not very reactive so as to have a "pot life" for the binder of about 24 hours.
Une des caractéristiques fondamentales des compositions selon l'invention étant de ne contenir que très peu de liant par rapport aux compositions usuelles destinées aux propergols ou aux poudres à faible vulnérabilité du type "LOVA", une difficulté non négligeable de formulation des compositions selon l'invention consiste à réussir à imprégner l'ensemble des constituants solides, et notamment le nitrate d'ammonium, avec cette faible quantité de liant liquide.One of the fundamental characteristics of compositions according to the invention being to contain only very little binder compared to usual compositions for propellants or low powders "LOVA" type vulnerability, a difficulty not negligible formulation of compositions according to the invention consists in successfully permeating the whole solid constituents, and in particular nitrate ammonium, with this small amount of liquid binder.
A cette fin le liant liquide sera avantageusement introduit dans le malaxeur sous forme diluée dans un solvant très volatil et inerte vis à vis des constituants de la composition. Par exemple avec un liant polyépoxy on utilisera avantageusement du trichloréthane comme diluant.To this end, the liquid binder will advantageously be introduced into the mixer in diluted form in a solvent very volatile and inert towards constituents of the composition. For example with a polyepoxy binder advantageously use trichloroethane as a diluent.
Le malaxeur est alors mis en route et on le laisse tourner, cuve couverte, pendant environ une heure. Dans ces conditions on peut imprégner l'ensemble des constituants solides par le liant et la totalité du diluant a été éliminée par évaporation au cours de l'opération de malaxage.The mixer is then started and left on turn, bowl covered, for about an hour. In these conditions we can permeate all of the solid constituents by the binder and all of the diluent was removed by evaporation during the mixing operation.
La composition qui se présente à ce stade sous l'aspect d'une poudre légèrement humide, est mise à la forme voulue par compression. En général elle est mise sous forme de pastilles.The composition which appears at this stage under the appearance of a slightly wet powder, is brought to the desired shape by compression. In general it is put in the form of pellets.
La polymérisation du liant se fait à une température voisine de 100°C et au bout de 7 heures, dans le cas d'un liant polyépoxy, les chargements pyrotechniques obtenus présentent une bonne tenue mécanique permettant leur emploi dans un générateur pyrotechnique de gaz.The polymerization of the binder takes place at a temperature close to 100 ° C and after 7 hours, in the case of a polyepoxy binder, the loads pyrotechnics obtained show good performance mechanical allowing their use in a generator gas pyrotechnics.
Les compositions selon l'invention contiennent un faible taux de liant qui n'est pas suffisant pour combler tous les interstices entre les grains de nitrate d'ammonium. De ce fait la mise sous forme de pastilles par compression conduit à des objets présentant une porosité naturelle correspondant à un accroissement de la surface offerte à la combustion, ce qui est très favorable au niveau de la vitesse de combustion de la composition.The compositions according to the invention contain a low level of binder which is not sufficient for fill all the gaps between the nitrate grains ammonium. Therefore putting into the form of pellets by compression leads to objects having a natural porosity corresponding to an increase in the area available for combustion, which is very favorable in terms of the rate of combustion of the composition.
Par ailleurs l'utilisation d'un nitrate d'ammonium stabilisé tel que décrit plus haut favorise la conservation dans le temps des propriétés du matériau générateur de gaz. Furthermore the use of an ammonium nitrate stabilized as described above promotes the conservation over time of the material's properties gas generator.
Les exemples qui suivent illustrent, à titre non limitatif, certaines possibilités de mise en oeuvre de l'invention.The examples which follow illustrate, without title limiting, certain possibilities of implementation of the invention.
On a fabriqué des pastilles ayant les compositions
suivantes figurant au tableau 1.
Dans ce tableau les parties sont indiquées en poids.In this table the parts are indicated in weight.
L'exemple 1 concerne une composition telle que décrite dans la demande de brevet français 96.08050 et est donné à titre de comparaison.Example 1 relates to a composition such that described in French patent application 96.08050 and is given for comparison.
Les pastilles ainsi obtenues ont servi à constituer les chargements pyrotechniques de générateurs de gaz destinés à gonfler des coussins de 60 litres. Les résultats de tir figurent dans le tableau n°2 dans lequel les abréviations suivantes ont été utilisées :
- Tc =
- température de combustion en K.
- Rdt/Tc =
- rendement gazeux (en litres/g) à la température de combustion.
- COppm =
- teneur des gaz en monoxyde de carbone à la sortie du générateur exprimé en ppm.
- NOxppm =
- teneur des gaz en oxydes d'azote à la sortie
du générateur exprimée en ppm.
Exemple 1 Exemple 2 Exemple 3 Exemple 4 Exemple 5 Exemple 6 Tc 2186 2311 2007 2010 2219 2289 Rdt/Tc 5,61 6,32 5,53 5,71 6,12 6,10 COppm 85 513 29 30 19710 3056 NOxppm 4389 3791 2736 2649 56 703
- Tc =
- combustion temperature in K.
- Yd / Tc =
- gas yield (in liters / g) at combustion temperature.
- COppm =
- carbon monoxide content of the gases at the generator outlet expressed in ppm.
- NOxppm =
- nitrogen oxide gas content at the generator outlet expressed in ppm.
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Tc 2186 2311 2007 2010 2219 2289 Yd / Tc 5.61 6.32 5.53 5.71 6.12 6.10 COppm 85 513 29 30 19710 3056 NOxppm 4389 3791 2736 2649 56 703
De l'examen des tableaux 1 et 2 il ressort que toutes les compositions selon l'invention (exemple 2 à 6) permettent d'abaisser la teneur des gaz en oxydes d'azote par rapport à la référence (exemple 1), les résultats les plus spectaculaires étant obtenus avec l'oxamide (exemple 5 et 6). Néanmoins les compositions avec l'oxamide fournissent des gaz trop riches en monoxyde de carbone pour la sécurité automobile. Ce sont les compositions riches en nitrate d'ammonium et utilisant de la nitroguanidine (exemples 3 et 4) qui fournissent les gaz les plus intéressants pour la sécurité automobile.Examination of Tables 1 and 2 shows that all the compositions according to the invention (example 2 to 6) reduce the oxide content of the gases nitrogen compared to the reference (example 1), the most dramatic results being achieved with oxamide (examples 5 and 6). Nevertheless the compositions with oxamide provide gases too rich in carbon monoxide for automotive safety. Those are compositions rich in ammonium nitrate and using nitroguanidine (examples 3 and 4) which provide the most attractive gases for the automotive safety.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9716216A FR2772750B1 (en) | 1997-12-22 | 1997-12-22 | PYROTECHNIC COMPOSITION CLEAN GAS, LOW NITROGEN OXIDE CONTENT, AND PELLETS OF SUCH A COMPOSITION |
| FR9716216 | 1997-12-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0924177A1 true EP0924177A1 (en) | 1999-06-23 |
| EP0924177B1 EP0924177B1 (en) | 2002-08-14 |
Family
ID=9514887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98403120A Expired - Lifetime EP0924177B1 (en) | 1997-12-22 | 1998-12-10 | Pyrotechnic composition for generating of a clean gas with a low nitrogen oxide content and pellets thereof |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6024811A (en) |
| EP (1) | EP0924177B1 (en) |
| DE (1) | DE69807177T2 (en) |
| FR (1) | FR2772750B1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE20010154U1 (en) | 2000-06-07 | 2000-09-07 | Trw Airbag Sys Gmbh & Co Kg | Ignition mixture for use in gas generators |
| US6875295B2 (en) | 2001-12-27 | 2005-04-05 | Trw Inc. | Cool burning gas generating material for a vehicle occupant protection apparatus |
| US7811397B2 (en) | 2004-09-27 | 2010-10-12 | Daicel Chemical Industries, Ltd. | Gas generating agent |
| US8980023B2 (en) * | 2011-07-27 | 2015-03-17 | Autoliv Asp, Inc. | Gas generation via elemental carbon-based compositions |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0619284A1 (en) * | 1993-04-08 | 1994-10-12 | Trw Inc. | Gas generator for vehicle occupant restraint |
| WO1995004710A1 (en) * | 1993-08-04 | 1995-02-16 | Automotive Systems Laboratory, Inc. | Law residue azide-free gas generant composition |
| FR2713632A1 (en) * | 1993-12-07 | 1995-06-16 | Poudres & Explosifs Ste Nale | Clean, nontoxic, gas generating pyrotechnic compositions containing a thermoplastic elastomeric binder. |
| DE19516818A1 (en) * | 1994-05-09 | 1995-11-16 | Nof Corp | Gas generation compsn. for use in inflatable safety devices |
| US5536339A (en) * | 1994-09-27 | 1996-07-16 | Conducting Materials Corporation | Air bag inflator gas compositions and inflator containing the same |
| US5545272A (en) * | 1995-03-03 | 1996-08-13 | Olin Corporation | Thermally stable gas generating composition |
| FR2750422A1 (en) * | 1996-06-28 | 1998-01-02 | Poudres & Explosifs Ste Nale | PYROTECHNIC COMPOSITIONS GENERATING CLEAN GAS AND APPLICATION TO A GAS GENERATOR FOR MOTOR VEHICLE SAFETY |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3725516A (en) * | 1964-04-17 | 1973-04-03 | Us Navy | Mixing process and extrusion of solid propellants |
| US4929290A (en) * | 1988-07-25 | 1990-05-29 | Hercules Incorporated | Crash bag propellant composition and method for generating nitrogen gas |
| US5035757A (en) * | 1990-10-25 | 1991-07-30 | Automotive Systems Laboratory, Inc. | Azide-free gas generant composition with easily filterable combustion products |
| US5898126A (en) * | 1992-07-13 | 1999-04-27 | Daicel Chemical Industries, Ltd. | Air bag gas generating composition |
| DE4412871C2 (en) * | 1993-04-15 | 1997-08-14 | Nof Corp | Gas generator compositions |
| US5656793A (en) * | 1994-05-09 | 1997-08-12 | Eiwa Chemical Ind. Co., Ltd. | Gas generator compositions |
| US5780768A (en) * | 1995-03-10 | 1998-07-14 | Talley Defense Systems, Inc. | Gas generating compositions |
| US5850053A (en) * | 1995-03-31 | 1998-12-15 | Atlantic Research Corporation | Eutectic mixtures of ammonium nitrate, guanidine nitrate and potassium perchlorate |
| US5670740A (en) * | 1995-10-06 | 1997-09-23 | Morton International, Inc. | Heterogeneous gas generant charges |
| FR2743797B1 (en) * | 1996-01-24 | 1998-02-13 | Poudres & Explosifs Ste Nale | STABILIZED AMMONIUM NITRATE |
| US5756929A (en) * | 1996-02-14 | 1998-05-26 | Automotive Systems Laboratory Inc. | Nonazide gas generating 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 |
| JPH09328387A (en) * | 1996-06-03 | 1997-12-22 | Daicel Chem Ind Ltd | Gas producing agent composition |
| US5936195A (en) * | 1997-06-10 | 1999-08-10 | Atlantic Research Corporation | Gas generating composition with exploded aluminum powder |
-
1997
- 1997-12-22 FR FR9716216A patent/FR2772750B1/en not_active Expired - Fee Related
-
1998
- 1998-12-03 US US09/204,466 patent/US6024811A/en not_active Expired - Lifetime
- 1998-12-10 DE DE69807177T patent/DE69807177T2/en not_active Expired - Lifetime
- 1998-12-10 EP EP98403120A patent/EP0924177B1/en not_active Expired - Lifetime
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0619284A1 (en) * | 1993-04-08 | 1994-10-12 | Trw Inc. | Gas generator for vehicle occupant restraint |
| WO1995004710A1 (en) * | 1993-08-04 | 1995-02-16 | Automotive Systems Laboratory, Inc. | Law residue azide-free gas generant composition |
| FR2713632A1 (en) * | 1993-12-07 | 1995-06-16 | Poudres & Explosifs Ste Nale | Clean, nontoxic, gas generating pyrotechnic compositions containing a thermoplastic elastomeric binder. |
| EP0659712A1 (en) * | 1993-12-07 | 1995-06-28 | Societe Nationale Des Poudres Et Explosifs | Pyrotechnic compositions for producing clean non-toxic gases containing an elastomeric thermoplastic binder |
| DE19516818A1 (en) * | 1994-05-09 | 1995-11-16 | Nof Corp | Gas generation compsn. for use in inflatable safety devices |
| US5536339A (en) * | 1994-09-27 | 1996-07-16 | Conducting Materials Corporation | Air bag inflator gas compositions and inflator containing the same |
| US5545272A (en) * | 1995-03-03 | 1996-08-13 | Olin Corporation | Thermally stable gas generating composition |
| FR2750422A1 (en) * | 1996-06-28 | 1998-01-02 | Poudres & Explosifs Ste Nale | PYROTECHNIC COMPOSITIONS GENERATING CLEAN GAS AND APPLICATION TO A GAS GENERATOR FOR MOTOR VEHICLE SAFETY |
| EP0816307A1 (en) * | 1996-06-28 | 1998-01-07 | Societe Nationale Des Poudres Et Explosifs | Clean-gas generating pyrotechnic compositions and use thereof in a gas generator employed in a protection system in motor vehicles |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69807177D1 (en) | 2002-09-19 |
| DE69807177T2 (en) | 2003-07-24 |
| FR2772750B1 (en) | 2000-01-28 |
| EP0924177B1 (en) | 2002-08-14 |
| US6024811A (en) | 2000-02-15 |
| FR2772750A1 (en) | 1999-06-25 |
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