EP1496036A2 - Pyrotechnic gas generating composition for car safety systems having a combustion temperature below 2200 degree K - Google Patents
Pyrotechnic gas generating composition for car safety systems having a combustion temperature below 2200 degree K Download PDFInfo
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- EP1496036A2 EP1496036A2 EP04291733A EP04291733A EP1496036A2 EP 1496036 A2 EP1496036 A2 EP 1496036A2 EP 04291733 A EP04291733 A EP 04291733A EP 04291733 A EP04291733 A EP 04291733A EP 1496036 A2 EP1496036 A2 EP 1496036A2
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- EP
- European Patent Office
- Prior art keywords
- composition
- composition according
- binder
- ammonium perchlorate
- charge
- Prior art date
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- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 140
- 238000002485 combustion reaction Methods 0.000 title claims description 24
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims abstract description 34
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005751 Copper oxide Substances 0.000 claims abstract description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 10
- MJFQUUWPZOGYQT-UHFFFAOYSA-O diaminomethylideneazanium;nitrate Chemical compound NC(N)=[NH2+].[O-][N+]([O-])=O MJFQUUWPZOGYQT-UHFFFAOYSA-O 0.000 claims abstract description 9
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 claims abstract description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011230 binding agent Substances 0.000 claims description 37
- 230000001590 oxidative effect Effects 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 9
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 7
- 150000001912 cyanamides Chemical class 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- -1 nitrogenous organic compound Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- HVICWZVYCLJXNW-UHFFFAOYSA-N cyanamide;zinc Chemical group [Zn].NC#N HVICWZVYCLJXNW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 1
- 229920002451 polyvinyl alcohol Polymers 0.000 claims 1
- 239000007789 gas Substances 0.000 description 24
- 229910052760 oxygen Inorganic materials 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910002651 NO3 Inorganic materials 0.000 description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 11
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000032683 aging Effects 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 description 5
- 235000010344 sodium nitrate Nutrition 0.000 description 5
- 239000004317 sodium nitrate Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003517 fume Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HHEFNVCDPLQQTP-UHFFFAOYSA-N ammonium perchlorate Chemical compound [NH4+].[O-]Cl(=O)(=O)=O HHEFNVCDPLQQTP-UHFFFAOYSA-N 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000001033 granulometry Methods 0.000 description 2
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical group 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methyl alcohol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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 generation pyrotechnic gas, in particular to inflate protective cushions used in protection of the occupants of a motor vehicle.
- the invention relates more particularly to pyrotechnic compositions generating at temperatures acceptable for the automotive safety of clean gases, so-called "cold", high in nitrogen and non-toxic.
- pyrotechnic gas generators For different pyrotechnic needs including to ensure proper inflation of the cushions protection, pyrotechnic gas generators must provide in extremely short times, the order of thirty milliseconds, clean gases that is to say free from solid particles likely to constitute hot spots that can damage the wall cushion, and non-toxic that is to say low levels of nitrogen oxides, carbon oxides and chlorinated products.
- compositions made up basically by an organic binder and by a oxidizing charge such as perchlorate ammonium. These compositions are very interesting because they have a good rate of combustion and a excellent aging stability.
- compositions based ammonium perchlorate and sodium nitrate mixed with nitro compounds such as azides or metal nitrides are for example described in US Patent 3,814,694. However, due to the presence of azides making them very toxic in operation, these compositions are not recommended.
- U.S. Patent 4,909,549 discloses compositions consisting of a mixture of ammonium perchlorate and of sodium nitrate combined with a nitrogen compound of triazole or tetrazole. Such compositions generate many clean, nitrogen-rich gases, but these gases are relatively toxic and need to be diluted with air for safe use automobile.
- a pyrotechnic composition generating of burning gas at relatively low temperatures between 2000 and 2200 K, including in particular reducing charge constituted by nitroguanidine and a oxidizing agent composed for example of an alkaline nitrate or alkaline earth metal or a metal oxide or mix of both.
- This composition comprises, for example from 20 to 80% by weight of nitroguanidine and from 80 to 20% by weight mass of oxidizing agent.
- This type of composition generates gas at temperatures below 2200 K, which is an advantage for safe use automobile.
- the burning rates of these compositions remain too weak to be used effectively in gas generators intended for automotive safety.
- Patent No. FR 2,772,370 or its corresponding US Pat. No. 6,533,878 discloses a generating composition clean, non-toxic gases at high temperatures acceptable for automotive safety, that is to say less than 2200 K.
- This composition contains more particularly a crosslinked reducing binder and a main oxidizing charge consisting of a mixture of ammonium perchlorate combined with a chlorine sensor selected from the group consisting of nitrate sodium, potassium carbonate and carbonate of lithium.
- This composition also includes additives containing at least one copper compound as copper oxide and a nitrogenous organic compound like for example nitroguanidine or nitrate guanidinium. This composition burns at combustion and at temperatures quite suitable for use in automobile safety.
- ammonium perchlorate is largely in the majority. Although it is true that ammonium perchlorate is highly oxidizing and has a very good gas yield, it increases the temperature of burning of the composition and helps to increase strongly the creation of chlorine-based products as hydrogen chloride, these products forming droplets and particles difficult to filter and abundant sources of smoke. However, the formation of fumes is a phenomenon that needs to be maximum.
- a gas generating composition comprising 20 to 60% of a fuel and 40 to 80% of an oxidizing mixture.
- the fuel contains at least 95% of an organic compound nitrogen (guanidine nitrate), while the mixture oxidant comprises from 20 to 80% of a metal oxide, 0 to 50% basic nitrate of copper, from 1 to 15% of a metal chlorate or ammonium perchlorate and 1 at 15% of an alkaline or alkaline earth nitrate.
- This composition has a level of ammonium perchlorate low which limits the formation of fumes and the production of hydrogen chloride (HCl).
- ammonium perchlorate makes it possible to give the composition a good gas yield, a rather high burning speed and good ignitability. Moreover, by regulating the granulometry of ammonium perchlorate, it is possible to adjust the ballistics of the composition. Low use ammonium perchlorate content in the composition described in application No. DE 298 21 541 does not allow take full advantage of these benefits. Finally, this composition that is based on majority employment metal oxides can only be implemented by pelletizing. The low level of ammonium perchlorate, which has a high oxygen balance, does not allow not the use of a binder in very large quantities and therefore does not allow the implementation by extrusion.
- the object of the invention is therefore to propose a pyrotechnic composition generating clean gases, no toxic, at low temperatures below 2200K, having a ballistic interest, guaranteeing a good gas performance and good ignitability and creating little fumes and little hydrogen chloride.
- composition pyrotechnic gas generator this composition characterized in that it comprises a first oxidizing charge consisting of ammonium perchlorate present at a weight content between 15 and 30% of the total weight of the composition, and a second charge oxidizing agent consisting of a metal oxide selected from group consisting of copper oxide, oxide of manganese and a mixture of these two compounds, the ratio weight first oxidizing charge / second charge oxidant being less than 1, said composition also comprising a reducing charge in the form a nitrogenous organic compound selected from the group consisting of nitroguanidine, nitrate guanidinium, oxamide, dicyandiamide and metallic cyanamides.
- the weight content of the first oxidizing charge is between 15 and 30% of the total weight of the composition.
- Ammonium perchlorate is a very strong oxidant and has a very good performance gaseous. Its strongly oxidizing nature makes it particularly to increase the proportion of reducing charge and therefore for example guanidinium nitrate in the composition, the latter having a very good gas yield.
- the presence of ammonium perchlorate in the composition makes it possible to obtain a speed of combustion of the high composition.
- the speed of combustion is adjustable by the particle size of the ammonium perchlorate present in the compound pyrotechnic to burn.
- the burning speed can also be regulated by the use of catalysts combustion of the composition.
- ammonium perchlorate conferring on the composition a high combustion rate, also allows to avoid variations in thicknesses that may appear on the compound to be burned during its manufacturing and therefore avoid deviations from functioning related to these variations during the combustion of the compound.
- the combustion of a pyrotechnic compound is primarily a chemical reaction, so it is temperature dependent.
- the use of ammonium perchlorate makes it possible to lower the pressure exponent, which makes the composition less dependent on the pressure and therefore less dependent on the temperature.
- the pressure exponent is particularly low, much lower than 0.7, which makes it possible to operate the pyrotechnic compound at temperatures between -35 ° C and 85 ° C.
- the composition according to the invention can therefore be used in a motor vehicle.
- composition according to the invention does not comprise necessarily binder.
- a binder can be added in the composition.
- compositions must have a balanced oxygen balance (called OB for "Oxygen Balance").
- OB Olygen Balance
- a composition is said to be balanced in oxygen when the composition comprises sufficient oxygen so that after reaction, the various compounds of the composition are found in the form of CO 2 , H 2 O and N 2 .
- the oxygen balances of the binders are generally very low and often need to be compensated.
- the presence of ammonium perchlorate in a composition allows such compensation.
- the ammonium perchlorate should not be at a rate too high in the composition to avoid the disadvantages associated with its use as the production of hydrogen chloride or the creation of fumes.
- the oxygen balance of the binder must be the least low possible. An adjustment of the oxygen balance around the balance also helps to limit the amount of chlorides formed.
- the proportion high level of ammonium perchlorate in the composition according to the invention makes it possible to incorporate a binder at a sufficient rate to be able to implement the extrusion composition.
- the composition comprises a binder selected from the group consisting of methyl cellulose and alcohol Polyvinyl.
- the binder retained is the sodium carboxymethylcellulose (hereinafter CMC-Na).
- CMC-Na sodium carboxymethylcellulose
- the binder chosen is the sodium carboxymethylcellulose.
- This binder has a oxygen balance of -103.5% (degree of substitution of 0.7) which is notably much higher than the Oxygen balance of elastomeric type binders.
- the sodium carboxymethylcellulose binder is suitable also very good at extrusion, granulation and compression and so will perfectly adapted for the implementation of the composition in the form of pellets, discs or monolithic blocks.
- the composition described in the patent application No. 2,772,370 comprises a reducing binder crosslinked based on silicone resin or resin-based epoxy.
- the binder is present in this composition at a between 6% and 10% of the total weight of the composition.
- a composition must have a minimum binder rate of around 4% or 5% of the total weight of the composition and requires the use a solvent of the binder.
- the binders retained in this composition of the prior art require the use of organic or halogenated solvents. But the use of halogenated solvents such as for example the trichlorethylene is regulated which complicates greatly the manufacture of such a composition and increases its manufacturing cost. Similarly, the use of organic solvents leads to the establishment of complex solutions to control emissions from volatile organic compounds (VOCs).
- VOCs volatile organic compounds
- the binder for example the sodium carboxymethylcellulose is soluble in water which makes it possible to avoid having recourse, as in the art prior to halogenated or organic solvents when granulation or extrusion steps in the manufacture of pyrotechnic compounds.
- the weight content of the binder represents not more than 6% of the total weight of the composition.
- the binder presents as a rule a very low oxygen balance. So as not to penalize the balance too much oxygen content of the composition, the proportion of binder in the composition must therefore remain very low.
- the composition contains additives facilitating its manufacture.
- additives are for example calcium stearate and allow when the composition according to the invention has no binder to facilitate its manufacture.
- the nitrogenous organic compound chosen from nitroguanidine, guanidinium nitrate, oxamide, dicyandiamide and metallic cyanamides is at a grade between 30 and 50% of the total weight of the composition.
- the organic compound nitrogen is the reducing charge and is a constituent part of the composition, the binder, when it is present, intervening rather as an additive.
- the reducing load chosen is the guanidinium nitrate.
- the nitrate of guanidinium has a very good behavior in aging measured by the 400-hour test at 107 ° C.
- the presence of guanidinium nitrate in the composition improves the gas yield of the composition.
- Guanidinium nitrate has a enthalpy of negative training also having for effect of lowering the combustion temperature of the composition.
- the weight content of the second oxidizing charge is between 30 and 45% of the total weight of the composition.
- This second oxidizing charge makes it possible in particular to limit the amount of ammonium perchlorate in the composition.
- ammonium perchlorate is a strong oxidant and has interesting properties in combustion, its use in a composition leads to the achievement of high combustion temperatures and the generation of gas. combustion with a fairly high rate of hydrogen chloride.
- This second oxidizing charge is a metal oxide and preferably copper oxide CuO or manganese oxide MnO 2 . A mixture of these two oxides can also be used as the second oxidizing charge.
- This second oxidizing charge is present at a very high level in the composition and at a rate higher than that of ammonium perchlorate. It has a low formation enthalpy so as to lower the combustion temperature of the composition. Indeed, for example, the formation enthalpy of copper oxide CuO is -155 KJ / mol. Copper oxide also has the advantage of being an excellent combustion catalyst ammonium perchlorate which allows to give the composition a high rate of combustion making it very suitable for use in automotive safety.
- the composition may also include solid particle trapping agents emitted during combustion in order to create residues of a sufficiently large size to can be filtered.
- solid particle trapping agents emitted during combustion in order to create residues of a sufficiently large size to can be filtered.
- Well known additives in the domain of automotive safety compositions like for example alumina or silica can be added in the composition according to the invention.
- the metal cyanamides optionally present in the composition are constituted by cyanamides of sodium, zinc and copper.
- the metal cyanamide chosen is zinc cyanamide ZnCN 2 .
- pyrotechnic compounds having a composition as described above can be manufactured at high speed by compression discs or by pelletizing.
- a powder preparation step must to be implemented. This step is not just a simple dry mixing of the various constituents. In effect, in order to be able to implement the pelletizing, it is necessary to obtain a powder which flows well.
- This preparation step is a granulation operation consisting of different matters forming part of the constitution of the composition according to the invention and present in form powdery to make grains with more granulometry high of the order of a few hundred microns. A once this powder obtained, the pelletizing operation can be implemented.
- the pyrotechnic products can also be obtained by extrusion using of a twin-screw extruder.
- a binder such as carboxymethylcellulose of sodium in the composition and use a solvent.
- the sodium carboxymethylcellulose is soluble in water.
- the use of sodium carboxymethylcellulose does not therefore require the use of halogenated solvents or organic. A small proportion of water is incorporated to the mixture so as to avoid solubilization of the ammonium perchlorate.
- the method for obtaining pyrotechnic compounds having a composition according to the invention as described above first of all involves a step of feeding into continuous mixing and extrusion apparatus, such as for example a twin-screw extruder, on the one hand with the two oxidizing charges and secondly with the compound organic nitrogen premixed with the binder, i.e. with sodium carboxymethylcellulose.
- continuous mixing and extrusion apparatus such as for example a twin-screw extruder
- the extruder extrude a rod profile which is hardened in an oven and cut to length wanted, for example to form aggregates.
- Binder CMC-Na Glycerides PA MnO 2 CuO G. nitrate Temp (K) BO (%) Yld. Res.
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Abstract
Description
La présente invention concerne la génération pyrotechnique de gaz, notamment pour gonfler des coussins de protection utilisés dans les systèmes de protection des occupants d'un véhicule automobile. L'invention concerne plus particulièrement 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 generation pyrotechnic gas, in particular to inflate protective cushions used in protection of the occupants of a motor vehicle. The invention relates more particularly to pyrotechnic compositions generating at temperatures acceptable for the automotive safety of clean gases, so-called "cold", high 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 including to ensure proper inflation of the cushions protection, pyrotechnic gas generators must provide in extremely short times, the order of thirty milliseconds, clean gases that is to say free from solid particles likely to constitute hot spots that can damage the wall cushion, and non-toxic that is to say low levels of nitrogen oxides, carbon oxides and chlorinated products.
Diverses familles de compositions ont été développées dans ce but. L'une de ces familles concerne les compositions "composites" constituées fondamentalement par un liant organique et par une charge oxydante comme notamment le perchlorate d'ammonium. Ces compositions sont très intéressantes car elles présentent une bonne vitesse de combustion et une excellente stabilité au vieillissement.Various families of compositions have been developed for this purpose. One of these families concerns Composite compositions made up basically by an organic binder and by a oxidizing charge such as perchlorate ammonium. These compositions are very interesting because they have a good rate of combustion and a excellent aging stability.
Il a ainsi été proposé dans le brevet n°FR 2 137 619 ou dans son correspondant n°US 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 been proposed in the patent No. FR 2 137 619 or in his correspondent No. US 3,723,205 of compositions whose binder is a polyvinyl chloride and whose oxidizing charge is ammonium perchlorate in the presence of sodium nitrate as an internal sensor chlorine. Nevertheless, the use of a chlorinated binder in presence of energy charges is a delicate work, particularly in terms of security and the non-toxicity of the gases generated.
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. Des compositions de ce type sont par exemple décrites dans le brevet US 3,814,694. Cependant, du fait de la présence d'azotures les rendant très toxiques en fonctionnement, ces compositions sont peu recommandées.It has also been proposed compositions based ammonium perchlorate and sodium nitrate mixed with nitro compounds such as azides or metal nitrides. Compositions of this type are for example described in US Patent 3,814,694. However, due to the presence of azides making them very toxic in operation, these compositions are not recommended.
Le brevet US 4,909,549 décrit 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 générent 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.U.S. Patent 4,909,549 discloses compositions consisting of a mixture of ammonium perchlorate and of sodium nitrate combined with a nitrogen compound of triazole or tetrazole. Such compositions generate many clean, nitrogen-rich gases, but these gases are relatively toxic and need to be diluted with air for safe use automobile.
Il a aussi été proposé des compositions constituées par un liant silicone et par un mélange de perchlorate d'ammonium et de nitrate de sodium. De telles compositions décrites par exemple dans le brevet n°FR 2 728 562 ou dans son correspondant américain n°US 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 have also been proposed by a silicone binder and a mixture of perchlorate ammonium and sodium nitrate. Such compositions described for example in Patent No. FR 2 728,562 or in his US correspondent US No. 5,610,444, generate many clean gases, rich in nitrogen and non-toxic but have the disadvantage of burn at very high temperatures.
Il est connu également par la demande de brevet n°US 6,190,474 une composition pyrotechnique génératrice de gaz brûlant à des températures relativement faibles comprises entre 2000 et 2200 K, comportant notamment une charge réductrice constituée par la nitroguanidine et un agent oxydant composé par exemple, d'un nitrate alcalin ou alcalino-terreux ou d'un oxyde métallique ou d'un mélange des deux. Cette composition comporte par exemple de 20 à 80% en masse de nitroguanidine et de 80 à 20% en masse d'agent oxydant. Ce type de composition génère des gaz à des températures inférieures à 2200 K, ce qui constitue un avantage pour une utilisation en sécurité automobile. Toutefois, les vitesses de combustion de ces compositions demeurent trop faibles pour pouvoir être utilisées efficacement dans des générateurs de gaz destinés à la sécurité automobile.It is also known from the patent application No. 6,190,474 a pyrotechnic composition generating of burning gas at relatively low temperatures between 2000 and 2200 K, including in particular reducing charge constituted by nitroguanidine and a oxidizing agent composed for example of an alkaline nitrate or alkaline earth metal or a metal oxide or mix of both. This composition comprises, for example from 20 to 80% by weight of nitroguanidine and from 80 to 20% by weight mass of oxidizing agent. This type of composition generates gas at temperatures below 2200 K, which is an advantage for safe use automobile. However, the burning rates of these compositions remain too weak to be used effectively in gas generators intended for automotive safety.
Le brevet n°FR 2 772 370 ou son correspondant américain n°US 6,533,878 décrit une composition générant des gaz propres et non toxiques, à des températures acceptables pour la sécurité automobile, c'est-à-dire inférieures à 2200 K. Cette composition comporte plus particulièrement un liant réducteur réticulé et une charge oxydante principale constituée d'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 potassium et le carbonate de lithium. Cette composition comporte également des additifs contenant au moins un composé du cuivre comme l'oxyde de cuivre et un composé organique azoté comme par exemple la nitroguanidine ou le nitrate de guanidinium. Cette composition brûle à des vitesses de combustion et à des températures tout à fait adaptées à une utilisation en sécurité automobile.Patent No. FR 2,772,370 or its corresponding US Pat. No. 6,533,878 discloses a generating composition clean, non-toxic gases at high temperatures acceptable for automotive safety, that is to say less than 2200 K. This composition contains more particularly a crosslinked reducing binder and a main oxidizing charge consisting of a mixture of ammonium perchlorate combined with a chlorine sensor selected from the group consisting of nitrate sodium, potassium carbonate and carbonate of lithium. This composition also includes additives containing at least one copper compound as copper oxide and a nitrogenous organic compound like for example nitroguanidine or nitrate guanidinium. This composition burns at combustion and at temperatures quite suitable for use in automobile safety.
Cette demande de brevet décrit certaines compositions dans lesquelles le perchlorate d'ammonium est largement majoritaire. Or, même s'il est vrai que le perchlorate d'ammonium est très oxydant et présente un très bon rendement gazeux, il accroít la température de combustion de la composition et contribue à augmenter fortement la création de produits à base de chlore comme le chlorure d'hydrogène, ces produits formant des gouttelettes et des particules difficiles à filtrer et sources de fumées abondantes. Or, la formation de fumées est un phénomène qu'il est nécessaire de limiter au maximum.This patent application describes certain compositions in which ammonium perchlorate is largely in the majority. Although it is true that ammonium perchlorate is highly oxidizing and has a very good gas yield, it increases the temperature of burning of the composition and helps to increase strongly the creation of chlorine-based products as hydrogen chloride, these products forming droplets and particles difficult to filter and abundant sources of smoke. However, the formation of fumes is a phenomenon that needs to be maximum.
Il est connu également par la demande de brevet n°DE 298 21 541 (correspondant n°EP 1 006 096) une composition génératrice de gaz comportant 20 à 60% d'un combustible et 40 à 80% d'un mélange oxydant. Le combustible comporte au moins 95% d'un composé organique azoté (nitrate de guanidine), tandis que le mélange oxydant comporte de 20 à 80% d'un oxyde métallique, 0 à 50% de nitrate basique de cuivre, de 1 à 15% d'un chlorate métallique ou de perchlorate d'ammonium et de 1 à 15% d'un nitrate alcalin ou alcalino-terreux. Cette composition présente un taux de perchlorate d'ammonium faible ce qui permet de limiter la formation de fumées et la production de chlorure d'hydrogène (HCl). Cependant, le perchlorate d'ammonium permet notamment de conférer à la composition un bon rendement gazeux, une vitesse de combustion plutôt élevée et une bonne allumabilité. De plus, en réglant la granulométrie des du perchlorate d'ammonium, il est possible de régler la balistique de la composition. L'utilisation à faible taux du perchlorate d'ammonium dans la composition décrite dans la demande n°DE 298 21 541 ne permet pas de profiter pleinement de ces avantages. Enfin, cette composition qui est basée sur l'emploi majoritaire d'oxydes métalliques ne peut être mise en oeuvre que par pastillage. Le faible taux de perchlorate d'ammonium, qui présente une balance en oxygène élevée, n'autorise pas l'utilisation d'un liant en très grande quantité et donc ne permet pas la mise en oeuvre par extrusion.It is also known from the patent application No. DE 298 21 541 (corresponding No. EP 1 006 096) a gas generating composition comprising 20 to 60% of a fuel and 40 to 80% of an oxidizing mixture. The fuel contains at least 95% of an organic compound nitrogen (guanidine nitrate), while the mixture oxidant comprises from 20 to 80% of a metal oxide, 0 to 50% basic nitrate of copper, from 1 to 15% of a metal chlorate or ammonium perchlorate and 1 at 15% of an alkaline or alkaline earth nitrate. This composition has a level of ammonium perchlorate low which limits the formation of fumes and the production of hydrogen chloride (HCl). However, ammonium perchlorate makes it possible to give the composition a good gas yield, a rather high burning speed and good ignitability. Moreover, by regulating the granulometry of ammonium perchlorate, it is possible to adjust the ballistics of the composition. Low use ammonium perchlorate content in the composition described in application No. DE 298 21 541 does not allow take full advantage of these benefits. Finally, this composition that is based on majority employment metal oxides can only be implemented by pelletizing. The low level of ammonium perchlorate, which has a high oxygen balance, does not allow not the use of a binder in very large quantities and therefore does not allow the implementation by extrusion.
Dans la demande n°EP 1 130 008 (correspondant n°US 6,592,778) est décrite une composition génératrice de gaz comportant 45% de nitrate de guanidine, 13% d'oxyde de cuivre, 25% de nitrate basique de cuivre, 4% de perchlorate d'ammonium, 3% de nitrate de sodium, 10% d'oxyde de fer et 24% d'une solution à 2% d'hydroxyéthylcellulose. L'hydroxyéthylcellulose est utilisé comme agent épaississant de la composition. Comme dans la demande n°DE 298 21 541, la composition décrite dans cette demande n°EP 1 130 008 présente un faible taux de perchlorate d'ammonium. Cette composition présente donc les mêmes inconvénients que celle décrite précédemment. Cependant, ce document décrit un procédé permettant une production par extrusion par l'utilisation d'un agent épaississant.In the application No. EP 1 130 008 (corresponding US No. 6,592,778) is described a composition generating gas with 45% guanidine nitrate, 13% oxide of copper, 25% of basic copper nitrate, 4% of ammonium perchlorate, 3% sodium nitrate, 10% of iron oxide and 24% of a 2% solution hydroxyethyl cellulose. Hydroxyethylcellulose is used as a thickening agent of the composition. As in application no DE 298 21 541, the composition described in this application No. EP 1 130 008 discloses a low level of ammonium perchlorate. This composition therefore has the same disadvantages as described previously. However, this document describes a process allowing extrusion production by the use of a thickening agent.
Le but de l'invention est donc de proposer une composition pyrotechnique générant des gaz propres, non toxiques, à des températures faibles inférieures à 2200K, ayant un intérêt balistique, garantissant un bon rendement gazeux et une bonne allumabilité et créant peu de fumées et peu de chlorure d'hydrogène.The object of the invention is therefore to propose a pyrotechnic composition generating clean gases, no toxic, at low temperatures below 2200K, having a ballistic interest, guaranteeing a good gas performance and good ignitability and creating little fumes and little hydrogen chloride.
Ce but est atteint par une composition pyrotechnique génératrice de gaz, cette composition étant caractérisée en ce qu'elle comporte une première charge oxydante constituée par du perchlorate d'ammonium présent à une teneur pondérale comprise entre 15 et 30% du poids total de la composition, et une seconde charge oxydante constituée d'un oxyde métallique choisi dans le groupe constitué par l'oxyde de cuivre, l'oxyde de manganèse et un mélange de ces deux composés, le rapport pondéral première charge oxydante/seconde charge oxydante étant inférieur à 1, ladite composition comprenant également une charge réductrice sous la forme d'un composé organique azoté choisi dans le groupe constitué par la nitroguanidine, le nitrate de guanidinium, l'oxamide, le dicyandiamide et les cyanamides métalliques.This goal is achieved by a composition pyrotechnic gas generator, this composition characterized in that it comprises a first oxidizing charge consisting of ammonium perchlorate present at a weight content between 15 and 30% of the total weight of the composition, and a second charge oxidizing agent consisting of a metal oxide selected from group consisting of copper oxide, oxide of manganese and a mixture of these two compounds, the ratio weight first oxidizing charge / second charge oxidant being less than 1, said composition also comprising a reducing charge in the form a nitrogenous organic compound selected from the group consisting of nitroguanidine, nitrate guanidinium, oxamide, dicyandiamide and metallic cyanamides.
Selon l'invention, la teneur pondérale de la première charge oxydante, c'est-à-dire de perchlorate d'ammonium, est comprise entre 15 et 30% du poids total de la composition. Le perchlorate d'ammonium est un oxydant très fort et présente un très bon rendement gazeux. Son caractère fortement oxydant permet notamment d'accroítre la proportion de charge réductrice et donc par exemple de nitrate de guanidinium dans la composition, ce dernier ayant lui aussi un très bon rendement gazeux. La présence du perchlorate d'ammonium dans la composition permet d'obtenir une vitesse de combustion de la composition élevée. La vitesse de combustion est réglable par la granulométrie du perchlorate d'ammonium présent dans le composé pyrotechnique à brûler. La vitesse de combustion peut également être réglée par l'emploi de catalyseurs de combustion de la composition. Le fait de disposer d'une composition dont la vitesse de combustion est de par la nature de ses constituants très forte, présente un certain avantage. En effet, en sécurité automobile, la quasi-totalité de la composition pyrotechnique doit avoir brûlé, sous une pression de l'ordre de 200 MPa, en 30 à 40 millisecondes pour une utilisation dans un airbag passager ou conducteur ou en 10 millisecondes pour une utilisation dans un airbag latéral. Ces temps de combustion constituent un impératif à respecter dans une composition destinée à la sécurité automobile. La durée de combustion étant directement le quotient de l'épaisseur à brûler sur la vitesse de combustion, l'on voit tout de suite que si la vitesse de combustion de la composition est importante, il sera possible de réaliser des blocs monolithiques plus épais donc éventuellement extrudables ou des pastilles plus épaisses donc plus simples à fabriquer tout en conservant des durées de combustion faibles. Selon l'invention, l'utilisation du perchlorate d'ammonium, conférant à la composition une vitesse de combustion élevée, permet également de s'affranchir des variations d'épaisseurs pouvant apparaítre sur le composé à brûler lors de sa fabrication et donc d'éviter des écarts de fonctionnement liés à ces variations lors de la combustion du composé.According to the invention, the weight content of the first oxidizing charge, that is perchlorate of ammonium, is between 15 and 30% of the total weight of the composition. Ammonium perchlorate is a very strong oxidant and has a very good performance gaseous. Its strongly oxidizing nature makes it particularly to increase the proportion of reducing charge and therefore for example guanidinium nitrate in the composition, the latter having a very good gas yield. The presence of ammonium perchlorate in the composition makes it possible to obtain a speed of combustion of the high composition. The speed of combustion is adjustable by the particle size of the ammonium perchlorate present in the compound pyrotechnic to burn. The burning speed can also be regulated by the use of catalysts combustion of the composition. Having a composition whose rate of combustion is by the nature of its constituents very strong, presents a some advantage. Indeed, in car safety, the almost all of the pyrotechnic composition must burned under a pressure of the order of 200 MPa, 30 to 40 milliseconds for use in a passenger or driver airbag or in 10 milliseconds for use in a side airbag. These days combustion are an imperative to be respected in a composition for automotive safety. The duration of combustion being directly the quotient of the thickness to burn on the burning rate, one see right away that if the burning speed of the composition is important, it will be possible to achieve thicker monolithic blocks so possibly extrudable or thicker pellets so more simple to manufacture while maintaining durations of low combustion. According to the invention, the use of ammonium perchlorate, conferring on the composition a high combustion rate, also allows to avoid variations in thicknesses that may appear on the compound to be burned during its manufacturing and therefore avoid deviations from functioning related to these variations during the combustion of the compound.
De plus, lorsque le produit pyrotechnique obtenu brûle en couches parallèles, la vitesse de combustion Vc répond à la loi suivante : Vc = a*pn dans laquelle a est une constante et n l'exposant de pression. La combustion d'un composé pyrotechnique est avant tout une réaction chimique, elle est donc dépendante de la température. Or, l'utilisation du perchlorate d'ammonium permet de baisser l'exposant de pression, ce qui rend la composition moins dépendante de la pression et donc moins dépendante de la température. Selon l'invention, l'exposant de pression est particulièrement faible, largement inférieur à 0,7, ce qui permet de pouvoir faire fonctionner le composé pyrotechnique à des températures comprises entre -35°C et 85°C. La composition selon l'invention pourra donc être utilisée dans un véhicule automobile.Moreover, when the pyrotechnic product obtained burns in parallel layers, the combustion rate V c corresponds to the following law: V c = a * p n in which a is a constant and n is the pressure exponent. The combustion of a pyrotechnic compound is primarily a chemical reaction, so it is temperature dependent. However, the use of ammonium perchlorate makes it possible to lower the pressure exponent, which makes the composition less dependent on the pressure and therefore less dependent on the temperature. According to the invention, the pressure exponent is particularly low, much lower than 0.7, which makes it possible to operate the pyrotechnic compound at temperatures between -35 ° C and 85 ° C. The composition according to the invention can therefore be used in a motor vehicle.
La composition selon l'invention ne comporte pas forcément de liant. Toutefois, pour conférer une bonne tenue mécanique aux composés pyrotechniques finaux obtenus comme des pastilles, des disques ou des blocs monolithiques, un liant peut être ajouté dans la composition.The composition according to the invention does not comprise necessarily binder. However, to confer a good mechanical resistance to final pyrotechnic compounds obtained as pellets, discs or blocks monolithic, a binder can be added in the composition.
Il est connu que dans le domaine de la sécurité automobile, les compositions doivent disposer d'une balance en oxygène (dénommé OB pour "Oxygen Balance") équilibrée. Par définition, une composition est dite équilibrée en oxygène lorsque la composition comporte suffisamment d'oxygène pour qu'après réaction, les divers composés de la composition se retrouvent sous la forme de CO2, d'H2O et de N2. Les balances en oxygène des liants sont en général très faibles et nécessitent souvent d'être compensées. La présence de perchlorate d'ammonium dans une composition permet une telle compensation. Cependant, le perchlorate d'ammonium ne doit pas être à un taux trop élevé dans la composition afin d'éviter les inconvénients liés à son utilisation comme la production de chlorure d'hydrogène ou la création de fumées. It is known that in the field of automotive safety, the compositions must have a balanced oxygen balance (called OB for "Oxygen Balance"). By definition, a composition is said to be balanced in oxygen when the composition comprises sufficient oxygen so that after reaction, the various compounds of the composition are found in the form of CO 2 , H 2 O and N 2 . The oxygen balances of the binders are generally very low and often need to be compensated. The presence of ammonium perchlorate in a composition allows such compensation. However, the ammonium perchlorate should not be at a rate too high in the composition to avoid the disadvantages associated with its use as the production of hydrogen chloride or the creation of fumes.
La balance en oxygène du liant doit être la moins faible possible. Un ajustement de la balance en oxygène autour de l'équilibre permet également de limiter la quantité de chlorures formés.The oxygen balance of the binder must be the least low possible. An adjustment of the oxygen balance around the balance also helps to limit the amount of chlorides formed.
Selon l'invention, la proportion relativement élevée de perchlorate d'ammonium dans la composition selon l'invention permet de pouvoir incorporer un liant à un taux suffisant pour pouvoir mettre en oeuvre la composition par extrusion.According to the invention, the proportion high level of ammonium perchlorate in the composition according to the invention makes it possible to incorporate a binder at a sufficient rate to be able to implement the extrusion composition.
Selon un mode de réalisation de l'invention, la composition comporte un liant choisi dans le groupe constitué par une méthyl-cellulose et l'alcool polyvinylique. Selon un mode de réalisation préféré de l'invention, le liant retenu est la carboxyméthylcellulose de sodium (ci-après CMC-Na). En effet, selon l'invention, ce liant présente notamment une bonne tenue en vieillissement mesurée lors du test de vieillissement effectué pendant 400 heures à 107°C.According to one embodiment of the invention, the composition comprises a binder selected from the group consisting of methyl cellulose and alcohol Polyvinyl. According to a preferred embodiment of the invention, the binder retained is the sodium carboxymethylcellulose (hereinafter CMC-Na). In effect, according to the invention, this binder presents in particular a good aging performance measured during the test of aging carried out for 400 hours at 107 ° C.
Selon l'invention, le liant choisi est la carboxyméthylcellulose de sodium. Ce liant présente une balance en oxygène de -103,5% (degré de substitution de 0,7) ce qui est notamment beaucoup plus élevée que la balance en oxygène de liants de type élastomérique. Le liant carboxyméthylcellulose de sodium se prête également très bien à l'extrusion, à des opérations de granulation et à la compression et sera donc parfaitement adapté pour la mise en oeuvre de la composition sous forme de pastilles, de disques ou de blocs monolithiques.According to the invention, the binder chosen is the sodium carboxymethylcellulose. This binder has a oxygen balance of -103.5% (degree of substitution of 0.7) which is notably much higher than the Oxygen balance of elastomeric type binders. The sodium carboxymethylcellulose binder is suitable also very good at extrusion, granulation and compression and so will perfectly adapted for the implementation of the composition in the form of pellets, discs or monolithic blocks.
La composition décrite dans la demande de brevet antérieure n°FR 2 772 370 comporte un liant réducteur réticulé à base de résine silicone ou à base de résine époxy. Le liant est présent dans cette composition à un taux compris entre 6% et 10% du poids total de la composition. Pour pouvoir être obtenue par extrusion avec une extrudeuse bi-vis, une composition doit comporter un taux minimal de liant de l'ordre de 4 ou 5% du poids total de la composition et nécessite l'emploi d'un solvant du liant. Les liants retenus dans cette composition de l'art antérieur imposent l'emploi de solvants organiques ou halogénés. Or l'utilisation de solvants halogénés tels que par exemple le trichloréthylène est réglementée ce qui complique grandement la fabrication d'une telle composition et augmente son coût de fabrication. De même l'emploi de solvants organiques amène à mettre en place des solutions complexes pour maítriser les émissions de composés organiques volatiles (COV).The composition described in the patent application No. 2,772,370 comprises a reducing binder crosslinked based on silicone resin or resin-based epoxy. The binder is present in this composition at a between 6% and 10% of the total weight of the composition. To be obtained by extrusion with a twin-screw extruder, a composition must have a minimum binder rate of around 4% or 5% of the total weight of the composition and requires the use a solvent of the binder. The binders retained in this composition of the prior art require the use of organic or halogenated solvents. But the use of halogenated solvents such as for example the trichlorethylene is regulated which complicates greatly the manufacture of such a composition and increases its manufacturing cost. Similarly, the use of organic solvents leads to the establishment of complex solutions to control emissions from volatile organic compounds (VOCs).
Selon l'invention, le liant comme par exemple la carboxyméthylcellulose de sodium est soluble dans l'eau ce qui permet d'éviter d'avoir recours, comme dans l'art antérieur, à des solvants halogénés ou organiques lors des étapes de granulation ou d'extrusion intervenant dans la fabrication des composés pyrotechniques.According to the invention, the binder, for example the sodium carboxymethylcellulose is soluble in water which makes it possible to avoid having recourse, as in the art prior to halogenated or organic solvents when granulation or extrusion steps in the manufacture of pyrotechnic compounds.
Selon une particularité, la teneur pondérale du liant représente au maximum 6% du poids total de la composition. Comme décrit ci-dessus, le liant présente en règle générale une balance en oxygène très faible. Pour ne pas pénaliser trop fortement la balance en oxygène de la composition, la proportion de liant dans la composition doit donc rester très faible.According to a particularity, the weight content of the binder represents not more than 6% of the total weight of the composition. As described above, the binder presents as a rule a very low oxygen balance. So as not to penalize the balance too much oxygen content of the composition, the proportion of binder in the composition must therefore remain very low.
Selon une autre particularité, la composition comporte des additifs facilitant sa fabrication. Ces additifs sont par exemple le stéarate de calcium et permettent lorsque la composition selon l'invention ne comporte pas de liant de faciliter sa fabrication.According to another particularity, the composition contains additives facilitating its manufacture. These additives are for example calcium stearate and allow when the composition according to the invention has no binder to facilitate its manufacture.
Selon un mode de réalisation de l'invention, le composé organique azoté, choisi parmi la nitroguanidine, le nitrate de guanidinium, l'oxamide, le dicyandiamide et les cyanamides métalliques, est à une teneur pondérale comprise entre 30 et 50% du poids total de la composition. Dans la composition, le composé organique azoté est la charge réductrice et est un constituant à part entière de la composition, le liant, lorsqu'il est présent, intervenant alors plutôt comme additif. Préférentiellement, la charge réductrice choisie est le nitrate de guanidinium. En effet le nitrate de guanidinium présente une très bonne tenue en vieillissement mesurée par le test de 400 heures à 107°C. De plus, la présence du nitrate de guanidinium dans la composition améliore le rendement gazeux de la composition. Le nitrate de guanidinium présente une enthalpie de formation négative ayant également pour effet d'abaisser la température de combustion de la composition.According to one embodiment of the invention, the nitrogenous organic compound chosen from nitroguanidine, guanidinium nitrate, oxamide, dicyandiamide and metallic cyanamides, is at a grade between 30 and 50% of the total weight of the composition. In the composition, the organic compound nitrogen is the reducing charge and is a constituent part of the composition, the binder, when it is present, intervening rather as an additive. Preferably, the reducing load chosen is the guanidinium nitrate. Indeed the nitrate of guanidinium has a very good behavior in aging measured by the 400-hour test at 107 ° C. In addition, the presence of guanidinium nitrate in the composition improves the gas yield of the composition. Guanidinium nitrate has a enthalpy of negative training also having for effect of lowering the combustion temperature of the composition.
Selon un mode de réalisation préféré de l'invention, la teneur pondérale de la seconde charge oxydante est comprise entre 30 et 45% du poids total de la composition. La présence de cette seconde charge oxydante permet notamment de limiter la quantité de perchlorate d'ammonium dans la composition. Même si, comme décrit ci-dessus, le perchlorate d'ammonium est un oxydant fort et présente des propriétés intéressantes en combustion, son emploi dans une composition conduit en effet à l'obtention de températures de combustion élevées et à la génération de gaz de combustion comportant un taux assez élevé de chlorure d'hydrogène. Cette seconde charge oxydante est un oxyde métallique et préférentiellement l'oxyde de cuivre CuO ou l'oxyde de manganèse MnO2. Un mélange de ces deux oxydes peut également être utilisé comme seconde charge oxydante. Cette seconde charge oxydante est présente à un taux très élevé dans la composition et à un taux supérieur à celui du perchlorate d'ammonium. Elle présente une enthalpie de formation faible de manière à abaisser la température de combustion de la composition. En effet, par exemple, l'enthalpie de formation de l'oxyde de cuivre CuO est de -155 KJ/mol. L'oxyde de cuivre présente également l'avantage d'être un excellent catalyseur de combustion du perchlorate d'ammonium ce qui permet de conférer à la composition une vitesse de combustion élevée la rendant très adaptée pour une utilisation en sécurité automobile.According to a preferred embodiment of the invention, the weight content of the second oxidizing charge is between 30 and 45% of the total weight of the composition. The presence of this second oxidizing charge makes it possible in particular to limit the amount of ammonium perchlorate in the composition. Although, as described above, ammonium perchlorate is a strong oxidant and has interesting properties in combustion, its use in a composition leads to the achievement of high combustion temperatures and the generation of gas. combustion with a fairly high rate of hydrogen chloride. This second oxidizing charge is a metal oxide and preferably copper oxide CuO or manganese oxide MnO 2 . A mixture of these two oxides can also be used as the second oxidizing charge. This second oxidizing charge is present at a very high level in the composition and at a rate higher than that of ammonium perchlorate. It has a low formation enthalpy so as to lower the combustion temperature of the composition. Indeed, for example, the formation enthalpy of copper oxide CuO is -155 KJ / mol. Copper oxide also has the advantage of being an excellent combustion catalyst ammonium perchlorate which allows to give the composition a high rate of combustion making it very suitable for use in automotive safety.
Selon l'invention, la composition peut également comprendre des agents de piégeage des particules solides émises lors de la combustion de manière à créer des résidus d'une taille suffisamment importante pour pouvoir être filtrées. Des additifs bien connus dans le domaine des compositions pour sécurité automobile comme par exemple l'alumine ou la silice peuvent être ajoutées dans la composition selon l'invention.According to the invention, the composition may also include solid particle trapping agents emitted during combustion in order to create residues of a sufficiently large size to can be filtered. Well known additives in the domain of automotive safety compositions like for example alumina or silica can be added in the composition according to the invention.
Selon une particularité, les cyanamides métalliques éventuellement présentes dans la composition sont constituées par les cyanamides de sodium, de zinc et de cuivre. Préférentiellement la cyanamide métallique choisie est la cyanamide de zinc ZnCN2.According to a feature, the metal cyanamides optionally present in the composition are constituted by cyanamides of sodium, zinc and copper. Preferably, the metal cyanamide chosen is zinc cyanamide ZnCN 2 .
Selon l'invention, des composés pyrotechniques ayant une composition telle que décrite ci-dessus peuvent être fabriqués à cadence élevée par compression de disques ou par pastillage. Avant l'opération de pastillage, une étape de préparation de la poudre doit être mise en oeuvre. Cette étape ne se réduit pas à un simple mélange à sec des différents constituants. En effet, pour pouvoir mettre en oeuvre l'opération de pastillage, il est nécessaire d'obtenir une poudre qui s'écoule bien. Cette étape de préparation est une opération de granulation consistant à partir des différentes matières entrant dans la constitution de la composition selon l'invention et présentes sous forme pulvérulente à faire des grains à granulométrie plus élevée de l'ordre de quelques centaines de microns. Une fois cette poudre obtenue, l'opération de pastillage peut être mise en oeuvre. According to the invention, pyrotechnic compounds having a composition as described above can be manufactured at high speed by compression discs or by pelletizing. Before the operation pelletizing, a powder preparation step must to be implemented. This step is not just a simple dry mixing of the various constituents. In effect, in order to be able to implement the pelletizing, it is necessary to obtain a powder which flows well. This preparation step is a granulation operation consisting of different matters forming part of the constitution of the composition according to the invention and present in form powdery to make grains with more granulometry high of the order of a few hundred microns. A once this powder obtained, the pelletizing operation can be implemented.
Selon l'invention, les produits pyrotechniques peuvent également être obtenus par extrusion à l'aide d'une extrudeuse bi-vis. Pour cela, il est nécessaire d'incorporer un liant tel que la carboxyméthylcellulose de sodium dans la composition et d'utiliser un solvant. Comme décrit ci-dessus, contrairement à certains liants et notamment à ceux utilisés dans l'art antérieur, la carboxyméthylcellulose de sodium est soluble dans l'eau. L'utilisation de la carboxyméthylcellulose de sodium n'impose donc pas l'emploi de solvants halogénés ou organiques. Une faible proportion d'eau est incorporée au mélange de manière à éviter la solubilisation du perchlorate d'ammonium. Selon l'invention, le procédé d'obtention de composés pyrotechniques ayant une composition selon l'invention telle que décrite ci-dessus comporte tout d'abord une étape d'alimentation en continu d'un appareil de malaxage et d'extrusion, comme par exemple une extrudeuse bi-vis, d'une part avec les deux charges oxydantes et d'autre part avec le composé organique azoté prémélangé avec le liant, c'est-à-dire avec la carboxyméthylcellulose de sodium. Après malaxage, à l'aide de l'extrudeuse, on extrude un jonc profilé qui est durci en étuve et découpé à la longueur voulue, par exemple pour former des granulats.According to the invention, the pyrotechnic products can also be obtained by extrusion using of a twin-screw extruder. For this, it is necessary to incorporate a binder such as carboxymethylcellulose of sodium in the composition and use a solvent. As described above, unlike some binders and in particular to those used in the prior art, the sodium carboxymethylcellulose is soluble in water. The use of sodium carboxymethylcellulose does not therefore require the use of halogenated solvents or organic. A small proportion of water is incorporated to the mixture so as to avoid solubilization of the ammonium perchlorate. According to the invention, the method for obtaining pyrotechnic compounds having a composition according to the invention as described above first of all involves a step of feeding into continuous mixing and extrusion apparatus, such as for example a twin-screw extruder, on the one hand with the two oxidizing charges and secondly with the compound organic nitrogen premixed with the binder, i.e. with sodium carboxymethylcellulose. After mixing, using the extruder, extrude a rod profile which is hardened in an oven and cut to length wanted, for example to form aggregates.
Le tableau présenté ci-dessous montre quelques
exemples de formulation de la composition selon
l'invention et les performances affichées par chacune de
ces formulations/
Dans ce tableau, les abréviations suivantes ont été
employées :
Nous remarquons qu'une certaine quantité de glycérine peut être ajoutée à la composition. We notice that a certain amount of glycerin can be added to the composition.
Pour un tir dans un tank de 60 litres de 24 grammes
d'une composition comprenant 2% de liant CMC-Na, 26,4%
de perchlorate d'ammonium, 30% d'oxyde de cuivre et
41,6% de nitrate de guanidinium, pour une masse de
composition de 24 grammes, nous obtenons les résultats
suivants :
Le tableau ci-après présente les résultats obtenus pour un tir dans un tank de 60 litres de 18 grammes d'une composition comprenant 2% de liant CMC-Na, 26,4% de perchlorate d'ammonium, 30% d'oxyde de cuivre et 41,6% de nitrate de guanidinium, à t0, après un vieillissement de 400 heures à 107 °C, et après un cyclage. Le cyclage consiste à appliquer ici 183 cycles sur la composition définie ci-dessus, un cycle étant composé :
- D'un maintien de la composition pendant 40 minutes à -40°C,
- D'une montée en température en 60 minutes jusqu'à 107°C,
- D'un maintien pendant 40 minutes à cette température de 107°C,
- D'une descente en température en 60 minutes jusqu'à
-40°C.
t0 Après 400h à 107°C Après cyclage Vc (20 MPa) en mm/s 29,6 31 30 n (15-30 MPa) 0,30 0,42 0,41 Tirs en tank 60 litres (18g de composition) : CO (ppm) NOx (ppm) 2300
5202320
4202730
430Pmax tank (MPa) 0,170 0,183 0,176 n = Exposant de pression
- Maintaining the composition for 40 minutes at -40 ° C.
- From a rise in temperature in 60 minutes to 107 ° C,
- Hold for 40 minutes at this temperature of 107 ° C,
- From a temperature drop in 60 minutes to -40 ° C.
t 0 After 400h at 107 ° C After cycling Vc (20 MPa) in mm / s 29.6 31 30 n (15-30 MPa) 0.30 0.42 0.41 Shots in tank 60 liters (18g of composition): CO (ppm) NOx (ppm) 2300
5202320
4202730
430P max tank (MPa) 0,170 0.183 0.176 n = Pressure exponent
Après un vieillissement de 400 heures à 107°C, la composition a perdu 0,24% de sa masse globale. Au bout de 200 heures, la composition avait déjà perdu 0,23% de sa masse globale. Après ce vieillissement de 400 heures à 107°C, nous remarquons en outre que la composition présente des performances équivalentes à celles existantes avant vieillissement.After an aging of 400 hours at 107 ° C, the composition lost 0.24% of its overall mass. At the end 200 hours, the composition had already lost 0.23% of its overall mass. After this aging of 400 hours at 107 ° C, we also notice that the composition performance equivalent to those existing before aging.
Il doit être évident pour les personnes versées dans l'art que la présente invention permet des modes de réalisation sous de nombreuses autres formes spécifiques sans l'éloigner du domaine d'application de l'invention comme revendiqué. Par conséquent, les présents modes de réalisation doivent être considérés à titre d'illustration, mais peuvent être modifiés dans le domaine défini par la portée des revendications jointes, et l'invention ne doit pas être limitée aux détails donnés ci-dessus.It must be obvious to the people paid in the art that the present invention allows modes of realization in many other specific forms without departing from the scope of the invention as claimed. Therefore, the present modes of realization should be considered illustration but can be modified in the defined by the scope of the attached claims, and the invention should not be limited to details given above.
Claims (12)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0308475 | 2003-07-10 | ||
| FR0308475A FR2857359B1 (en) | 2003-07-10 | 2003-07-10 | GAS GENERATING PYROTECHNIC COMPOSITION FOR MOTOR VEHICLE SAFETY AND BURNING AT COMBUSTION TEMPERATURES LESS THAN 2200 K |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1496036A2 true EP1496036A2 (en) | 2005-01-12 |
Family
ID=33443261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP04291733A Pending EP1496036A2 (en) | 2003-07-10 | 2004-07-08 | Pyrotechnic gas generating composition for car safety systems having a combustion temperature below 2200 degree K |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20050067077A1 (en) |
| EP (1) | EP1496036A2 (en) |
| FR (1) | FR2857359B1 (en) |
| NO (1) | NO20042888L (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2950624A1 (en) * | 2009-09-25 | 2011-04-01 | Snpe Materiaux Energetiques | Pyrotechnic compound comprising ammonium perchlorate oxidative charge, nitrogenous organic charge of at least one compound comprising e.g. triazoles and metal oxide charge, useful in gas generator for airbag and inflate cushioning pillows |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2887247B1 (en) * | 2005-06-15 | 2007-10-12 | Snpe Materiaux Energetiques | PROCESS FOR MANUFACTURING GAS GENERATOR PELLETS COMPRISING A DRY GRANULATION STEP |
| FR2892117B1 (en) * | 2005-10-13 | 2008-05-02 | Snpe Materiaux Energetiques Sa | FAST GAS GENERATING PYROTECHNIC COMPOSITION AND PROCESS FOR OBTAINING THE SAME |
| US8980023B2 (en) * | 2011-07-27 | 2015-03-17 | Autoliv Asp, Inc. | Gas generation via elemental carbon-based compositions |
| ES2870712T3 (en) | 2013-02-01 | 2021-10-27 | Emd Acquisition Llc | Improved Lithium Manganese Oxide Compositions |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5470406A (en) * | 1992-04-10 | 1995-11-28 | Nof Corporation | Gas generator composition and process for manufacturing the same |
| US5962808A (en) * | 1997-03-05 | 1999-10-05 | Automotive Systems Laboratory, Inc. | Gas generant complex oxidizers |
| US6224099B1 (en) * | 1997-07-22 | 2001-05-01 | Cordant Technologies Inc. | Supplemental-restraint-system gas generating device with water-soluble polymeric binder |
| FR2772370B1 (en) * | 1997-12-12 | 2000-01-07 | Poudres & Explosifs Ste Nale | PYROTECHNIC COMPOSITIONS GENERATING NON-TOXIC GASES BASED ON AMMONIUM PERCHLORATE |
| DE29806504U1 (en) * | 1998-04-08 | 1998-08-06 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azide-free, gas generating composition |
| US6096147A (en) * | 1998-07-30 | 2000-08-01 | Autoliv Asp, Inc. | Ignition enhanced gas generant and method |
| DE29821541U1 (en) * | 1998-12-02 | 1999-02-18 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azide-free, gas generating composition |
| JP2001002488A (en) * | 1999-06-17 | 2001-01-09 | Daicel Chem Ind Ltd | Gas generating composition for pretensioner |
| DE10009819A1 (en) * | 2000-03-01 | 2001-09-06 | Trw Airbag Sys Gmbh & Co Kg | A sealed fuel-molded article (sic) useful for gas generators and automobile safety devices prepared by extrusion of a paste contains added thickening agent and required a decreased amount of solvent for paste formation |
| FR2818636B1 (en) * | 2000-12-22 | 2003-02-28 | Poudres & Explosifs Ste Nale | HYDROCARBON BINDER GAS GENERATING PYROTECHNIC COMPOSITIONS AND CONTINUOUS MANUFACTURING METHOD |
-
2003
- 2003-07-10 FR FR0308475A patent/FR2857359B1/en not_active Expired - Fee Related
-
2004
- 2004-07-07 NO NO20042888A patent/NO20042888L/en not_active Application Discontinuation
- 2004-07-08 EP EP04291733A patent/EP1496036A2/en active Pending
- 2004-09-22 US US10/946,073 patent/US20050067077A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2950624A1 (en) * | 2009-09-25 | 2011-04-01 | Snpe Materiaux Energetiques | Pyrotechnic compound comprising ammonium perchlorate oxidative charge, nitrogenous organic charge of at least one compound comprising e.g. triazoles and metal oxide charge, useful in gas generator for airbag and inflate cushioning pillows |
Also Published As
| Publication number | Publication date |
|---|---|
| NO20042888L (en) | 2005-01-11 |
| FR2857359A1 (en) | 2005-01-14 |
| US20050067077A1 (en) | 2005-03-31 |
| FR2857359B1 (en) | 2006-12-01 |
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