EP1496036A2 - Pyrotechnische gaserzeugende Zusammensetzung für Kraftfahrzeugsicherheitsanlage mit einer Verbrennungstemperatur unter 2200 Grad K - Google Patents
Pyrotechnische gaserzeugende Zusammensetzung für Kraftfahrzeugsicherheitsanlage mit einer Verbrennungstemperatur unter 2200 Grad 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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Links
- 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Air Bags (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0308475 | 2003-07-10 | ||
| FR0308475A FR2857359B1 (fr) | 2003-07-10 | 2003-07-10 | Composition pyrotechnique generatrice de gaz destinee a la securite automobile et brulant a des temperatures de combustion inferieures a 2200 k |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1496036A2 true EP1496036A2 (de) | 2005-01-12 |
Family
ID=33443261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP04291733A Pending EP1496036A2 (de) | 2003-07-10 | 2004-07-08 | Pyrotechnische gaserzeugende Zusammensetzung für Kraftfahrzeugsicherheitsanlage mit einer Verbrennungstemperatur unter 2200 Grad K |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20050067077A1 (de) |
| EP (1) | EP1496036A2 (de) |
| FR (1) | FR2857359B1 (de) |
| NO (1) | NO20042888L (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2950624A1 (fr) * | 2009-09-25 | 2011-04-01 | Snpe Materiaux Energetiques | Compose pyrotechnique generateur de gaz |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2887247B1 (fr) * | 2005-06-15 | 2007-10-12 | Snpe Materiaux Energetiques | Procede de fabrication de pastilles generatrices de gaz comportant une etape de granulation par voie seche |
| FR2892117B1 (fr) * | 2005-10-13 | 2008-05-02 | Snpe Materiaux Energetiques Sa | Composition pyrotechnique generatrice de gaz rapide et procede d'obtention |
| US8980023B2 (en) * | 2011-07-27 | 2015-03-17 | Autoliv Asp, Inc. | Gas generation via elemental carbon-based compositions |
| CN105050960A (zh) | 2013-02-01 | 2015-11-11 | 特罗诺克斯有限公司 | 改善的锂锰氧化物组合物 |
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 (fr) * | 1997-12-12 | 2000-01-07 | Poudres & Explosifs Ste Nale | Compositions pyrotechniques generatrices de gaz non toxiques a base de perchlorate d'ammonium |
| DE29806504U1 (de) * | 1998-04-08 | 1998-08-06 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azidfreie, gaserzeugende Zusammensetzung |
| US6096147A (en) * | 1998-07-30 | 2000-08-01 | Autoliv Asp, Inc. | Ignition enhanced gas generant and method |
| DE29821541U1 (de) * | 1998-12-02 | 1999-02-18 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azidfreie, gaserzeugende Zusammensetzung |
| JP2001002488A (ja) * | 1999-06-17 | 2001-01-09 | Daicel Chem Ind Ltd | プリテンショナー用ガス発生剤組成物 |
| DE10009819A1 (de) * | 2000-03-01 | 2001-09-06 | Trw Airbag Sys Gmbh & Co Kg | Verfahren zur Herstellung von Treibstoff-Formlingen |
| FR2818636B1 (fr) * | 2000-12-22 | 2003-02-28 | Poudres & Explosifs Ste Nale | Compositions pyrotechniques generatrices de gaz a liant hydrocarbone et procede de fabrication en continu |
-
2003
- 2003-07-10 FR FR0308475A patent/FR2857359B1/fr not_active Expired - Fee Related
-
2004
- 2004-07-07 NO NO20042888A patent/NO20042888L/no not_active Application Discontinuation
- 2004-07-08 EP EP04291733A patent/EP1496036A2/de 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 (fr) * | 2009-09-25 | 2011-04-01 | Snpe Materiaux Energetiques | Compose pyrotechnique generateur de gaz |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2857359B1 (fr) | 2006-12-01 |
| NO20042888L (no) | 2005-01-11 |
| FR2857359A1 (fr) | 2005-01-14 |
| US20050067077A1 (en) | 2005-03-31 |
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