US20120055593A1 - Gas generating composition - Google Patents
Gas generating composition Download PDFInfo
- Publication number
- US20120055593A1 US20120055593A1 US13/321,426 US201013321426A US2012055593A1 US 20120055593 A1 US20120055593 A1 US 20120055593A1 US 201013321426 A US201013321426 A US 201013321426A US 2012055593 A1 US2012055593 A1 US 2012055593A1
- Authority
- US
- United States
- Prior art keywords
- gas generating
- nitrate
- mass
- generating composition
- bcc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 239000007800 oxidant agent Substances 0.000 claims abstract description 24
- 229940116318 copper carbonate Drugs 0.000 claims abstract description 23
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000000446 fuel Substances 0.000 claims abstract description 11
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 229910002010 basic metal nitrate Inorganic materials 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000007789 gas Substances 0.000 description 70
- 230000000052 comparative effect Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 11
- 230000035945 sensitivity Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- -1 tetrazole compounds Chemical class 0.000 description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 229920000609 methyl cellulose Polymers 0.000 description 6
- 239000001923 methylcellulose Substances 0.000 description 6
- 235000010981 methylcellulose Nutrition 0.000 description 6
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229940105329 carboxymethylcellulose Drugs 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 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 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- 150000002357 guanidines Chemical class 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- 229910001120 nichrome Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229920000896 Ethulose Polymers 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- QGWDKKHSDXWPET-UHFFFAOYSA-E pentabismuth;oxygen(2-);nonahydroxide;tetranitrate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[O-2].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QGWDKKHSDXWPET-UHFFFAOYSA-E 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229940068984 polyvinyl alcohol Drugs 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 description 2
- 229920002907 Guar gum Polymers 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000003862 amino acid derivatives Chemical class 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000000665 guar gum Substances 0.000 description 2
- 235000010417 guar gum Nutrition 0.000 description 2
- 229960002154 guar gum Drugs 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000008108 microcrystalline cellulose Substances 0.000 description 2
- 229940016286 microcrystalline cellulose Drugs 0.000 description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- MJVUDZGNBKFOBF-UHFFFAOYSA-N n-nitronitramide Chemical compound [O-][N+](=O)N[N+]([O-])=O MJVUDZGNBKFOBF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 125000000561 purinyl group Chemical class N1=C(N=C2N=CNC2=C1)* 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- CZGWDPMDAIPURF-UHFFFAOYSA-N (4,6-dihydrazinyl-1,3,5-triazin-2-yl)hydrazine Chemical compound NNC1=NC(NN)=NC(NN)=N1 CZGWDPMDAIPURF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- LPXQRXLUHJKZIE-UHFFFAOYSA-N 8-azaguanine Chemical compound NC1=NC(O)=C2NN=NC2=N1 LPXQRXLUHJKZIE-UHFFFAOYSA-N 0.000 description 1
- 229960005508 8-azaguanine Drugs 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910001964 alkaline earth metal nitrate Inorganic materials 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 210000003127 knee Anatomy 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
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- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- CSGNMMLYYZTWBB-UHFFFAOYSA-N nitric acid;1,3,5-triazine-2,4,6-triamine Chemical compound O[N+]([O-])=O.NC1=NC(N)=NC(N)=N1 CSGNMMLYYZTWBB-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
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- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- ZFPPQTYHQHJOOI-UHFFFAOYSA-N perchloric acid;1,3,5-triazine-2,4,6-triamine Chemical compound [O-]Cl(=O)(=O)=O.NC1=NC(N)=[NH+]C(N)=N1 ZFPPQTYHQHJOOI-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229940032147 starch Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 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 a gas generating composition that can be used for an inflator of a vehicle airbag apparatus.
- a combustion temperature of a gas generating agent needs to be reduced in order to obtain a small and light inflator for a vehicle airbag apparatus, which is highly demanded in recent years.
- reducing the combustion temperature of the gas generating agent often leads to a decrease in burning rate and an amount of generated gas.
- a method for increasing the amount of the gas generating agent for charging an inflator is considered, but with this method, a small and light inflator cannot be obtained.
- basic metal nitrate is disclosed as an oxygen-containing oxidizing agent, which is selected from among basic copper nitrate, basic cobalt nitrate, basic zinc nitrate, basic manganese nitrate, basic iron nitrate, basic molybdenum nitrate, basic bismuth nitrate and basic cerium nitrate, and it is described that the calorific value can be suppressed by adding aluminum hydroxide thereto.
- basic metal nitrate selected from among basic copper nitrate, basic cobalt nitrate, basic zinc nitrate, basic manganese nitrate, basic iron nitrate, basic molybdenum nitrate, basic bismuth nitrate and basic cerium nitrate can be used as an oxidizing agent.
- an oxygen-containing oxidizing agent selected from among metal nitrate, ammonium nitrate, a metal perchlorate salt, ammonium perchlorate, metal nitrite, metal chlorate, basic copper nitrate, basic cobalt nitrate, basic zinc nitrate, and basic manganese nitrate.
- JP-A No. 2006-76849 such a gas generating composition is disclosed that the content of basic copper carbonate exceeds 20% by weight, but is equal to or lower than 40 wt %, but because the content of the basic copper carbonate in the embodiments is only 22.0 wt %, the effects obtained in the cases including 30 or more wt % basic copper carbonate are not confirmed.
- the present invention provides a gas generating composition for use in an inflator of a vehicle airbag apparatus and the like, such that a reduction of the calorific value per mol of generated gas is achieved without impairing burning rate or gas output, and the gas generating composition having no problem with the amount of mist or harmful gas concentration generated in combustion, solving such problems that have not been fully solved in the above prior arts.
- the invention 1 provides a gas generating composition, containing fuel and an oxidizing agent, the oxidizing agent comprising basic copper carbonate, the composition having the content of the basic copper carbonate of more than 40% by mass and 60% by mass or lower, satisfying the following requirements (a) to (c):
- the gas generating composition of the present invention can reduce the calorific value per mol of generated gas without impairing the burning rate or the gas output, by utilizing a predetermined amount of basic copper carbonate, and is free of problems regarding the amount of mist or harmful gas concentration generated in combustion. Therefore, the gas generating composition of the present invention is useful for an inflator of a vehicle airbag apparatus.
- the present invention includes the following preferred embodiments 2 to 6:
- the gas generating composition according to the invention described above further including a carboxymethyl cellulose salt as a binder.
- the gas generating composition of the present invention or a molded article obtained therefrom can be used for, for example, an airbag inflator of a driver's side, an airbag inflator of a passenger side next to the driver, a side airbag inflator, an inflator for an inflatable curtain, an inflator for a knee bolster, an inflator for an inflatable seat belt, an inflator for a tubular system, and a gas generator for a pretensioner, of various vehicles.
- the gas generating composition of the present invention or an inflator that uses a molded article obtained from the gas generating composition may be of a pyrotechnic type in which a gas supply source is only a gas generating agent or of a hybrid type that uses both compressed gas, such as argon, and a gas generating agent.
- gas generating composition of the present invention or a molded article obtained therefrom can be also used as an igniting agent called an enhancer or a booster, which serves to transmit the energy of a detonator or a squib to the gas generating agent.
- the fuel used in the present invention can be a known fuel for a gas generating composition, for example, at least one selected from guanidine compounds, tetrazole compounds, triazine compounds, purine compounds, and amino-acid derivatives.
- Preferred guanidine compounds include guanidine nitrate, nitroguanidine, and guanylurea dinitramide.
- Preferred tetrazole compounds include 5-aminotetrazole and bitetrazole ammonium salt.
- Preferred triazine compounds include melamine, melamine cyanurate, melamine nitrate, melamine perchlorate, trihydrazinotriazine, and a nitrocompound of melamine.
- Preferred purine compounds include 8-azaguanine.
- Preferred amino-acid derivatives include glycine.
- the fuel used in the present invention can be two or more types of mixtures if necessary.
- problems are caused in the burning rate and the ignition ability of the gas generating composition, although the calorific value thereof can be made relatively low.
- the gas output of the gas generating composition becomes relatively low, although there are no problems in the burning rate or the ignition ability thereof.
- the guanidine nitrate and the nitroguanidine can be mixed to obtain a fuel that takes the advantages of the guanidine nitrate and the nitroguanidine and overcomes the disadvantages thereof.
- the content of the fuel used in the present invention is preferably 20 to 60% by mass, more preferably 25 to 55% by mass, or even more preferably 30 to 50% by mass, in the gas generating composition.
- the oxidizing agent used in the present invention contains basic copper carbonate.
- the content of the basic copper carbonate exceeds 40% by mass but is equal to or lower than 60% by mass, or preferably 42 to 60% by mass, in the gas generating composition.
- the basic copper carbonate in an amount of 40% by mass or lower cannot exert the effect of reducing the calorific value, and the basic copper carbonate exceeding 60% by mass impairs the ignition ability.
- An average particle diameter of the basic copper carbonate is preferably equal to or less than 5 ⁇ m, more preferably equal to or less than 3 ⁇ m, or even more preferably equal to or less than 1 ⁇ m.
- the average particle diameter was measured by particle size distribution measurement method based on laser scattering.
- a sample was dispersed in ion-exchange water and irradiated with 50-W ultrasonic waves for 60 seconds. The 50% accumulated value of particle volume was obtained. Average values obtained by two measurements were taken as average particle diameters.
- the oxidizing agent can further contain known oxidizing agent, such as one or more selected from among nitrate, basic metal nitrate, ammonium nitrate, metal perchlorate, ammonium perchlorate, metal nitrite, metal chlorate and the like.
- Examples of basic metal nitrate include one or more selected from among basic copper nitrate, basic cobalt nitrate, basic zinc nitrate, basic manganese nitrate, basic iron nitrate, basic molybdenum nitrate, basic bismuth nitrate and basic cerium nitrate.
- basic copper nitrate is preferred.
- nitrate examples include one or more selected from among alkali metal nitrates such as potassium nitrate and sodium nitrate, as well as alkaline earth metal nitrates such as strontium nitrate. Among these, strontium nitrate is preferred.
- the total content of the oxidizing agent used in the present invention is preferably 50 to 80% by mass, more preferably 50 to 75% by mass, or even more preferably 50 to 70% by mass in the gas generating composition.
- the gas generating composition according to the present invention can contain a known binder of a gas generating composition, if necessary.
- the binder include one or more selected from among carboxymethyl cellulose (CMC), carboxymethyl cellulose sodium salt (CMCNa), carboxymethyl cellulose potassium salt (CMCK), carboxymethyl cellulose ammonium salt (CMCNH 4 ), cellulose acetate, cellulose acetate butyrate (CAB), methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), ethyl hydroxyethyl cellulose (EHEC), hydroxypropyl cellulose (HPC), carboxymethyl ethyl cellulose (CMEC), microcrystalline cellulose, polyacrylamides, aminated compounds of polyacrylamide, polyacryl hydrazide, a copolymer of acrylamide and a metal salt of acrylic acid, a copolymer of polyacrylamide and a polyacrylic acid ester compound, polyvinyl alcohol (PVA
- Water-soluble cellulose derivatives (CMC, CMCNa, CMCK, CMCNH 4 , MC, EC, HEC, EHEC, HPC, CMEC), which are water-soluble binders, microcrystalline cellulose, PVA, guar gum, and starch are preferred as the binder. Above all, the water-soluble cellulose derivatives are preferred, CMC, CMCNa, CMCK and CMCNH 4 are more preferred, and CMCNa is even more preferred.
- the content of the binder used in the present invention is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, or even more preferably 2 to 15 parts by mass, with respect to a total of 100 parts by mass of the fuel and the oxidizing agent.
- the gas generating composition according to the present invention can include a known additive of a gas generating composition, such as a combustion catalyst, a heat absorbing agent, a slag forming agent, a lubricant or the like, according to necessity.
- a gas generating composition such as a combustion catalyst, a heat absorbing agent, a slag forming agent, a lubricant or the like
- the known additive include metal oxides such as copper oxide, iron oxide, zinc oxide, cobalt oxide, manganese oxide, molybdenum oxide, nickel oxide, bismuth oxide, silica, and alumina; metal hydroxides such as aluminum hydroxide, cobalt hydroxide, iron hydroxide, and magnesium hydroxide; metal carbonates or basic metal carbonates such as cobalt carbonate, calcium carbonate, and basic zinc carbonate; complex compounds of metal oxides or hydroxides, such as Japanese acid clay, kaolin, talc, bentonite, diatomaceous earth, and hydrotalcite; ammonium
- the additive used in the present invention may be in such an amount that does not have a great impact on the advantageous effects of the present invention in the calorific value, the gas output and the burning rate.
- the content of the additive is preferably 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, or even more preferably 2 to 20 parts by mass, with respect to a total of 100 parts by mass of the fuel and the oxidizing agent.
- the gas generating composition according to the present invention satisfies the following requirements (a) to (c), and preferably, also satisfies a requirement (d):
- composition according to the present invention can be molded into a desired shape, and a cylindrical molded article, a cylindrical molded article with a single hole, a perforated cylindrical molded article, or a pellet-shaped molded article can be obtained.
- These molded articles can be manufactured by a method in which water or an organic solvent is added to and mixed with the composition and the obtained mixture is extrusion-molded (into the cylindrical molded article, the cylindrical molded article with a single hole, or a perforated cylindrical molded article), or by a compression-molding method using a pelletizer or the like (the pellet-shaped molded article).
- the components of the gas generating composition were adequately mixed in the proportions shown in Table 1, and thereafter 30 g thereof was obtained.
- Water in an amount of 6 g was added thereto, which was then mixed in an antistatic plastic bag for 5 minutes or longer.
- the resultant mass was pulverized into small pieces and dried at 110° C. for two hours.
- the resultant product was then pulverized into powder in a mortar. 1.7 to 2.2 g of the powder was poured into a mold and the pressure of approximately 220 MPa (2250 kgf/cm 2 ) was applied with a hydraulic pump, which was maintained for five seconds, to obtain a cylindrical strand (with a outer diameter of 9.55 mm and a length of 12.70 mm).
- the measuring strand obtained in the manner described above was left in a temperature of 110° C. for 16 hours to eliminate water therefrom. Subsequently, an epoxy resin adhesive “Bond Quick 30” was applied twice to the side surface and one side of the measuring strand so as to ignite and combust the measuring strand from an end surface thereof.
- the resultant strand was installed in an SUS sealed bomb (internal volume thereof was 1 L), and the bomb was pressurized up to 7 MPa, while the inside thereof was purged with nitrogen.
- a voltage of 12 V was applied to a nichrome wire in contact with the end surface of the measuring strand, thereby igniting and combusting the measuring strand by means of the fusing energy of the nichrome wire.
- the length of the measuring strand obtained prior to the combustion was divided by the time that has elapsed since the start of the combustion until when the peak of pressure rise was obtained, and the value obtained by this calculation was taken as the burning rate.
- the gas output, the calorific value per mol of generated gas, and the combustion temperature were calculated through a simulation using a thermochemical equilibrium calculation program “NEWPEP.”
- Powdered ingredients to include in the gas generating composition were each weighed such that the mass of the gas generating composition would be 1 g, and they were mixed adequately.
- the friction sensitivity and the drop-hammer sensitivity of the obtained powder sample were measured based on the explosive performance test method disclosed in Japanese Industrial Standard (JIS) K4810-1979.
- thermogravimetry The same gas generating composition as the one used in the method for measuring the friction sensitivity and the drop-hammer sensitivity was used to perform thermogravimetry by using a thermobalance (TGDTA6300 manufactured by Seiko Epson Corporation). The temperature at which the mass is reduced was taken as a decomposition temperature.
- the measuring strand (with an outer diameter of 9.55 mm and mass of 2.00 g) obtained in the same method as the one described above was left in a temperature of 110° C. for 16 hours to eliminate water therefrom, the measuring strand was installed in an SUS sealed bomb (internal volume thereof was 1 L), and the bomb was pressurized up to 7 MPa, while the inside thereof was purged with nitrogen. After the pressure inside the bomb was stabilized, a predetermined current was passed into a nichrome wire in contact with the end surface of the measuring strand, thereby igniting and combusting the measuring strand by means of the fusing energy of the nichrome wire.
- compositions shown in Table 1 were measured in the manners shown in Table 1.
- Example 1 NQ/BCC/BCN 38.70/42.00/19.30 7.4
- Example 2 GUDN/BCC/BCN 47.84/42.00/10.16 7.9
- Example 3 NQ/BCC/SrN 37.49/52.00/10.51 8.3
- Example 4 GN/NQ/BCC/BCN 15.95/23.93/42.00/18.12 7.7
- Example 5 GN/NQ/BCC/BCN 20.09/20.09/42.00/17.82 7.5
- Example 6 GN/NQ/BCC/BCN 18.77/18.77/52.00/10.46 7.0
- Example 7 GN/NQ/BCC/BCN 27.14/13.57/42.00/17.29 7.0
- Example 8 GN/NQ/BCC/SrN 21.14/21.14/42.00/15.72 7.5
- Example 9 GN/NQ/BCC/SrN 19.38/19.38/52.00/9.24
- Example 1 2.37 86.4 1692
- Example 2 2.57 74.2 1425
- Example 3 2.32 88.2 1736
- Example 4 2.46 82.9 1605
- Example 5 2.48 81.4 1584
- Example 6 2.38 74.6 1440
- Example 7 2.51 79.0 1532
- Example 8 2.51 90.4 1791
- Example 9 2.40 80.2 1568
- Example 10 2.33 73.7 1425
- Example 11 2.43 81.3 1584
- Example 12 2.39 77.6 1508
- Example 13 2.55 82.5 1623
- Example 14 2.46 77.4 1509
- Example 15 2.43 87.9 1744
- Example 16 2.36 83.0 1636
- Example 17 2.57 89.1 1775
- Example 18 2.45 79.4 1556
- Example 19 2.30 70.3 1329
- Example 20 2.30 65.7 1253
- GN Guanidine nitrate NQ: Nitroguanidine GUDN: Guanylurea dinitramide Mel: Melamine MC: Melamine cyanurate BCC: Basic copper carbonate (average particle diameter is approximately 1 ⁇ m) BCN: Basic copper nitrate SrN: Strontium nitrate CMCNa: Carboxymethyl cellulose sodium salt Al (OH) 3 : Aluminum hydroxide
- compositions shown in Table 2 were measured in the manners shown in Table 2.
- the friction sensitivities were, according to the JIS grades, Grade 7, indicating that the compositions are in the safest level, or Grade 6, indicating that the compositions can be handled safely.
- the drop-hammer sensitivities were, according to the JIS grades, Grade 8, indicating that the compositions are in the safest level.
- a decomposition start temperature was 150° C. or above, which is in a decomposition start temperature range where the compositions can withstand during welding for manufacturing an inflator. Therefore, it is confirmed that all of the compositions are less dangerous, can be manufactured safely, and are practical.
- compositions shown in Table 3 were measured in the manners shown in Table 3.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Air Bags (AREA)
Abstract
The present invention is a gas generating composition including fuel and an oxidizing agent, which can be used for an inflator of a vehicle airbag apparatus, wherein the oxidizing agent includes basic copper carbonate, the gas generating composition having the content of the basic copper carbonate of more than 40% by mass and 60% by mass or lower, and satisfying the following requirements (a) to (c):
-
- (a) the burning rate is 7.0 mm/sec or above;
- (b) the gas output is 2.30 mol/100 g or above; and
- (c) the calorific value per mol of generated gas is 100 kJ/mol or lower.
Description
- The present invention relates to a gas generating composition that can be used for an inflator of a vehicle airbag apparatus.
- A combustion temperature of a gas generating agent needs to be reduced in order to obtain a small and light inflator for a vehicle airbag apparatus, which is highly demanded in recent years. However, reducing the combustion temperature of the gas generating agent often leads to a decrease in burning rate and an amount of generated gas. In order to mend this problem, a method for increasing the amount of the gas generating agent for charging an inflator is considered, but with this method, a small and light inflator cannot be obtained. In order to solve such a problem, it is desired to use “calorific value per mol of generated gas” as an index. It is normally desired that appropriate burning rate or gas output be realized, while keeping a calorific value per mol of generated gas of. approximately 100 kJ/mol or less.
- In JP-A No. 2004-155645, basic metal nitrate is disclosed as an oxygen-containing oxidizing agent, which is selected from among basic copper nitrate, basic cobalt nitrate, basic zinc nitrate, basic manganese nitrate, basic iron nitrate, basic molybdenum nitrate, basic bismuth nitrate and basic cerium nitrate, and it is described that the calorific value can be suppressed by adding aluminum hydroxide thereto.
- In JP-A No. 2001-220282, it is described that basic metal nitrate selected from among basic copper nitrate, basic cobalt nitrate, basic zinc nitrate, basic manganese nitrate, basic iron nitrate, basic molybdenum nitrate, basic bismuth nitrate and basic cerium nitrate can be used as an oxidizing agent.
- In JP-B No. 3907548, it is described that an oxygen-containing oxidizing agent selected from among metal nitrate, ammonium nitrate, a metal perchlorate salt, ammonium perchlorate, metal nitrite, metal chlorate, basic copper nitrate, basic cobalt nitrate, basic zinc nitrate, and basic manganese nitrate.
- In JP-A No. 2006-76849, such a gas generating composition is disclosed that the content of basic copper carbonate exceeds 20% by weight, but is equal to or lower than 40 wt %, but because the content of the basic copper carbonate in the embodiments is only 22.0 wt %, the effects obtained in the cases including 30 or more wt % basic copper carbonate are not confirmed.
- The present invention provides a gas generating composition for use in an inflator of a vehicle airbag apparatus and the like, such that a reduction of the calorific value per mol of generated gas is achieved without impairing burning rate or gas output, and the gas generating composition having no problem with the amount of mist or harmful gas concentration generated in combustion, solving such problems that have not been fully solved in the above prior arts.
- The invention 1 provides a gas generating composition, containing fuel and an oxidizing agent, the oxidizing agent comprising basic copper carbonate, the composition having the content of the basic copper carbonate of more than 40% by mass and 60% by mass or lower, satisfying the following requirements (a) to (c):
-
- (a) the burning rate is 7.0 mm/sec or above;
- (b) the gas output is 2.30 mol/100 g or above; and
- (c) the calorific value per mol of the generated gas is 100 kJ/mol or lower.
- The gas generating composition of the present invention can reduce the calorific value per mol of generated gas without impairing the burning rate or the gas output, by utilizing a predetermined amount of basic copper carbonate, and is free of problems regarding the amount of mist or harmful gas concentration generated in combustion. Therefore, the gas generating composition of the present invention is useful for an inflator of a vehicle airbag apparatus.
- The present invention includes the following preferred embodiments 2 to 6:
- 2. The gas generating composition according to the invention described above, wherein the content of the basic copper carbonate is 42 to 60% by mass.
- 3. The gas generating composition according to the invention described above, wherein the oxidizing agent is a combination of the basic copper carbonate and a basic metal nitrate and/or a nitrate, and the total content of the oxidizing agent is 50 to 80% by mass.
- 4. The gas generating composition according to the invention described above, wherein the oxidizing agent is a combination of the basic copper carbonate and basic copper nitrate and/or strontium nitrate, and the total content of the oxidizing agent is 50 to 80% by mass.
- 5. The gas generating composition according to the invention described above, further including a carboxymethyl cellulose salt as a binder.
- 6. The gas generating composition according to the invention described above, further including aluminum hydroxide.
- The gas generating composition of the present invention or a molded article obtained therefrom can be used for, for example, an airbag inflator of a driver's side, an airbag inflator of a passenger side next to the driver, a side airbag inflator, an inflator for an inflatable curtain, an inflator for a knee bolster, an inflator for an inflatable seat belt, an inflator for a tubular system, and a gas generator for a pretensioner, of various vehicles.
- The gas generating composition of the present invention or an inflator that uses a molded article obtained from the gas generating composition may be of a pyrotechnic type in which a gas supply source is only a gas generating agent or of a hybrid type that uses both compressed gas, such as argon, and a gas generating agent.
- Furthermore, the gas generating composition of the present invention or a molded article obtained therefrom can be also used as an igniting agent called an enhancer or a booster, which serves to transmit the energy of a detonator or a squib to the gas generating agent.
- <Fuel>
- The fuel used in the present invention can be a known fuel for a gas generating composition, for example, at least one selected from guanidine compounds, tetrazole compounds, triazine compounds, purine compounds, and amino-acid derivatives.
- Preferred guanidine compounds include guanidine nitrate, nitroguanidine, and guanylurea dinitramide. Preferred tetrazole compounds include 5-aminotetrazole and bitetrazole ammonium salt. Preferred triazine compounds include melamine, melamine cyanurate, melamine nitrate, melamine perchlorate, trihydrazinotriazine, and a nitrocompound of melamine. Preferred purine compounds include 8-azaguanine. Preferred amino-acid derivatives include glycine.
- The fuel used in the present invention can be two or more types of mixtures if necessary. A mixture of two or more guanidines or a mixture of guanidines and another substance, is preferred. For example, in the case of using only guanidine nitrate, problems are caused in the burning rate and the ignition ability of the gas generating composition, although the calorific value thereof can be made relatively low. In the case of using only nitroguanidine, the gas output of the gas generating composition becomes relatively low, although there are no problems in the burning rate or the ignition ability thereof. In order to handle these problems, the guanidine nitrate and the nitroguanidine can be mixed to obtain a fuel that takes the advantages of the guanidine nitrate and the nitroguanidine and overcomes the disadvantages thereof.
- The content of the fuel used in the present invention is preferably 20 to 60% by mass, more preferably 25 to 55% by mass, or even more preferably 30 to 50% by mass, in the gas generating composition.
- <Oxidizing Agent>
- The oxidizing agent used in the present invention contains basic copper carbonate. The content of the basic copper carbonate exceeds 40% by mass but is equal to or lower than 60% by mass, or preferably 42 to 60% by mass, in the gas generating composition. The basic copper carbonate in an amount of 40% by mass or lower cannot exert the effect of reducing the calorific value, and the basic copper carbonate exceeding 60% by mass impairs the ignition ability.
- An average particle diameter of the basic copper carbonate is preferably equal to or less than 5 μm, more preferably equal to or less than 3 μm, or even more preferably equal to or less than 1 μm. When the average particle diameter is large, the burning rate slows down, deteriorating the ignition ability. The average particle diameter was measured by particle size distribution measurement method based on laser scattering. A particle size meter MICROTRAC, Model No. 9320-X100, manufactured by Neede+Northrop Company, was used for the measurements. A sample was dispersed in ion-exchange water and irradiated with 50-W ultrasonic waves for 60 seconds. The 50% accumulated value of particle volume was obtained. Average values obtained by two measurements were taken as average particle diameters.
- The oxidizing agent can further contain known oxidizing agent, such as one or more selected from among nitrate, basic metal nitrate, ammonium nitrate, metal perchlorate, ammonium perchlorate, metal nitrite, metal chlorate and the like.
- Examples of basic metal nitrate include one or more selected from among basic copper nitrate, basic cobalt nitrate, basic zinc nitrate, basic manganese nitrate, basic iron nitrate, basic molybdenum nitrate, basic bismuth nitrate and basic cerium nitrate. Among these, basic copper nitrate is preferred.
- Examples of nitrate include one or more selected from among alkali metal nitrates such as potassium nitrate and sodium nitrate, as well as alkaline earth metal nitrates such as strontium nitrate. Among these, strontium nitrate is preferred.
- The total content of the oxidizing agent used in the present invention is preferably 50 to 80% by mass, more preferably 50 to 75% by mass, or even more preferably 50 to 70% by mass in the gas generating composition.
- <Binder>
- The gas generating composition according to the present invention can contain a known binder of a gas generating composition, if necessary. Examples of the binder include one or more selected from among carboxymethyl cellulose (CMC), carboxymethyl cellulose sodium salt (CMCNa), carboxymethyl cellulose potassium salt (CMCK), carboxymethyl cellulose ammonium salt (CMCNH4), cellulose acetate, cellulose acetate butyrate (CAB), methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), ethyl hydroxyethyl cellulose (EHEC), hydroxypropyl cellulose (HPC), carboxymethyl ethyl cellulose (CMEC), microcrystalline cellulose, polyacrylamides, aminated compounds of polyacrylamide, polyacryl hydrazide, a copolymer of acrylamide and a metal salt of acrylic acid, a copolymer of polyacrylamide and a polyacrylic acid ester compound, polyvinyl alcohol (PVA), acryl rubber, guar gum, starch, and silicone.
- Water-soluble cellulose derivatives (CMC, CMCNa, CMCK, CMCNH4, MC, EC, HEC, EHEC, HPC, CMEC), which are water-soluble binders, microcrystalline cellulose, PVA, guar gum, and starch are preferred as the binder. Above all, the water-soluble cellulose derivatives are preferred, CMC, CMCNa, CMCK and CMCNH4 are more preferred, and CMCNa is even more preferred.
- The content of the binder used in the present invention is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, or even more preferably 2 to 15 parts by mass, with respect to a total of 100 parts by mass of the fuel and the oxidizing agent.
- <Additives>
- The gas generating composition according to the present invention can include a known additive of a gas generating composition, such as a combustion catalyst, a heat absorbing agent, a slag forming agent, a lubricant or the like, according to necessity. Examples of the known additive include metal oxides such as copper oxide, iron oxide, zinc oxide, cobalt oxide, manganese oxide, molybdenum oxide, nickel oxide, bismuth oxide, silica, and alumina; metal hydroxides such as aluminum hydroxide, cobalt hydroxide, iron hydroxide, and magnesium hydroxide; metal carbonates or basic metal carbonates such as cobalt carbonate, calcium carbonate, and basic zinc carbonate; complex compounds of metal oxides or hydroxides, such as Japanese acid clay, kaolin, talc, bentonite, diatomaceous earth, and hydrotalcite; ammonium dihydrogenphosphate, ammonium polyphosphate, metal acid salts such as sodium silicate, mica molybdate, cobalt molybdate, and ammonium molybdate; silicone, molybdenum disulfide, calcium stearate, silicon nitride, silicon carbide, boric acid, metaboric acid, anhydrous boric acid, and the like.
- The additive used in the present invention may be in such an amount that does not have a great impact on the advantageous effects of the present invention in the calorific value, the gas output and the burning rate. The content of the additive is preferably 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, or even more preferably 2 to 20 parts by mass, with respect to a total of 100 parts by mass of the fuel and the oxidizing agent.
- The gas generating composition according to the present invention satisfies the following requirements (a) to (c), and preferably, also satisfies a requirement (d):
-
- (a) The burning rate is preferably 7.0 mm/sec or above, or more preferably 7.4 mm/sec or above;
- (b) The gas output is 2.30 mol/100 g or above, or more preferably 2.37 mol/100 g or above;
- (c) The calorific value per mol of generated gas is 100 kJ/mol or lower, or more preferably 90 kJ/mol or lower; and
- (d) The combustion temperature is preferably 2000 K or lower, or more preferably 1800 K or lower.
- The composition according to the present invention can be molded into a desired shape, and a cylindrical molded article, a cylindrical molded article with a single hole, a perforated cylindrical molded article, or a pellet-shaped molded article can be obtained.
- These molded articles can be manufactured by a method in which water or an organic solvent is added to and mixed with the composition and the obtained mixture is extrusion-molded (into the cylindrical molded article, the cylindrical molded article with a single hole, or a perforated cylindrical molded article), or by a compression-molding method using a pelletizer or the like (the pellet-shaped molded article).
- <Measuring the Burning Rate>
- [Method for Forming a Measuring Strand]
- The components of the gas generating composition were adequately mixed in the proportions shown in Table 1, and thereafter 30 g thereof was obtained. Water in an amount of 6 g was added thereto, which was then mixed in an antistatic plastic bag for 5 minutes or longer. The resultant mass was pulverized into small pieces and dried at 110° C. for two hours. The resultant product was then pulverized into powder in a mortar. 1.7 to 2.2 g of the powder was poured into a mold and the pressure of approximately 220 MPa (2250 kgf/cm2) was applied with a hydraulic pump, which was maintained for five seconds, to obtain a cylindrical strand (with a outer diameter of 9.55 mm and a length of 12.70 mm).
- [Method of Measurement]
- The measuring strand obtained in the manner described above was left in a temperature of 110° C. for 16 hours to eliminate water therefrom. Subsequently, an epoxy resin adhesive “Bond Quick 30” was applied twice to the side surface and one side of the measuring strand so as to ignite and combust the measuring strand from an end surface thereof. The resultant strand was installed in an SUS sealed bomb (internal volume thereof was 1 L), and the bomb was pressurized up to 7 MPa, while the inside thereof was purged with nitrogen. After the pressure inside the bomb was stabilized, a voltage of 12 V was applied to a nichrome wire in contact with the end surface of the measuring strand, thereby igniting and combusting the measuring strand by means of the fusing energy of the nichrome wire. The length of the measuring strand obtained prior to the combustion was divided by the time that has elapsed since the start of the combustion until when the peak of pressure rise was obtained, and the value obtained by this calculation was taken as the burning rate.
- [Calculating the Gas Output, the Calorific Value Per Mol of Generated Gas, and the Combustion Temperature]
- The gas output, the calorific value per mol of generated gas, and the combustion temperature were calculated through a simulation using a thermochemical equilibrium calculation program “NEWPEP.”
- [Method for Measuring Friction Sensitivity and Drop-Hammer Sensitivity]
- Powdered ingredients to include in the gas generating composition were each weighed such that the mass of the gas generating composition would be 1 g, and they were mixed adequately. The friction sensitivity and the drop-hammer sensitivity of the obtained powder sample were measured based on the explosive performance test method disclosed in Japanese Industrial Standard (JIS) K4810-1979.
- [Method for Measuring Decomposition Temperature]
- The same gas generating composition as the one used in the method for measuring the friction sensitivity and the drop-hammer sensitivity was used to perform thermogravimetry by using a thermobalance (TGDTA6300 manufactured by Seiko Epson Corporation). The temperature at which the mass is reduced was taken as a decomposition temperature.
- [Method for Measuring Exhaust Gas Concentration]
- After the measuring strand (with an outer diameter of 9.55 mm and mass of 2.00 g) obtained in the same method as the one described above was left in a temperature of 110° C. for 16 hours to eliminate water therefrom, the measuring strand was installed in an SUS sealed bomb (internal volume thereof was 1 L), and the bomb was pressurized up to 7 MPa, while the inside thereof was purged with nitrogen. After the pressure inside the bomb was stabilized, a predetermined current was passed into a nichrome wire in contact with the end surface of the measuring strand, thereby igniting and combusting the measuring strand by means of the fusing energy of the nichrome wire. Thus generated exhaust gas was obtained 60 seconds later, and the concentration thereof was measured using a gas detector (GV-100S manufactured by Gastec Corporation) and a gas detection tube (No. 10: for NO, No. 3L and 3M: for detecting NH3, No. 1L: for CO, manufactured by Gastec Corporation).
- The compositions shown in Table 1 were measured in the manners shown in Table 1.
-
TABLE 1 (a)Burning Component ratio rate No Composition (% by mass) (mm/sec.) Example 1 NQ/BCC/BCN 38.70/42.00/19.30 7.4 Example 2 GUDN/BCC/BCN 47.84/42.00/10.16 7.9 Example 3 NQ/BCC/SrN 37.49/52.00/10.51 8.3 Example 4 GN/NQ/BCC/BCN 15.95/23.93/42.00/18.12 7.7 Example 5 GN/NQ/BCC/BCN 20.09/20.09/42.00/17.82 7.5 Example 6 GN/NQ/BCC/BCN 18.77/18.77/52.00/10.46 7.0 Example 7 GN/NQ/BCC/BCN 27.14/13.57/42.00/17.29 7.0 Example 8 GN/NQ/BCC/SrN 21.14/21.14/42.00/15.72 7.5 Example 9 GN/NQ/BCC/SrN 19.38/19.38/52.00/9.24 7.2 Example 10 GN/NQ/BCC/SrN 18.33/18.33/58.00/5.34 7.1 Example 11 GN/NQ/BCC/BCN/SrN 19.72/19.72/48.00/6.28/6.28 7.5 Example 12 GN/NQ/BCC/SrN/BCN 19.10/19.10/52.00/4.90/4.90 7.3 Example 13 GN/GUDN/BCC/BCN 22.31/22.31/42.00/13.38 7.6 Example 14 GN/GUDN/BCC/BCN 21.13/21.13/50.00/7.74 7.0 Example 15 NQ/GUDN/BCC/BCN 20.97/20.97/45.00/13.06 7.9 Example 16 NQ/GUDN/BCC/BCN 19.98/19.98/52.00/8.04 7.7 Example 17 GN/GUDN/BCC/SrN 23.17/23.17/42.00/11.66 7.5 Example 18 GN/GUDN/BCC/SrN 21.24/21.24/52.00/5.52 7.5 Example 19 GN/Mel/BCC/BCN 25.46/6.37/42.00/26.17 7.7 Example 20 GN/MC/BCC/BCN 24.87/8.29/42.00/24.84 7.5 Example 21 GN/NQ/BCC/BCN/CMCNa 16.75/16.75/42.00/21.50/3.00 8.5 Example 22 GN/NQ/BCC/SrN/CMCNa 18.01/18.01/42.00/18.98/3.00 7.1 Example 23 GN/NQ/BCC/SrN/BCN/CMCNa 17.42/17.42/42.00/10.08/10.08/3.00 7.4 Example 24 GN/NQ/BCC/BCN/CMCNa/Al (OH)3 16.49/16.49/42.00/21.02/3.00/1.00 7.0 Comparative Ex. 1 GN/BCC/BCN 42.35/40.00/17.65 4.2 Comparative Ex. 2 GN/BCC/SrN 44.5/40.00/15.5 not ignited Comparative Ex. 3 GN/BCC/SrN 46.32/35.00/18.68 4.1 Comparative Ex. 4 GN/BCC/SrN 51.78/20.00/28.22 5.3 Comparative Ex. 5 GN/NQ/BCC 22.91/11.46/65.63 not ignited Comparative Ex. 6 GN/NQ/BCC/BCN 17.44/17.44/62.00/3.12 not ignited Comparative Ex. 7 GN/NQ/BCC/SrN 17.63/17.63/62.00/2.74 6.5 Comparative Ex. 8 GN/NQ/BCC/SrN/BCN 17.54/17.54/62.00/1.46/1.46 not ignited (c) (d) (b)Gas calorific Combustion output value per temperature No (mol/100 g) mol (kJ/mo1l) (K) Example 1 2.37 86.4 1692 Example 2 2.57 74.2 1425 Example 3 2.32 88.2 1736 Example 4 2.46 82.9 1605 Example 5 2.48 81.4 1584 Example 6 2.38 74.6 1440 Example 7 2.51 79.0 1532 Example 8 2.51 90.4 1791 Example 9 2.40 80.2 1568 Example 10 2.33 73.7 1425 Example 11 2.43 81.3 1584 Example 12 2.39 77.6 1508 Example 13 2.55 82.5 1623 Example 14 2.46 77.4 1509 Example 15 2.43 87.9 1744 Example 16 2.36 83.0 1636 Example 17 2.57 89.1 1775 Example 18 2.45 79.4 1556 Example 19 2.30 70.3 1329 Example 20 2.30 65.7 1253 Example 21 2.35 79.3 1503 Example 22 2.38 90.6 1753 Example 23 2.43 79.1 1555 Example 24 2.34 78.0 1471 Comparative Ex. 1 2.59 75.4 1451 Comparative Ex. 2 2.62 83.9 1645 Comparative Ex. 3 2.68 88.2 2013 Comparative Ex. 4 2.86 99.8 1743 Comparative Ex. 5 2.41 66.8 1269 Comparative Ex. 6 2.28 70.3 1349 Comparative Ex. 7 2.27 71.5 1330 Comparative Ex. 8 2.28 70.3 1318 GN: Guanidine nitrate NQ: Nitroguanidine GUDN: Guanylurea dinitramide Mel: Melamine MC: Melamine cyanurate BCC: Basic copper carbonate (average particle diameter is approximately 1 μm) BCN: Basic copper nitrate SrN: Strontium nitrate CMCNa: Carboxymethyl cellulose sodium salt Al (OH)3: Aluminum hydroxide - It was confirmed in any of Examples 1 to 23 that the calorific value per mol of generated gas was sufficiently controlled (to 100 kJ/mol or lower) without impairing the practical burning rate (7.0 mm/sec or above) and the gas output (2.30 mol/100 g or above), in spite of the use of a large amount of basic copper carbonate (exceeding 40% by mass but equal to or lower than 60% by mass), which has a great heat absorption effect. However, Comparative Examples 1 to 8 show that either the gas output or the burning rate is not enough, causing a problem in practicality of these compositions.
- The compositions shown in Table 2 were measured in the manners shown in Table 2.
-
TABLE 2 Drop- Decomposition Oxygen Friction hammer starting Component ratio balance sensitivity sensitivity temperature No Composition (% by mass) (g/g) (N) (cm) (° C.) Example 25 GUDN/BCC/BCN 47.84/42.00/10.16 0.000 >353 >60 153 Example 26 GN/NQ/BCC/BCN 18.77/18.77/52.00/10.46 0.000 157 to 235 >60 175 Example 27 GN/NQ/BCC/SrN 19.38/19.38/52.00/9.24 0.000 157 to 235 >60 173 Example 28 GN/NQ/BCC/BCN/SrN 19.72/19.72/48.00/6.28/6.28 0.000 157 to 235 >60 153 Example 29 GN/GUDN/BCC/BCN 22.31/22.31/42.00/13.38 0.000 >353 >60 154 Example 30 NQ/GUDN/BCC/BCN 19.98/19.98/52.00/8.04 0.000 157 to 235 >60 158 Example 31 GN/GUDN/BCC/SrN 21.24/21.24/52.00/5.52 0.000 >353 >60 158 Example 32 GN/Mel/BCC/BCN 25.46/6.37/42.00/26.17 0.000 >353 >60 158 Example 33 GN/MC/BCC/BCN 24.87/8.29/42.00/24.84 0.000 >353 >60 160 Example 34 GN/NQ/BCC/BCN/CMCNa 16.75/16.75/42.00/21.50/3.00 0.000 157 to 235 >60 175 Example 35 GN/NQ/BCC/SrN/BCN/CMCNa 17.42/17.42/42.00/10.08/10.08/3.00 0.000 157 to 235 >60 155 - According to Table 2, the friction sensitivities were, according to the JIS grades, Grade 7, indicating that the compositions are in the safest level, or Grade 6, indicating that the compositions can be handled safely. The drop-hammer sensitivities were, according to the JIS grades, Grade 8, indicating that the compositions are in the safest level. Furthermore, a decomposition start temperature was 150° C. or above, which is in a decomposition start temperature range where the compositions can withstand during welding for manufacturing an inflator. Therefore, it is confirmed that all of the compositions are less dangerous, can be manufactured safely, and are practical.
- The compositions shown in Table 3 were measured in the manners shown in Table 3.
-
TABLE 3 Concentration of exhaust Component ratio gas (ppm) No Composition (% by mass) NO NH3 CO Example 36 GN/NQ/BCC/BCN 18.77/18.77/52.00/10.46 10 40 80 Example 37 GN/NQ/BCC/SrN 19.38/19.38/52.00/9.24 5 15 50 Example 38 GN/NQ/BCC/BCN/CMCNa 16.75/16.75/42.00/21.50/3.00 9 16 90 Example 39 GN/NQ/BCC/SrN/BCN/CMCNa 17.42/17.42/42.00/10.08/10.08/3.00 20 60 95 - According to Table 3, it is confirmed that there are no problems in the concentrations of the hazardous exhaust gases NO, NH3 and CO.
Claims (6)
1. A gas generating composition, comprising fuel and an oxidizing agent, the oxidizing agent comprising basic copper carbonate, the composition having the content of the basic copper carbonate of more than 40% by mass and 60% by mass or lower, satisfying the following requirements (a) to (c):
(a) the burning rate is 7 0 mm/sec or above;
(b) the gas output is 2.30 mol/100 g or above; and
(c) the calorific value per mol of the generated gas is 100 kJ/mol or lower.
2. The gas generating composition according to claim 1 , wherein the content of the basic copper carbonate is 42 to 60% by mass.
3. The gas generating composition according to claim 1 , wherein the oxidizing agent is a combination of the basic copper carbonate and a basic metal nitrate and/or a nitrate, and the total content of the oxidizing agent is 50 to 80% by mass.
4. The gas generating composition according to claim 1 , wherein the oxidizing agent is a combination of the basic copper carbonate and basic copper nitrate and/or strontium nitrate, and the total content of the oxidizing agent is 50 to 80% by mass.
5. The gas generating composition according to claim 1 , further comprising a carboxymethyl cellulose salt as a binder.
6. The gas generating composition according to claim 1 , further comprising aluminum hydroxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009122918A JP5441497B2 (en) | 2009-05-21 | 2009-05-21 | Gas generant composition |
| JP2009122918 | 2009-05-21 | ||
| PCT/JP2010/058154 WO2010134466A1 (en) | 2009-05-21 | 2010-05-14 | Gas generant composition |
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| US20120055593A1 true US20120055593A1 (en) | 2012-03-08 |
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| US13/321,426 Abandoned US20120055593A1 (en) | 2009-05-21 | 2010-05-14 | Gas generating composition |
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| US (1) | US20120055593A1 (en) |
| EP (1) | EP2444383B1 (en) |
| JP (1) | JP5441497B2 (en) |
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| WO (1) | WO2010134466A1 (en) |
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| US20130340900A1 (en) * | 2011-03-31 | 2013-12-26 | Daicel Corporation | Gas generating composition |
| US9321956B2 (en) | 2012-11-28 | 2016-04-26 | Halliburton Energy Services, Inc. | Methods for hindering the settling of particulates in a subterranean formation |
| EP2910538A4 (en) * | 2012-10-18 | 2016-06-29 | Daicel Corp | AGENT COMPOSITION GENERATING GAS |
| US9487454B2 (en) | 2011-03-23 | 2016-11-08 | Diacel Corporation | Gas generating composition |
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| CN112010719B (en) * | 2019-05-29 | 2021-11-30 | 南京理工大学 | Aluminum-containing explosive and preparation method thereof |
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| JP3907548B2 (en) | 2002-08-05 | 2007-04-18 | ダイセル化学工業株式会社 | Gas generator composition for inflator containing melamine cyanurate |
| JP4302442B2 (en) | 2002-09-12 | 2009-07-29 | ダイセル化学工業株式会社 | Gas generant composition |
| JP4672975B2 (en) * | 2002-10-31 | 2011-04-20 | ダイセル化学工業株式会社 | Gas generant composition |
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| JP5422096B2 (en) * | 2006-11-02 | 2014-02-19 | 株式会社ダイセル | Gas generant composition |
| JP5085926B2 (en) * | 2006-12-21 | 2012-11-28 | 株式会社ダイセル | Gas generant composition |
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- 2009-05-21 JP JP2009122918A patent/JP5441497B2/en active Active
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- 2010-05-14 WO PCT/JP2010/058154 patent/WO2010134466A1/en not_active Ceased
- 2010-05-14 CN CN201080021550.1A patent/CN102428056B/en active Active
- 2010-05-14 US US13/321,426 patent/US20120055593A1/en not_active Abandoned
- 2010-05-14 EP EP10777699.9A patent/EP2444383B1/en active Active
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| US5386775A (en) * | 1993-06-22 | 1995-02-07 | Automotive Systems Laboratory, Inc. | Azide-free gas generant compositions and processes |
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| US9458065B2 (en) * | 2011-03-31 | 2016-10-04 | Daicel Corporation | Gas generating composition |
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| EP2910538A4 (en) * | 2012-10-18 | 2016-06-29 | Daicel Corp | AGENT COMPOSITION GENERATING GAS |
| US9321956B2 (en) | 2012-11-28 | 2016-04-26 | Halliburton Energy Services, Inc. | Methods for hindering the settling of particulates in a subterranean formation |
| US9790774B2 (en) | 2014-01-02 | 2017-10-17 | Halliburton Energy Services, Inc. | Generating and maintaining conductivity of microfractures in tight formations by generating gas and heat |
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| US20170334802A1 (en) * | 2016-05-23 | 2017-11-23 | Tk Holdings Inc. | Gas generating compositions and methods of making and using thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2010269969A (en) | 2010-12-02 |
| EP2444383A4 (en) | 2014-01-01 |
| WO2010134466A1 (en) | 2010-11-25 |
| EP2444383B1 (en) | 2019-08-07 |
| JP5441497B2 (en) | 2014-03-12 |
| CN102428056A (en) | 2012-04-25 |
| CN102428056B (en) | 2014-03-12 |
| EP2444383A1 (en) | 2012-04-25 |
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