US20010042577A1 - Temperature fuse - Google Patents
Temperature fuse Download PDFInfo
- Publication number
- US20010042577A1 US20010042577A1 US09/835,358 US83535801A US2001042577A1 US 20010042577 A1 US20010042577 A1 US 20010042577A1 US 83535801 A US83535801 A US 83535801A US 2001042577 A1 US2001042577 A1 US 2001042577A1
- Authority
- US
- United States
- Prior art keywords
- accordance
- temperature fuse
- nitrate
- gas
- substances
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 claims abstract description 54
- 239000000126 substance Substances 0.000 claims abstract description 24
- 238000005474 detonation Methods 0.000 claims abstract description 20
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 14
- -1 compound class of oxalates Chemical class 0.000 claims description 13
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims description 11
- QJTIRVUEVSKJTK-UHFFFAOYSA-N 5-nitro-1,2-dihydro-1,2,4-triazol-3-one Chemical compound [O-][N+](=O)C1=NC(=O)NN1 QJTIRVUEVSKJTK-UHFFFAOYSA-N 0.000 claims description 11
- 229940105296 zinc peroxide Drugs 0.000 claims description 9
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002360 explosive Substances 0.000 claims description 7
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims description 7
- FNMYQWAUHXSWPY-UHFFFAOYSA-N calcium;2h-tetrazol-5-amine Chemical compound [Ca].NC=1N=NNN=1.NC=1N=NNN=1 FNMYQWAUHXSWPY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- TVIRJXQLFRFUCD-UHFFFAOYSA-N nitric acid;2h-tetrazol-5-amine Chemical compound O[N+]([O-])=O.NC1=NN=NN1 TVIRJXQLFRFUCD-UHFFFAOYSA-N 0.000 claims description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 4
- NPLZZSLZTJVZSX-UHFFFAOYSA-L iron(2+);oxalate;dihydrate Chemical compound O.O.[Fe+2].[O-]C(=O)C([O-])=O NPLZZSLZTJVZSX-UHFFFAOYSA-L 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 3
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 3
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 claims description 2
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004153 Potassium bromate Substances 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- WPADTLKJFUUWIK-UHFFFAOYSA-N azane iron oxalic acid Chemical compound N.N.N.[Fe].OC(=O)C(O)=O.OC(=O)C(O)=O.OC(=O)C(O)=O WPADTLKJFUUWIK-UHFFFAOYSA-N 0.000 claims description 2
- 229940044172 calcium formate Drugs 0.000 claims description 2
- 235000019255 calcium formate Nutrition 0.000 claims description 2
- 239000004281 calcium formate Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- 229910001337 iron nitride Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 235000019396 potassium bromate Nutrition 0.000 claims description 2
- 229940094037 potassium bromate Drugs 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- 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 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 1
- 239000008240 homogeneous mixture Substances 0.000 claims 1
- OCATYIAKPYKMPG-UHFFFAOYSA-M potassium bromate Chemical compound [K+].[O-]Br(=O)=O OCATYIAKPYKMPG-UHFFFAOYSA-M 0.000 claims 1
- 239000000020 Nitrocellulose Substances 0.000 description 7
- 229920001220 nitrocellulos Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- ACLQBCPOWXJYEI-UHFFFAOYSA-N sodium 5-nitro-1,2,4-triazol-3-one nitrate Chemical compound [N+](=O)([O-])C=1N=NC(N1)=O.[N+](=O)([O-])[O-].[Na+] ACLQBCPOWXJYEI-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- GDABQXUUHGDZNX-UHFFFAOYSA-N [Na+].[O-][N+]([O-])=O.NC(N)=N[N+]([O-])=O Chemical compound [Na+].[O-][N+]([O-])=O.NC(N)=N[N+]([O-])=O GDABQXUUHGDZNX-UHFFFAOYSA-N 0.000 description 3
- DZEVAAJRRSHMNM-UHFFFAOYSA-N [Zn].[N+](=O)([O-])C=1N=NC(N1)=O Chemical compound [Zn].[N+](=O)([O-])C=1N=NC(N1)=O DZEVAAJRRSHMNM-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- YUXJTKUUYSFSTN-UHFFFAOYSA-O azanium 5-nitro-1,2,4-triazol-3-one nitrate Chemical compound [N+](=O)([O-])[O-].[NH4+].[N+](=O)([O-])C=1N=NC(N1)=O YUXJTKUUYSFSTN-UHFFFAOYSA-O 0.000 description 3
- IHKWKTWFZBFRMN-UHFFFAOYSA-N calcium sodium 2H-tetrazol-5-amine trinitrate Chemical compound [Na+].[Ca++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.Nc1nnn[nH]1.Nc1nnn[nH]1 IHKWKTWFZBFRMN-UHFFFAOYSA-N 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- HUXHVWOOHIPETN-UHFFFAOYSA-N strontium 5-nitro-1,2,4-triazol-3-one dinitrate Chemical compound [Sr++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+](=O)C1=NC(=O)N=N1 HUXHVWOOHIPETN-UHFFFAOYSA-N 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- BFPACULRTNASOE-UHFFFAOYSA-M Cl(=O)(=O)(=O)[O-].[K+].[N+](=O)([O-])C=1N=NC(N1)=O Chemical compound Cl(=O)(=O)(=O)[O-].[K+].[N+](=O)([O-])C=1N=NC(N1)=O BFPACULRTNASOE-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- VFVUUUJUZZVFQS-UHFFFAOYSA-N iron(3+) oxygen(2-) 2H-tetrazol-5-amine nitrate Chemical compound [O-2].[Fe+3].[N+](=O)([O-])[O-].NC1=NN=NN1 VFVUUUJUZZVFQS-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 description 1
- IEZZCSVXCSHEKD-UHFFFAOYSA-N 5-nitro-1,2,4-triazol-3-one;potassium Chemical compound [K].[O-][N+](=O)C1=NC(=O)N=N1 IEZZCSVXCSHEKD-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- YNKVVRHAQCDJQM-UHFFFAOYSA-P diazanium dinitrate Chemical compound [NH4+].[NH4+].[O-][N+]([O-])=O.[O-][N+]([O-])=O YNKVVRHAQCDJQM-UHFFFAOYSA-P 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 description 1
- KDJBPYQBESSGJK-UHFFFAOYSA-N sodium nitric acid 2H-tetrazol-5-amine nitrate Chemical compound [N+](=O)([O-])[O-].[Na+].[N+](=O)(O)[O-].NC1=NN=NN1 KDJBPYQBESSGJK-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent 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
- 230000001960 triggered effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
- C06C9/00—Chemical contact igniters; Chemical lighters
Definitions
- the subject-matter of the present invention is temperature fuses which can be used, for example, in gas generators for motor vehicle safety systems.
- Gas-generating mixtures used in gas generators for motor vehicle safety systems are, as a rule, thermally very stable.
- temperature fuses are used in order to ignite the gas-generating mixture in a controlled manner at high ambient temperature, for example in the case of a vehicle fire.
- Such a fuse is necessary in order to prevent the gas-generating mixture self-igniting in an uncontrolled manner at unusually high temperatures. Namely, at high temperatures, the gas-generating mixture would not burn normally, but because of the increased temperature would react in a correspondingly accelerated and violent manner, in unfavourable cases explosively.
- the generator housing is not designed for this accelerated, violent reaction and would thereby be destroyed. A considerable risk to the motor vehicle passengers would be the result.
- the temperature fuse ensures that the reaction of the gas-generating mixture is thermally triggered well below this critical temperature. As a result of its early reaction and controlled ignition of the gas-generating mixture in such a case, it prevents the destruction of the generator housing and the dangers linked therewith.
- nitrocellulose or propellent charge powder derived therefrom, are generally used as a temperature fuse.
- a crucial disadvantage of nitrocellulose, however, is that it already begins to decompose slowly at temperatures which are still not sufficient for ignition. In the extreme case, the nitrocellulose decomposes completely. It can then no longer fulfil its task as a temperature fuse. Attempts have admittedly been made to improve the thermal stability of nitrocellulose. These attempts, however, are subject to narrow restrictions.
- An object of the present invention has therefore been to provide a temperature fuse which does not have the disadvantages of the nitrocellulose-based temperature fuse.
- Substances or mixtures of substances which have lower detonation points or decomposition points than the actual gas-generating mixture can be used as temperature fuses in accordance with the invention.
- the absolute level of the detonation points or decomposition points of the temperature fuses in accordance with the invention thereby depends on the respective construction and housing stability of the gas generator which is used. The more stable the generator housing, for example, the higher in general these values can be for the temperature fuse in accordance with the invention.
- iron(II)oxalate dihydrate which has a distinct decomposition point at 190° C., ammonium-iron-(III)-oxalate, the double salt of ammonium oxalate and iron oxalate with decomposition temperatures of 160-170° C.
- peroxidisulphates (persulphates) preferably ammonium persulphate, sodium persulphate or potassium persulphate, the thermal decomposition of which is suitable for starting the reaction
- permanganates preferably sodium permanganate or potassium permanganate
- formates preferably ammonium formate or calcium formate
- a nitrate preferably ammonium nitrate
- a sulphamate preferably ammonium sulphamate
- a nitride preferably iron nitride, as a bismuthate preferably sodium bismuthate
- bromate preferably potassium bromate
- Iron oxide and/or ferrocene can also be used.
- oxidizable components for example explosives having low detonation or decomposition points, preferably calcium bistetrazolamine, 3-nitro-1,2,4-triazol-5-one (NTO), 5-aminotetrazole nitrate, nitroguanidine (NIGU), guanidine nitrate and bistetrazolamine, can be used.
- the substances can be used individually or in a mixture.
- a specific thermal decomposition point of the temperature fuse in accordance with the invention can be adjusted by adjusting the mixture.
- the known explosives preferably calcium bistetrazolamine, 3-nitro-1,2,4-triazol-5-one (NTO), 5-aminotetrazole nitrate, nitroguanidine (NIGU), guanidine nitrate and bistetrazole amine can be used as fuels, and metal powder, preferably titanium powder, can be used as a reducing agent, for example.
- the explosives are used as a temperature fuse in accordance with the invention, having lower detonation or decomposition points than the gas-generating mixture which is used, then, in addition to the substances already mentioned above, guanidine nitrate, or even oxidizing agents such as potassium nitrate, sodium nitrate, strontium nitrate, potassium perchlorate or mixtures of these oxidizing agents, can be added in order to influence the detonation points and thus the range of effectiveness of the temperature fuse in accordance with the invention.
- guanidine nitrate or even oxidizing agents such as potassium nitrate, sodium nitrate, strontium nitrate, potassium perchlorate or mixtures of these oxidizing agents, can be added in order to influence the detonation points and thus the range of effectiveness of the temperature fuse in accordance with the invention.
- the temperature fuses in accordance with the invention can be used in a variety of ways. One use provides using them homogeneously in the gas-generating mixture. In particular, the temperature fuses in accordance with the invention that do not impair or impair only to an insignificant extent the actual characteristic of the gas-generating mixture are suitable herefor.
- the homogeneous distribution can take place according to mixing methods which are known per se, for example by sieving or tumbling the dry mixture or by kneading, extruding or extrusion moulding a moistened or solvent-containing mixture. The addition of a binding agent is likewise possible.
- the temperature fuses in accordance with the invention can constitute 0.1 to 20% by weight, preferably 0.1 to 5 by weight, of the gas-generating mixture.
- a further use provides for the temperature fuses in accordance with the invention in the generator housing to be separated from the actual gas-generating mixture. This use is always to be recommended if the temperature fuses in accordance with the invention that are used impair the actual characteristic of the gas-generating mixture.
- these temperature fuses in accordance with the invention are preferably provided at thermally exposed points on the generator housing. In this way, a reliable triggering of the temperature fuse in the case of heating from the outside is ensured, as a result of which the controlled ignition of the gas-generating mixture is ensured.
- the admixtures in accordance with the invention can be used in the form of tablets, for example. The production of such tablets takes place according to methods which are known per se.
- a further use provides including the temperature fuses in accordance with the invention in the normal ignition device of the gas-generating mixture.
- the temperature fuses in accordance with the invention are distributed homogeneously in the ignition mixture or are separated therefrom, for example in the form of a tablet.
- the purity of the substances which are used determines the instant of thermal triggering and the grain size determines the energy which is released locally.
- processing aids which are known per se, for example talc, graphite or boron nitride, can be used.
- the temperature fuses in accordance with the invention can also be used, for example, in pressure or safety elements for triggering movements of mechanical elements.
- the temperature fuses in accordance with the invention are compatible with the gas-generating mixture and its components and show, in accordance with the requirements, a temperature and storage stability that is sufficient for the instance of application and considerably improved in comparison with nitrocellulose.
- the problem of slow decomposition at comparatively high storage temperatures, which is to be noticed in the case of nitrocellulose, is not displayed by the temperature fuses in accordance with the invention. A thermal change at the required storage and operating temperatures could not be established.
- the specified components of the mixture were homogenised in the given weight ratios in screwed-down plastics containers in a dry-blend mixer for 30 minutes. According to need, there also took place tablet production and granulated-material production by breaking the molded bodies, or even, after addition of a binder, shaping by kneading and subsequent extrusion.
- the thermally initiable properties were characterised by establishing the detonation point or the calorific behaviour by recording the thermo-gravimetry and differential thermal analysis. The detonation point was determined by heating 100 or 300 mg of a substance (depending on the liveliness of the reaction) to a maximum of 400° C. with a heating rate of 20° C. per minute. The temperature at which a significant reaction takes place with formation of gases or formation of flames, or even deflagration, is given as the detonation point.
- thermal initiation of mixtures which contain a plurality of components or vary in terms of the selection of oxidizing agents: (Amounts in % by weight) ditetrazole detonation ammonium nitrate ammonium nitrate binder point 66.7 22.2 11.1 NPE none 66.7 22.2 11.1 PNP 298° C. iron potassium nitro- boron (III) zinc per- sodium detonation guanidine nitride oxide peroxide chlorate nitrate point 20 4 38 38 — — 188° C. 20 4 40 31 5 — 234° C. 20 2 40 30 4 4 203° C.
- Example of the thermal initiability of a pyrotechnic mixture as a function of the amount of the additive iron(II)oxalate dihydrate iron(II)oxalate detonation 5-aminotetrazole sodium nitrate dihydrate point 49.9 49.9 0.2 >400° C. 49.7 49.7 0.6 >400° C. 49.3 49.3 1.4 250° C. 48.5 48.5 3.0 251° C. 47 47 6.0 245° C.
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Abstract
Description
- The subject-matter of the present invention is temperature fuses which can be used, for example, in gas generators for motor vehicle safety systems.
- Gas-generating mixtures used in gas generators for motor vehicle safety systems are, as a rule, thermally very stable. In order to ignite the gas-generating mixture in a controlled manner at high ambient temperature, for example in the case of a vehicle fire, so-called temperature fuses are used. Such a fuse is necessary in order to prevent the gas-generating mixture self-igniting in an uncontrolled manner at unusually high temperatures. Namely, at high temperatures, the gas-generating mixture would not burn normally, but because of the increased temperature would react in a correspondingly accelerated and violent manner, in unfavourable cases explosively. The generator housing is not designed for this accelerated, violent reaction and would thereby be destroyed. A considerable risk to the motor vehicle passengers would be the result. The temperature fuse ensures that the reaction of the gas-generating mixture is thermally triggered well below this critical temperature. As a result of its early reaction and controlled ignition of the gas-generating mixture in such a case, it prevents the destruction of the generator housing and the dangers linked therewith.
- In the prior art, nitrocellulose, or propellent charge powder derived therefrom, are generally used as a temperature fuse. A crucial disadvantage of nitrocellulose, however, is that it already begins to decompose slowly at temperatures which are still not sufficient for ignition. In the extreme case, the nitrocellulose decomposes completely. It can then no longer fulfil its task as a temperature fuse. Attempts have admittedly been made to improve the thermal stability of nitrocellulose. These attempts, however, are subject to narrow restrictions.
- An object of the present invention has therefore been to provide a temperature fuse which does not have the disadvantages of the nitrocellulose-based temperature fuse.
- The underlying object of the invention was achieved by a temperature fuse having the characterising features of the main claim. Advantageous developments are characterised in the subclaims.
- Surprisingly, it has been established that the temperature fuses in accordance with the invention are able to ignite thermally the gas-generating mixtures normally used in gas generators in a controlled manner well below the critical temperature.
- Substances or mixtures of substances which have lower detonation points or decomposition points than the actual gas-generating mixture can be used as temperature fuses in accordance with the invention. The absolute level of the detonation points or decomposition points of the temperature fuses in accordance with the invention thereby depends on the respective construction and housing stability of the gas generator which is used. The more stable the generator housing, for example, the higher in general these values can be for the temperature fuse in accordance with the invention.
- Substances or mixtures of substances, the exothermal thermal decomposition of which takes place in a narrowly restricted temperature range, can be used for the temperature fuses in accordance with the invention. The evolution of heat which occurs must, in this case, be sufficient to compensate for energy losses in the gas-generating mixture, in order to achieve, or exceed, the activation energy needed to ignite the gas-generating mixture.
- Compounds selected from the compound classes of oxalates, peroxidisulphates (persulphates), permanganates, nitrides, perborates, bismuthates, formates, nitrates, sulphamates, bromates or peroxides can be used as substances or mixtures of substances for the temperature fuses in accordance with the invention. As oxalates, there can preferably be used iron(II)oxalate dihydrate which has a distinct decomposition point at 190° C., ammonium-iron-(III)-oxalate, the double salt of ammonium oxalate and iron oxalate with decomposition temperatures of 160-170° C.; as peroxidisulphates (persulphates) preferably ammonium persulphate, sodium persulphate or potassium persulphate, the thermal decomposition of which is suitable for starting the reaction; as permanganates preferably sodium permanganate or potassium permanganate; as formates preferably ammonium formate or calcium formate; as a nitrate preferably ammonium nitrate; as a sulphamate preferably ammonium sulphamate; as a nitride preferably iron nitride, as a bismuthate preferably sodium bismuthate; as a bromate preferably potassium bromate, and as a peroxide preferably zinc peroxide. Iron oxide and/or ferrocene, can also be used. Apart from this, oxidizable components, for example explosives having low detonation or decomposition points, preferably calcium bistetrazolamine, 3-nitro-1,2,4-triazol-5-one (NTO), 5-aminotetrazole nitrate, nitroguanidine (NIGU), guanidine nitrate and bistetrazolamine, can be used. The substances can be used individually or in a mixture. A specific thermal decomposition point of the temperature fuse in accordance with the invention can be adjusted by adjusting the mixture.
- Of these substances, those which have a lower detonation point or decomposition point than the gas-generating mixture which is used and thereby decompose exothermally can be used alone, without addition of a fuel, for example, as a temperature fuse in accordance with the invention. The substances which have a lower detonation point or decomposition point than the gas-generating mixture which is used but thereby decompose endothermally require at least one fuel and possibly a reducing agent in order to be able to be used as a temperature fuse in accordance with the invention. For example, the known explosives preferably calcium bistetrazolamine, 3-nitro-1,2,4-triazol-5-one (NTO), 5-aminotetrazole nitrate, nitroguanidine (NIGU), guanidine nitrate and bistetrazole amine can be used as fuels, and metal powder, preferably titanium powder, can be used as a reducing agent, for example.
- When the explosives are used as a temperature fuse in accordance with the invention, having lower detonation or decomposition points than the gas-generating mixture which is used, then, in addition to the substances already mentioned above, guanidine nitrate, or even oxidizing agents such as potassium nitrate, sodium nitrate, strontium nitrate, potassium perchlorate or mixtures of these oxidizing agents, can be added in order to influence the detonation points and thus the range of effectiveness of the temperature fuse in accordance with the invention.
- The temperature fuses in accordance with the invention can be used in a variety of ways. One use provides using them homogeneously in the gas-generating mixture. In particular, the temperature fuses in accordance with the invention that do not impair or impair only to an insignificant extent the actual characteristic of the gas-generating mixture are suitable herefor. The homogeneous distribution can take place according to mixing methods which are known per se, for example by sieving or tumbling the dry mixture or by kneading, extruding or extrusion moulding a moistened or solvent-containing mixture. The addition of a binding agent is likewise possible. In the case of this use, the temperature fuses in accordance with the invention can constitute 0.1 to 20% by weight, preferably 0.1 to 5 by weight, of the gas-generating mixture.
- A further use provides for the temperature fuses in accordance with the invention in the generator housing to be separated from the actual gas-generating mixture. This use is always to be recommended if the temperature fuses in accordance with the invention that are used impair the actual characteristic of the gas-generating mixture. In the case of this use, these temperature fuses in accordance with the invention are preferably provided at thermally exposed points on the generator housing. In this way, a reliable triggering of the temperature fuse in the case of heating from the outside is ensured, as a result of which the controlled ignition of the gas-generating mixture is ensured. In the case of this use, the admixtures in accordance with the invention can be used in the form of tablets, for example. The production of such tablets takes place according to methods which are known per se.
- A further use provides including the temperature fuses in accordance with the invention in the normal ignition device of the gas-generating mixture. In this case, two variants can be used: the temperature fuses in accordance with the invention are distributed homogeneously in the ignition mixture or are separated therefrom, for example in the form of a tablet.
- In all applications, the purity of the substances which are used determines the instant of thermal triggering and the grain size determines the energy which is released locally. For improved processing of the temperature fuses in accordance with the invention, processing aids which are known per se, for example talc, graphite or boron nitride, can be used.
- In addition to their use in safety systems, the temperature fuses in accordance with the invention can also be used, for example, in pressure or safety elements for triggering movements of mechanical elements.
- The temperature fuses in accordance with the invention are compatible with the gas-generating mixture and its components and show, in accordance with the requirements, a temperature and storage stability that is sufficient for the instance of application and considerably improved in comparison with nitrocellulose. The problem of slow decomposition at comparatively high storage temperatures, which is to be noticed in the case of nitrocellulose, is not displayed by the temperature fuses in accordance with the invention. A thermal change at the required storage and operating temperatures could not be established.
- The requirement for the substances used to be toxicologically safe is likewise fulfilled, as is the requirement for the gases and reaction products of the gas-generating mixture, which can be used when blowing up an air bag, for example, to be toxicologically safe; there is no need to fear the motor vehicle passengers being put at risk or harmed.
- The disposal of the gas-generating mixture with the temperature fuses in accordance with the invention is also safe; it is ensured with simple means and without expensive installations.
- The following examples are intended to explain the invention, but without restricting it.
- The specified components of the mixture were homogenised in the given weight ratios in screwed-down plastics containers in a dry-blend mixer for 30 minutes. According to need, there also took place tablet production and granulated-material production by breaking the molded bodies, or even, after addition of a binder, shaping by kneading and subsequent extrusion. The thermally initiable properties were characterised by establishing the detonation point or the calorific behaviour by recording the thermo-gravimetry and differential thermal analysis. The detonation point was determined by heating 100 or 300 mg of a substance (depending on the liveliness of the reaction) to a maximum of 400° C. with a heating rate of 20° C. per minute. The temperature at which a significant reaction takes place with formation of gases or formation of flames, or even deflagration, is given as the detonation point.
- Examples of thermal initiations as a function of the oxidizing agent:
Mass Detonation Components ratios point calcium bistetrazolamine 309° C. calcium bistetrazolamine zinc peroxide 2:1 264° C. calcium bistetrazolamine zinc peroxide 1:1 247° C. calcium bistetrazolamine zinc peroxide 1:2 240° C. calcium bistetrazolamine sodium nitrate 2:1 >400° C. calcium bistetrazolamine sodium nitrate 1:1 >400° C. calcium bistetrazolamine sodium nitrate 1:2 >400° C. 3-nitro-1,2,4-triazol-5-one 260° C. 3-nitro-1,2,4-triazol-5-one strontium nitrate 2:1 211° C. 3-nitro-1,2,4-triazol-5-one strontium nitrate 1:1 243° C. 3-nitro-1,2,4-triazol-5-one strontium nitrate 1:2 247° C. 3-nitro-1,2,4-triazol-5-one ammonium nitrate 2:1 187° C. 3-nitro-1,2,4-triazol-5-one ammonium nitrate 1:1 184° C. 3-nitro-1,2,4-triazol-5-one ammonium nitrate 1:2 192° C. 3-nitro-1,2,4-triazol-5-one zinc peroxide 2:1 251° C. 3-nitro-1,2,4-triazol-5-one zinc peroxide 1:1 239° C. 3-nitro-1,2,4-triazol-5-one zinc peroxide 1:2 235° C. 3-nitro-1,2,4-triazol-5-one potassium 2:1 244° C. perchlorate 3-nitro-1,2,4-triazol-5-one potassium 1:1 244° C. perchlorate 3-nitro-1,2,4-triazol-5-one potassium 1:2 220° C. perchlorate 5-aminotetrazole nitrate 166° C. 5-aminotetrazole nitrate sodium nitrate 1:0.46 166° C. 5-aminotetrazole nitrate iron(III)oxide 1:1 195° C. 5-aminotetrazole nitrate iron(III)oxide/ 1: 162° C. boron nitride* 1/0.1 - Examples of thermal initiations as a function of oxidizable components:
Mass Detonation Components ratios point sodium nitrate 3-nitro-1,2,4-triazol-5-one 2:1 200° C. sodium nitrate 3-nitro-1,2,4-triazol-5-one 1:1 200° C. sodium nitrate 3-nitro-1,2,4-triazol-5-one 1:2 185° C. sodium nitrate 3-nitro-1,2,4-triazol-5-one 1:4 196° C. sodium nitrate 3-nitro-1,2,4-triazol-5-one 1:6 185° C. nitroguanidine 232° C. sodium nitrate nitroguanidine 1:2 >400° C. sodium nitrate nitroguanidine 1:1 >400° C. sodium nitrate nitroguanidine 2:1 >400° C. bistetrazolamine 229° C. sodium nitrate bistetrazolamine 1:2 228° C. sodium nitrate bistetrazolamine 1:1 225° C. sodium nitrate bistetrazolamine 2:1 220° C. - Examples of the thermal initiation of mixtures which contain a plurality of components (for example also as binders) or vary in terms of the selection of oxidizing agents:
(Amounts in % by weight) ditetrazole detonation ammonium nitrate ammonium nitrate binder point 66.7 22.2 11.1 NPE none 66.7 22.2 11.1 PNP 298° C. iron potassium nitro- boron (III) zinc per- sodium detonation guanidine nitride oxide peroxide chlorate nitrate point 20 4 38 38 — — 188° C. 20 4 40 31 5 — 234° C. 20 2 40 30 4 4 203° C. Mass ratios 3-nitro-1,2,4-triazol-5- 40 40 40 34 39.5 one guanidine nitrate 40 39.5 39.5 34 39.5 sodium nitrate 20 20 — 30 — potassium nitrate — — 20 — — potassium perchlorate — — — — 20 graphite — 0.5 0.5 0.5 — boron nitride — — — 1 titanium — — — 1.5 — detonation point 162° C. 155° C. 155° C. 155° C. 150° C. - Example of the thermal initiability of a pyrotechnic mixture of 5-aminotetrazole, guanidine nitrate, sodium nitrate, graphite and an additive in the mass ratio 19.8:28.5:49.2:0.5:2, as a function of the type of additive:
pyrotechnic mixture admixture detonation point ″ titanium >400° C. ″ boron >400° C. ″ ferrocene 273° C. ″ iron(II)oxalate dihydrate 245° C. - Example of the thermal initiability of a pyrotechnic mixture as a function of the amount of the additive iron(II)oxalate dihydrate:
iron(II)oxalate detonation 5-aminotetrazole sodium nitrate dihydrate point 49.9 49.9 0.2 >400° C. 49.7 49.7 0.6 >400° C. 49.3 49.3 1.4 250° C. 48.5 48.5 3.0 251° C. 47 47 6.0 245° C.
Claims (14)
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US09/835,358 US6453816B2 (en) | 1996-07-20 | 2001-04-17 | Temperature fuse with lower detonation point |
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DE19629227.1 | 1996-07-20 | ||
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DE19648809 | 1996-11-26 | ||
US26901899A | 1999-03-17 | 1999-03-17 | |
US09/835,358 US6453816B2 (en) | 1996-07-20 | 2001-04-17 | Temperature fuse with lower detonation point |
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PCT/EP1997/003836 Continuation WO1998003448A1 (en) | 1996-07-20 | 1997-07-17 | Temperature fuse |
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