CN115286476B - Automatic ignition powder composition for gas generator and preparation method and application thereof - Google Patents
Automatic ignition powder composition for gas generator and preparation method and application thereof Download PDFInfo
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- CN115286476B CN115286476B CN202210770885.8A CN202210770885A CN115286476B CN 115286476 B CN115286476 B CN 115286476B CN 202210770885 A CN202210770885 A CN 202210770885A CN 115286476 B CN115286476 B CN 115286476B
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- Prior art keywords
- oxidant
- powder
- combustion catalyst
- ignition
- nitrate
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- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 239000000843 powder Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 86
- 230000001590 oxidative effect Effects 0.000 claims abstract description 65
- 238000002485 combustion reaction Methods 0.000 claims abstract description 48
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 239000000446 fuel Substances 0.000 claims abstract description 39
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 23
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 23
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005751 Copper oxide Substances 0.000 claims abstract description 17
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 17
- BAKYASSDAXQKKY-UHFFFAOYSA-N 4-Hydroxy-3-methylbenzaldehyde Chemical group CC1=CC(C=O)=CC=C1O BAKYASSDAXQKKY-UHFFFAOYSA-N 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 17
- 230000001070 adhesive effect Effects 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 239000004375 Dextrin Substances 0.000 claims description 11
- 229920001353 Dextrin Polymers 0.000 claims description 11
- 235000019425 dextrin Nutrition 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 235000019814 powdered cellulose Nutrition 0.000 claims description 2
- 229920003124 powdered cellulose Polymers 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 238000005550 wet granulation Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 28
- 238000000354 decomposition reaction Methods 0.000 abstract description 17
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract description 10
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 abstract description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 8
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 8
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 abstract description 7
- 229910001487 potassium perchlorate Inorganic materials 0.000 abstract description 7
- -1 guanidine amino nitrate Chemical compound 0.000 abstract description 5
- 239000000395 magnesium oxide Substances 0.000 abstract description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 5
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 abstract description 5
- 235000010344 sodium nitrate Nutrition 0.000 abstract description 5
- 239000004317 sodium nitrate Substances 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 3
- 238000005338 heat storage Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 33
- 238000012360 testing method Methods 0.000 description 30
- 229960004643 cupric oxide Drugs 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000003814 drug Substances 0.000 description 13
- 238000004880 explosion Methods 0.000 description 7
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000004449 solid propellant Substances 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000008194 pharmaceutical composition Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FYGDTMLNYKFZSV-MRCIVHHJSA-N dextrin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)OC1O[C@@H]1[C@@H](CO)OC(O[C@@H]2[C@H](O[C@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-MRCIVHHJSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
- B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
- B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
- B60R21/26—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
- C06B33/04—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide the material being an inorganic nitrogen-oxygen salt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
- B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
- B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
- B60R21/26—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow
- B60R2021/26029—Ignitors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Air Bags (AREA)
Abstract
The invention provides a igniting powder composition with an automatic igniting function, a preparation method and application thereof, and the igniting powder composition provided by the invention comprises the following components by taking the total weight of the automatic igniting powder composition as a reference: and (3) fuel: 5-15% of boron powder and 2-5% of 5-aminotetrazole; oxidizing agent: 30-50% of main oxidant and 8-25% of auxiliary oxidant; and 15-30% of a combustion catalyst, wherein the main oxidant is one or more of potassium nitrate, strontium nitrate and sodium nitrate, and the auxiliary oxidant is one or more of guanidine amino nitrate, potassium perchlorate and potassium chlorate; the combustion catalyst is one or more of copper oxide, ferric oxide and magnesium oxide. By utilizing reasonable proportion and performance complementation of various fuels and oxidants, the invention ensures that the decomposition temperature of the automatic ignition powder is lower, the heat release amount is large, the long-term heat storage is stable and high, the mechanical sensitivity is low, the automatic ignition performance is excellent, and the comprehensive performance is excellent.
Description
Technical Field
The invention relates to the technical field of automobile safety airbag ignition devices, in particular to an automatic ignition powder composition, a preparation method and application thereof, and especially relates to an automatic ignition powder composition with decomposition temperature and explosion point lower than those of gas generating powder and used for a gas generator, a preparation method thereof and application of the automatic ignition powder composition in the gas generator of an automobile safety airbag.
Background
With the rapid development of the automobile industry and the improvement of automobile performance, the safety technology of automobiles is also attracting attention, and therefore, an airbag system as an important component of passive safety of automobiles is particularly important. An airbag system is an inflatable device attached to one or more inflatable airbags installed in a vehicle and functions to rapidly generate large amounts of inflation fluid or gas in a short period of time, which can fill the airbag to prevent the front passenger of the vehicle and the occupant from being injured by the violent impact that is applied by inertia.
However, in the special case of a sudden temperature rise caused by a high temperature environment such as an external fire, the pyrotechnic charge of the gas generator will burn abnormally (the burning speed is abnormal and uncontrollable), even a severe reaction or even explosion will occur, the strength of the shell will be reduced due to the generated high temperature gas, and the shell fragments will be ejected, possibly bringing greater danger to drivers and passengers.
In order to avoid this and to ensure the safety, a filler with an auto-ignition function is newly provided, which can be automatically ignited according to the rise of the ambient temperature without the aid of a mechanical or electronic ignition device, i.e. without starting the gas generator squib, so as to detonate the gas generator and clear the pyrotechnic filler in the gas generator, thus achieving the aim of relieving the danger.
Therefore, the decomposition temperature of the auto-ignition charge is lower than the decomposition temperatures of the gas generating charge and the ignition charge of the airbag gas generating agent. Meanwhile, before the scrappage of the automobile, the automatic ignition powder assembled in the air bag gas generator needs to be stable in performance and long in service life.
At present, the prior art mentions an automatic ignition charge of nitroguanidine-basic copper nitrate, which is placed in a separate cartridge above the squib, so that the airbag is activated before the material strength is not attenuated. However, the ignition temperature of the automatic ignition powder is about 200 ℃, which is close to the thermal decomposition temperature of guanidine nitrate-basic copper nitrate gas generating powder commonly used in the existing air bag gas generator, so that the automatic ignition powder is unfavorable for early ignition of the gas generating powder in a high-temperature environment.
Disclosure of Invention
The invention aims to solve the problems of high decomposition temperature and unstable performance (mainly low mechanical sensitivity) of an automatic ignition powder in the prior art, and provides an automatic ignition medicament composition and a preparation method thereof, wherein the ignition temperature of the automatic ignition medicament composition is proper, namely, the automatic ignition powder can be instantaneously ignited, the reliable ignition is realized, and the ignition performance is obviously improved; while ensuring good long-term storage stability. The automobile safety airbag is suitable for long-time service life of automobiles and meets the requirements of safety airbags for protecting drivers and passengers.
A first object of the present invention is to provide an auto-ignition charge composition for a gas generator, wherein: the automatic ignition powder composition comprises the following components, wherein the automatic ignition powder composition comprises the following components by taking the total weight of the automatic ignition powder composition as a reference:
and (3) fuel: 5-15% of boron powder and 2-5% of 5-aminotetrazole;
oxidizing agent: 30-50% of main oxidant and 8-25% of auxiliary oxidant; and
15-30% of combustion catalyst,
wherein the main oxidant is one or more of potassium nitrate, strontium nitrate and sodium nitrate, and the auxiliary oxidant is one or more of aminoguanidine nitrate, potassium perchlorate and potassium chlorate;
the combustion catalyst is one or more of copper oxide, ferric oxide and magnesium oxide.
A second object of the present invention is to provide a method for preparing the auto-ignition charge composition, the method comprising: mixing fuel, oxidant and combustion catalyst to obtain the automatic ignition powder composition; wherein, based on the total weight of all raw materials, the dosage of each raw material is as follows:
and (3) fuel: 5-15% of boron powder and 2-5% of 5-aminotetrazole;
oxidizing agent: 30-50% of main oxidant and 8-25% of auxiliary oxidant; and
15-30% of combustion catalyst;
the main oxidant is one or more of potassium nitrate, strontium nitrate and sodium nitrate, and the auxiliary oxidant is one or more of aminoguanidine nitrate, potassium perchlorate and potassium chlorate;
the combustion catalyst is one or more of copper oxide, ferric oxide and magnesium oxide.
A third object of the present invention is to provide the use of an auto-ignition composition for a gas generator in an automotive airbag gas generator.
According to the invention, through the combined action of the fuel, the main oxidant, the auxiliary oxidant, the combustion catalyst and other materials, the automatic ignition powder provided by the invention can self-ignite through the environmental heat effect, is easy to ignite, has proper thermal decomposition temperature and large heat release amount. The automatic ignition powder has a real decomposition temperature of only 141.9-153.0 ℃, is easy to ignite, has an initial exothermic decomposition temperature of 177.9-195.6 ℃, can ensure basic thermal stability when used for a gas generator, can not randomly detonate the gas generator at a lower temperature, and can automatically ignite the gas generator under the condition that the temperature of the external environment is abnormally increased, thereby avoiding the explosion of the gas generator at a high temperature.
In particular, when the auxiliary oxidant is preferably guanidine amino nitrate (TAGN for short), the fuel gas has low average molecular weight and low-speed low-temperature combustion characteristic due to higher hydrogen-carbon ratio and nitrogen-carbon ratio. In addition, TAGN has good thermal stability, good compatibility with other components, no moisture absorption in air, and long-term storage without deterioration before use. The TAGN is subjected to nitric acid removal to obtain a triaminoguanidine free radical (TAG), the TAG can Be easily reacted with metals such as Al, mg, be and the like and B, the promotion effect of oxidation-reduction reaction of the automatic ignition powder combustion is enhanced, the thermal decomposition temperature is reduced, the ignition capability of the automatic ignition powder is enhanced, and the combustion heat of the automatic ignition powder can Be improved.
Detailed Description
The invention provides an automatic ignition powder composition for a gas generator, which is characterized in that: the automatic ignition powder composition comprises the following components by weight based on the total weight of the automatic ignition powder composition:
and (3) fuel: 5-15% of boron powder and 2-5% of 5-aminotetrazole;
oxidizing agent: 30-50% of main oxidant and 8-25% of auxiliary oxidant; and
15-30% of combustion catalyst;
wherein the main oxidant is one or more of potassium nitrate, strontium nitrate and sodium nitrate, and the auxiliary oxidant is one or more of aminoguanidine nitrate, potassium perchlorate and potassium chlorate;
the combustion catalyst is one or more of copper oxide, ferric oxide and magnesium oxide.
According to the auto-ignition charge composition provided by the present invention, in the fuel, the average particle diameter D50 of the boron powder is preferably 1 to 55, and the average particle diameter D50 of the 5-aminotetrazole is preferably 1 to 105. The fuel with smaller particles is adopted, so that the fuel is favorable for fully and uniformly mixing, and the gas production speed of the composition can be improved.
In the present invention, the main oxidizing agent is not particularly limited, and may be various oxidizing agents commonly used in the art, and preferably the main oxidizing agent is potassium nitrate. The primary oxidant preferably has an average particle diameter D50 of 50 to 100 mu 5. Grinding by a vibration mill, sieving by a vibration sieve, and taking 100-mesh undersize, wherein the undersize can be repeatedly ground and sieved for use. The oxidant with smaller particles is adopted, so that the raw materials are fully and uniformly mixed, the ignition performance of the composition can be improved, and the burning rate can be improved; considering that the particle size of the particles is large, mixing is not uniform and combustion is difficult.
In the present invention, the auxiliary oxidizing agent is preferably guanidine amino nitrate, and the average particle diameter D50 of the auxiliary oxidizing agent is preferably 10 to 20 μ 5. The addition of the amino guanidine nitrate can improve the combustion heat of the automatic ignition powder, and is beneficial to the ignition of the gas-generating powder by the automatic ignition powder composition.
Preferably, the combustion catalyst is copper oxide; the average particle diameter D50 of the combustion catalyst is preferably 1 to 5 mu 5.
The automatic ignition charge composition provided by the invention can further contain additives, wherein the additives comprise: an adhesive and/or a release agent. The amount of additive need not be excessive, otherwise the fuel and oxidant content of the medicament may be reduced. Preferably, the binder is contained in an amount of 2 to 5% by weight and the release agent is contained in an amount of 0.5 to 2% by weight, based on the total mass of the auto-ignition composition.
The binder is not particularly limited and may be various binders commonly used in the art, and in order to further enhance the binding effect of the auto-ignition powder, it is preferable that the particle size D50 is 10 to 200 mu 5, which is one or more of sucrose, lactose, glucose, powdered cellulose, dextrin and wood flour. Meanwhile, in order to further improve the bonding effect, hot water with the temperature of more than 80 ℃ is adopted for dissolution and then is used as an adhesive.
The adhesive solution used in the invention not only plays a role in adhesion, but also plays a role in coating the energetic material formed by mixing the oxidant, the auxiliary oxidant, the fuel and the additive, reduces the hygroscopicity of the main oxidant, especially potassium nitrate, reduces the sensitivity of the automatic ignition composition, and improves the stability and safety of the automatic ignition composition. Sensitivity refers to the difficulty of explosive combustion or decomposition of the pyrotechnic composition under the action of external stimulus energy. The binder has a certain reaction inertia, and can coat the medicament, thereby reducing the sensitivity of the medicament.
As for the release agent, detailed description will be made later.
In addition, it is preferred that the sum of the moisture content of the components of the auto-ignition pharmaceutical composition is not more than 0.4% by mass of the total mass of the components.
The invention also provides a method for preparing the automatic ignition powder composition, wherein: the method comprises the following steps: mixing fuel, oxidant and combustion catalyst to obtain the automatic ignition powder composition; wherein, based on the total weight of all raw materials, the dosage of each raw material is as follows:
and (3) fuel: 5-15% of boron powder and 2-5% of 5-aminotetrazole;
oxidizing agent: 30-50% of main oxidant and 8-25% of auxiliary oxidant; and
15-30% of combustion catalyst;
the main oxidant is one or more of potassium nitrate, strontium nitrate and sodium nitrate, and the auxiliary oxidant is one or more of aminoguanidine nitrate, potassium perchlorate and potassium chlorate;
the combustion catalyst is one or more of copper oxide, ferric oxide and magnesium oxide.
Preferably, the method further comprises: and carrying out wet granulation, drying and sieving on the obtained automatic ignition powder composition.
In order to ensure the appearance quality of the pressed tablet and improve the production efficiency, a certain proportion of release agent is preferably added in the pressing process, the selection of the release agent is not particularly limited, and the release agent is mainly selected from the factors of low cost, availability, safety, environmental protection and the like, and is preferably one or more of graphite, fumed silica, talcum powder and magnesium stearate, and the particle size D50 is preferably 10-100 mu 5.
In summary, according to the present invention, as a preferred embodiment, the self-ignition pharmaceutical composition comprises the following components in percentage by mass: 5% -15% of boron powder; 30% -50% of potassium nitrate; 8% -25% of amino guanidine nitrate; 15% -30% of copper oxide; 2% -5% of 5-aminotetrazole; 2% -5% of corn dextrin; 0.5 to 2 percent of talcum powder.
The invention also provides an application of the automatic ignition powder composition for the gas generator in the gas generator of the automobile safety airbag.
The automatic ignition powder composition of the invention can be used in air bag gas generators for protecting drivers and passengers in army civil products such as automobiles, airplanes, kayaks, ships and the like, and can also be used in other types of gas generators.
The invention is further illustrated by the following examples. The raw materials used in examples and comparative examples were all obtained by purchasing from suppliers. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. It should be noted that, all the raw materials used in the examples are commercially available, and the particle sizes thereof are within the scope of the present invention, and the particle sizes slightly vary due to the differences between the batches of the raw materials, so that a specific numerical point cannot be given.
Example 1
7.5 parts of fuel amorphous boron powder, 37.5 parts of main oxidant potassium nitrate, 22.5 parts of auxiliary oxidant aminoguanidine nitrate, 27.5 parts of combustion catalyst copper oxide and 2 parts of fuel 5-aminotetrazole are weighed; the preparation method comprises the steps of mixing dry powder of all components uniformly, adding a certain amount of solution containing 3 parts by weight of adhesive dextrin, wet mixing, sieving with a 20-mesh sieve, granulating, drying at 85 ℃ and removing spherical fine powder after wet granulating by using the 20-mesh sieve, thus obtaining the auto-ignition medicament, and recording as S1.
Example 2
Weighing 5 parts by weight of fuel amorphous boron powder, 45 parts by weight of main oxidant potassium nitrate, 16 parts by weight of auxiliary oxidant aminoguanidine nitrate, 22 parts by weight of combustion catalyst copper oxide and 4.4 parts by weight of fuel 5-aminotetrazole; the components are firstly and evenly mixed with dry powder, then a certain amount of solvent containing 3.6 parts by weight of adhesive dextrin is added for wet mixing, the mixture is sieved by a 20-mesh sieve for granulation, the mixture is dried at the temperature of 85 ℃ and the fine powder is removed by the 20-mesh sieve, and the auto-ignition medicament is obtained and is marked as S2.
Example 3
9.64 parts of fuel amorphous boron powder, 48.22 parts of main oxidant potassium nitrate, 16.07 parts of auxiliary oxidant aminoguanidine nitrate, 19.64 parts of combustion catalyst copper oxide and 2.57 parts of fuel 5-aminotetrazole are weighed; the preparation method comprises the steps of mixing dry powder of all components uniformly, adding a certain amount of solvent containing 2.86 parts by weight of adhesive dextrin, wet mixing, sieving with a 20-mesh sieve, granulating, drying at 85 ℃ and removing fine powder by using the 20-mesh sieve, adding 1 part by weight of talcum powder serving as a release agent into a screen material, and obtaining the auto-ignition medicament, which is marked as S3.
Example 4
9.83 parts of fuel amorphous boron powder, 49.14 parts of main oxidant potassium nitrate, 18.89 parts of auxiliary oxidant amino guanidine nitrate, 15.59 parts of combustion catalyst ferric oxide and 2.62 parts of fuel 5-amino tetrazole are weighed; the components are firstly and evenly mixed, then a certain amount of solvent containing 3.93 parts by weight of adhesive dextrin is added for wet mixing, and the mixture is filtered through a 20-mesh sieve for granulation, dried at 85 ℃ and removed by the 20-mesh sieve, and the mixture is marked as S4.
Example 5
15 parts of fuel amorphous boron powder, 50 parts of main oxidant potassium nitrate, 8 parts of auxiliary oxidant aminoguanidine nitrate, 20.33 parts of combustion catalyst cupric oxide and 2.67 parts of fuel 5-aminotetrazole; the components are firstly and evenly mixed with dry powder, then a certain amount of solvent containing 4 parts by weight of adhesive dextrin is added for wet mixing, the mixture is sieved by a 20-mesh sieve for granulation, the mixture is dried at the temperature of 85 ℃ and the fine powder is removed by the 20-mesh sieve, and the auto-ignition medicament is obtained and is marked as S5.
Example 6
In this example, an auto-ignition agent S6 was produced in the same manner as in example 1, except that the auxiliary oxidizing agent was changed from guanidine amino nitrate to potassium perchlorate. The specific method comprises the following steps:
7.5 parts of fuel amorphous boron powder, 37.5 parts of main oxidant potassium nitrate, 22.5 parts of auxiliary oxidant potassium perchlorate, 27.5 parts of combustion catalyst copper oxide and 2 parts of fuel 5-aminotetrazole are weighed; the components are firstly and evenly mixed with dry powder, then a certain amount of solution containing 3 parts by weight of adhesive dextrin is added for wet mixing, the mixture is sieved by a 20-mesh sieve for granulation, the mixture is dried at the temperature of 85 ℃ and the fine powder is removed by the 20-mesh sieve, and the auto-ignition medicament is obtained and is marked as S6.
Comparative example 1
In this comparative example, an auto-ignition agent DS1 was produced in the same manner as in example 1, except that the combustion catalyst was changed from copper oxide to ferric oxide. The specific method comprises the following steps:
7.5 parts of fuel amorphous boron powder, 37.5 parts of main oxidant potassium nitrate, 22.5 parts of auxiliary oxidant amino guanidine nitrate, 27.5 parts of combustion catalyst ferric oxide and 2 parts of fuel 5-amino tetrazole; the components are firstly and evenly mixed with dry powder, then a certain amount of solution containing 3 parts by weight of adhesive dextrin is added for wet mixing, and the mixture is subjected to 20-mesh sieving and granulating, and is dried at 85 ℃ and is subjected to 20-mesh sieving to remove fine powder, so that the automatic ignition medicament is obtained and is marked as DS1.
Comparative example 2
In this comparative example, an automatic ignition agent DS2 was produced in the same manner as in example 5, except that the amount of potassium nitrate as the main oxidizing agent was changed from 50 parts by weight to 56.25 parts by weight and the amount of copper oxide as the combustion catalyst was changed from 20.33 parts by weight to 14.08 parts by weight. The specific method comprises the following steps:
15 parts of fuel amorphous boron powder, 56.25 parts of main oxidant potassium nitrate, 8 parts of auxiliary oxidant aminoguanidine nitrate, 14.08 parts of combustion catalyst cupric oxide and 2.67 parts of fuel 5-aminotetrazole are weighed; the components are firstly and evenly mixed with dry powder, then a certain amount of solvent containing 4 parts by weight of adhesive dextrin is added for wet mixing, and the mixture is sieved by a 20-mesh sieve for granulation, dried at the temperature of 85 ℃ and removed by the 20-mesh sieve to obtain the auto-ignition medicament, which is denoted as DS2.
Comparative example 3
In this comparative example, an auto-ignition agent DS3 was produced in the same manner as in example 5, except that the amount of potassium nitrate as the main oxidizing agent was changed from 50 parts by weight to 60 parts by weight and the amount of copper oxide as the combustion catalyst was changed from 20.33 parts by weight to 10.33 parts by weight. The specific method comprises the following steps:
15 parts of fuel amorphous boron powder, 60 parts of main oxidant potassium nitrate, 8 parts of auxiliary oxidant aminoguanidine nitrate, 10.33 parts of combustion catalyst cupric oxide and 2.67 parts of fuel 5-aminotetrazole are weighed; the components are firstly and evenly mixed with dry powder, then a certain amount of solvent containing 4 parts by weight of adhesive dextrin is added for wet mixing, and the mixture is sieved by a 20-mesh sieve for granulation, dried at the temperature of 85 ℃ and removed by the 20-mesh sieve to obtain the auto-ignition medicament, which is denoted as DS3.
Comparative example 4
18 parts by weight of fuel amorphous boron powder, 67 parts by weight of main oxidant potassium nitrate and 12 parts by weight of fuel 5-aminotetrazole are weighed, all the components are firstly and evenly dry-mixed, then a certain amount of solution containing 3 parts by weight of adhesive polyvinyl alcohol is added for wet mixing, and the mixture is subjected to 20-mesh sieve granulation, dried at 85 ℃ and subjected to 20-mesh sieve removal of fine powder, so that the automatic ignition charge is obtained and is marked as DS4.
Performance testing
Performance testing is carried out on the automatic ignition powder prepared by S1-S6 and DS 1-DS 4:
(1) Heat of explosion
Test instrument: vacuum bomb precision temperature-regulating automatic calorimeter RF-C7000 (TJ) Z.
The test basis is as follows: standard QJ1359-88 method for testing explosion Heat of composite solid propellant
Test conditions: the sample amount was 4 g/time under vacuum, and the test was performed in parallel. The test results are shown in Table 1.
(2) Initial decomposition temperature and exothermic decomposition temperature
Test instrument: german relaxation-resistant STA449F3 ultra-high temperature synchronous thermal analyzer
According to the standard: method for testing thermal decomposition temperature of composite solid propellant, fourth institute of aerospace technology, group, standard number Q/G4A-2002
Test conditions: temperature range: -150 ℃ to +700 ℃; heating rate of 10 ℃/5in, N2 atmosphere, N2 flow rate of 605l/5in; the initial decomposition temperature and exothermic decomposition peak temperature of the auto-ignition charge were tested at a heating rate of 10 ℃/5 in.
The test results are shown in Table 1.
Table 1 combustion performance test data
| Test number | Explosion heat (KJ/Kg) | Initial decomposition temperature (. Degree. C.) | Exothermic decomposition temperature (. Degree. C.) |
| S1 | 5596 | 141.9 | 177.9 |
| S2 | 5138 | 142.0 | 181.3 |
| S3 | 5690 | 150.3 | 185.2 |
| S4 | 5984 | 153.0 | 189.8 |
| S5 | 6181 | 151.6 | 194.6 |
| S6 | 5436 | 143.1 | 171.5 |
| DS1 | 4397 | 165.1 | 204.7 |
| DS2 | 4236 | 173.2 | 203.2 |
| DS3 | 4394 | 173.7 | 216.7 |
| DS4 | 4249 | 175.4 | 229.6 |
As can be seen from the data in Table 1, the automatic ignitors S1 to S6 provided by the present invention have a combustion heat of 5138 to 6181KJ/Kg, which is significantly higher than that of the samples DS1 to DS4 of the comparative examples.
Through the combined action of fuel, oxidant, auxiliary oxidant and combustion catalyst, the automatic ignition powder provided by the invention can self-ignite through environmental heat effect, the initial decomposition temperature is only between 141.9 and 153.0 ℃, the ignition is easy, the thermal decomposition temperature is proper, the heat release amount is large, and the initial exothermic decomposition temperature is between 177.9 and 194.6 ℃. The automatic ignition powder ignition device is suitable for the combustion performance requirement of the automatic ignition powder of the automobile safety airbag gas generator, can ensure basic thermal stability, can not randomly ignite the gas generator at a lower temperature, can automatically ignite the gas generator when the temperature of the external environment is abnormally increased, and avoids the explosion danger of the gas generator at a high temperature.
In addition, as can be seen from Table 1, when the auxiliary oxidizing agent used in example 6 is not the aminoguanidine nitrate preferred in the present invention, the heat burst value is reduced by a certain amount, and the exothermic decomposition temperature is lower than that of examples 1 to 5, which is disadvantageous for the high temperature test and the external disturbance resistance of the airbag generator.
(3) Mechanical sensitivity
(1) Static spark sensitivity measurement
Test instrument: HT-201B type electrostatic sensor
According to the standard: standard QJ1469-1988 of the Ministry of the aerospace industry of the people's republic of China (method for testing electrostatic spark sensitivity of composite solid propellant and other explosives and powders)
Test conditions: the temperature is 20 ℃; relative humidity 35%; capacitance: 10000PF; needle gauge: 0.555.
the test results are shown in Table 2.1.
(2) Pendulum type friction sensitivity measurement
Test instrument: WM-1 pendulum friction sensitivity tester
According to the standard: method for measuring friction sensitivity of composite solid propellant according to national institute of aerospace industry, division standard QJ2913-1987
Test conditions: the temperature is 18 ℃; relative humidity 36%; pendulum angle: 90 °; pressure: 4.0MPa. The test results are shown in Table 2.2.
(3) Impact sensitivity measurement
Test instrument: WL-1 type vertical drop hammer tester
According to the standard: QJ3039 & 1998 method for measuring drop hammer impact sensitivity of composite solid propellant
Test conditions: the temperature is 18 ℃; relative humidity 32%; weight of drop hammer: 10kg. The test results are shown in Table 2.3.
Table 2.1 formulation agent static spark sensitivity test data
Table 2.2 formulation pendulum friction sensitivity test data
Table 2.3 formulation agent crash sensitivity test data
Note that: the above test data are averages of 3 or more tests in parallel.
As can be seen from the data in tables 2.1 to 2.3, the electrostatic spark sensitivity and impact sensitivity performances of the automatic ignitors S1 to S6 provided by the invention are superior to those of the samples DS1 to DS4 of the comparative examples; pendulum friction sensitivity examples were comparable to comparative test data. The lower mechanical sensitivity ensures the preparation process safety of the ignition powder component with the automatic ignition function, and has higher production guidance effect on realizing engineering mass production.
It can be seen from tables 2.1 and 2.3 that the mechanical sensitivity of the auxiliary oxidizing agent used in example 6 is higher than that of example 1 when it is not the aminoguanidine nitrate preferred in the present invention.
When the combustion catalyst used in comparative example 1 was not the combustion catalyst selected in the present invention, the electrostatic spark sensitivity and the impact sensitivity were higher than those of example 1.
In comparative examples 2 to 3, when the amounts of the main oxidizing agent and the combustion catalyst are not within the scope of the present invention, the electrostatic spark sensitivity and the impact sensitivity were higher than those of example 1.
Meanwhile, in comparative example 4, when the composition of the autoignition charge (only the fuel, the main oxidizing agent, and the binder, no auxiliary oxidizing agent, and no combustion catalyst) is different from the present invention, the electrostatic spark sensitivity, the impact sensitivity, and the friction sensitivity are all higher than those of the other examples and comparative examples.
The foregoing is merely illustrative of the best embodiments of the present invention, and the present invention is not limited thereto, but any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be construed as falling within the scope of the present invention.
Claims (9)
1. An automatic ignition charge composition for a gas generator, characterized by: the effective components of the automatic ignition powder composition are composed of the following components by taking the total weight of the automatic ignition powder composition as a reference:
and (3) fuel: 5-15% of boron powder and 2-5% of 5-aminotetrazole;
oxidizing agent: 30-50% of main oxidant and 8-25% of auxiliary oxidant; and
15-30% of combustion catalyst,
wherein the main oxidant is potassium nitrate;
the auxiliary oxidant is amino guanidine nitrate;
the combustion catalyst is copper oxide.
2. An auto-ignition charge composition according to claim 1, wherein: the main oxidant is potassium nitrate; the average particle diameter D50 of the main oxidant is 50-100 mu m.
3. An auto-ignition charge composition according to claim 1, wherein: the auxiliary oxidant is amino guanidine nitrate; the average particle diameter D50 of the auxiliary oxidant is 10-20 mu m.
4. An auto-ignition charge composition according to claim 1, wherein: the combustion catalyst is copper oxide; the average particle diameter D50 of the combustion catalyst is 1-5 mu m.
5. An auto-ignition charge composition according to claim 1, wherein: also contains additives, wherein the additives comprise: an adhesive and/or a release agent.
6. An auto-ignition charge composition according to claim 5, wherein:
based on the total weight of the auto-ignition charge composition: the content of the adhesive is 2-5%, and the content of the release agent is 0.5-2%;
the adhesive is one or more of sucrose, lactose, glucose, powdered cellulose, dextrin and wood flour, and the granularity D50 of the adhesive is 10-200 mu m;
the release agent is one or more of graphite, fumed silica, talcum powder and magnesium stearate, and the granularity D50 of the release agent is 10-100 mu m.
7. A method for producing an automatic ignition charge composition according to any one of claims 1 to 6, characterized by: the method comprises the following steps: mixing fuel, oxidant and combustion catalyst to obtain the automatic ignition powder composition; wherein, based on the total weight of all raw materials, the dosage of each raw material is as follows:
and (3) fuel: 5-15% of boron powder and 2-5% of 5-aminotetrazole;
oxidizing agent: 30-50% of main oxidant and 8-25% of auxiliary oxidant; and
15-30% of combustion catalyst;
the main oxidant is potassium nitrate;
the auxiliary oxidant is amino guanidine nitrate;
the combustion catalyst is copper oxide.
8. The method of claim 7, wherein the method further comprises: and carrying out wet granulation, drying and sieving on the obtained automatic ignition powder composition.
9. Use of an auto-ignition composition for a gas generator according to any one of claims 1 to 6 in an automotive airbag gas generator.
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| CN101466653A (en) * | 2006-04-19 | 2009-06-24 | 日本化药株式会社 | Explosive composition, explosive composition molded body, and their production methods |
| CN101687722A (en) * | 2007-07-16 | 2010-03-31 | 关键安全体系股份有限公司 | Gas generating compositions and airbag inflator |
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