EP2616413A2 - Pyrotechnic gas generator compounds - Google Patents
Pyrotechnic gas generator compoundsInfo
- Publication number
- EP2616413A2 EP2616413A2 EP11773097.8A EP11773097A EP2616413A2 EP 2616413 A2 EP2616413 A2 EP 2616413A2 EP 11773097 A EP11773097 A EP 11773097A EP 2616413 A2 EP2616413 A2 EP 2616413A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- compound according
- combustion
- composition
- compounds
- pressure
- 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
- 150000001875 compounds Chemical class 0.000 title claims abstract description 99
- 238000002485 combustion reaction Methods 0.000 claims abstract description 95
- 239000000203 mixture Substances 0.000 claims abstract description 59
- 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 abstract description 28
- 239000003607 modifier Substances 0.000 claims abstract description 28
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims abstract description 19
- 239000004615 ingredient Substances 0.000 claims abstract description 19
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000002360 explosive Substances 0.000 claims abstract description 10
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 15
- 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 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 8
- 239000008188 pellet Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000005751 Copper oxide Substances 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 description 31
- 238000005056 compaction Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- 238000010348 incorporation Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000670 limiting effect Effects 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000567 combustion gas Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 239000003380 propellant Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002927 oxygen compounds Chemical class 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000000028 HMX Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium 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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007937 lozenge Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000009490 roller compaction Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity 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
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
-
- 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
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0033—Shaping the mixture
- C06B21/0066—Shaping the mixture by granulation, e.g. flaking
-
- 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
- C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
- C06B29/02—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate of an alkali metal
- C06B29/08—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate of an alkali metal with an organic non-explosive or an organic non-thermic component
-
- 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
- C06D5/02—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by decompressing compressed, liquefied or solidified gases
-
- 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 pyrotechnic compounds gas generators, suitable for use in protective systems of occupants of motor vehicles, more particularly for the inflation of damping cushions (so-called “airbags”) and particularly for the inflation of side damping cushions (so-called “side airbags” (see below)).
- airbags damping cushions
- side airbags side damping cushions
- the technical field relating to the protection of occupants of motor vehicles has grown considerably over the last twenty years.
- the latest generation of vehicles now include in the cabin several airbag-type airbag safety systems whose functioning is provided by the combustion gases of pyrotechnic compounds.
- the cushioning type of systems there are mainly frontal airbags for frontal impact and side airbags for side impact.
- Side airbag systems differ from frontal airbag systems primarily in the time required for deployment and placement of the airbag. Typically, this time is shorter for a side airbag (of the order of 10-20 ms, against 40-50 ms for a front airbag).
- a side airbag the functional need for inflation of the bag over a short time requires the use of a pyrotechnic composition having a sufficiently high combustion rate (typically equal to or greater than 30 mm / s, or even 35 mm / s, at 20 MPa ) over the operating pressure range in the generator combustion chamber, in order to obtain an inflated surface flow rate value (product pxnx Te x Vc) sufficient.
- the pyrotechnic composition in order to ensure satisfactory system operation, must also have good reliability characteristics. Also, given the generally decreasing surface profile of the loadings employed (pellet type), the composition should ideally have a stable and sufficiently high combustion rate at low pressure. In fact, those skilled in the art are aware that the . - specifications of the side airbags is more restrictive than that of the front airbags. Of course, any technological advance in the field of said side airbags can also advantageously be declined in the field of frontal airbags.
- a low pressure is defined as a pressure P such that: 0.1 ⁇ P ⁇ 10 MPa, by medium pressure, a pressure P such that: 10 MPa ⁇ P ⁇ 30 MPa, by high pressure, a pressure P such that: P> 30 MPa.
- the desired increase in the rate of combustion of the pyrotechnic compound in question over the entire pressure range, including at low pressure, is therefore not only necessary to increase the gas flow to reach the inflation time specifications, but also to ensure the ignitability of the compound without resorting to the use of a relay charge and the safety of the products of combustion.
- said combustion temperature should not be too high (it must at least remain below 2400 K, more favorably below 2350 K) so that the temperature of the gases in the cushioning cushion does not affect the integrity physical of the occupant.
- a low combustion temperature makes it possible, on the one hand, to limit the thickness of the bag and, on the other hand, to simplify the design of the gas generator by making it possible to reduce the presence of baffles and filters within it. this.
- those skilled in the art are in search of pyrotechnic compounds which are suitable for use in fully pyrotechnic gas generators or in hybrid generators, more particularly intended for side airbags, that is to say simultaneously presenting a moderate combustion temperature of the order of 2000-2400 K, more favorably 2000-2350 K, and a high combustion rate over the entire operating pressure range (especially greater than 30 mm / s at 20 MPa, more favorably higher at 35 mm / s at 20 MPa, v included at low pressure.
- pyrotechnic compounds for airbags must also tend to meet the following requirements together:
- the gases generated by the combustion of the pyrotechnic charge (comprising a compound or n compounds) must be non-toxic, that is to say have a low content of carbon monoxide, oxides of nitrogen and chlorinated compounds; . _
- the gas yield ie the quantity of gas generated by the combustion
- the pressure exponent must be as low as possible, especially at medium and high pressure (typically less than 0.35 as described in the prior art) but also at low pressure.
- a low pressure exponent makes it possible to significantly reduce the variability of operation between the extreme low temperature (around -40 ° C) and the extreme high temperature (around 90 ° C) required in the field of use. The reproducibility of the operation is thereby improved and the size of the metal structure of the generator can be advantageously reduced;
- the basic ingredients of the compounds be pyrotechnically non-hazardous.
- ingredient (s) belonging to the class of explosives such as nitroguanidine, hexogen (RDX), octogen (H X) is advantageously avoided.
- Explosive ingredients are ingredients classified in risk division 1.1 according to standard NF T 70-502 (see also UN - Recommendations on the Transport of Dangerous Goods - Manual of Tests and Criteria, Fourth revised edition, ST / SG / AC.10 / ll / Rev.4, ISBN 92-1-239083-8ISSN 1014-7179 and STANAG 4488).
- Guanidine nitrate and potassium perchlorate, taken separately, are not ingredients in this risk division. They are not explosive ingredients, especially in the sense of the invention.
- These compounds also include in their composition a low level of a ballistic catalyst, consisting of an oxygen compound of a transition metal, advantageously with a high specific surface area, traditionally used in the field of propellants to increase the combustion rate at medium and high pressure (this catalyst accelerates the decomposition of the oxidizing charge).
- a ballistic catalyst consisting of an oxygen compound of a transition metal, advantageously with a high specific surface area, traditionally used in the field of propellants to increase the combustion rate at medium and high pressure (this catalyst accelerates the decomposition of the oxidizing charge).
- a high exponent of low-pressure pressure and the non-combustion at atmospheric pressure of the compounds in question are not a problem, since the pressure does not fall back, in the context of use of said compounds, to a low level before the end of pyrotechnic operation.
- This application for belt retractor devices does not require, for the gas generator, requirements as severe as those required in the context of the present invention (airbags, and especially side airbags), especially a high rate of combustion. at low pressure, a lowering of the limit threshold of combustion pressure (closer to atmospheric pressure) and a low pressure exponent over the entire range of combustion (especially at low pressure).
- pyrotechnic compounds that offer a good compromise, in terms of gas temperature, gas yield, emitted particulate levels and toxicity, contain, as main ingredients, guanidine nitrate (NG) in as a reducing filler and basic copper nitrate (BCN) as an oxidizing filler.
- NG guanidine nitrate
- BCN basic copper nitrate
- a combustion rate to 20 MPa slightly increased compared to compositions formulated based on guanidine nitrate (NG) and basic copper nitrate (BCN), but which remains insufficient for use in side airbags.
- NG guanidine nitrate
- BCN basic copper nitrate
- thermodynamic and ballistic characteristics of such a compound (reference compound 1), whose composition (“binary") contains only guanidine nitrate (NG) and potassium perchlorate (KCIO 4 ), are presented in Table 1 below. - -
- the given value is a relative pressure.
- a zero combustion pressure limit corresponds to the atmospheric pressure.
- Reference compound 1 has many of the advantages expected from a gas generator compound for an airbag system.
- the basic ingredients are simple and easily available, inexpensive, non-hazardous on the pyrotechnic aspects (no component of the class of explosive compounds) and non-toxic.
- the thermodynamic performances (gas yield, particle rate) are good and the combustion temperature remains moderate and therefore acceptable.
- the particles emitted by combustion are non-toxic (essentially KCl).
- the burning rate of the order of 26 mm / s to 20 MPa is only 20 to 30% higher than that of a compound based on _ Guanidine nitrate (NG) and basic copper nitrate (BCN), and remains low compared to the set specifications.
- NG Guanidine nitrate
- BCN basic copper nitrate
- compositions of the pyrotechnic gas-generating compounds of the invention (particularly suitable for airbag applications, especially lateral applications) contain:
- At least one combustion modifier chosen from transition metal oxides, precursors of such oxides and mixtures thereof,
- compositions of compounds of the invention consist (exclusively) in the ingredients listed above (NG + KCI0 4 + at least one combustion modifier + optionally at least one additive) taken at the levels indicated below. above.
- the ingredients of the first three types above generally represent more than 90% by weight of the total mass (of the composition) of the compounds of the invention, very generally at less than 94% by weight, or even more than 98% by weight.
- additive such as production auxiliaries (calcium stearate, silica, for example)
- the ingredients of the three types above can be quite 100% by weight of the total mass of the compounds of the invention.
- Guanidine nitrate representing 60 to 70% of the total mass, is also selected for reasons of pyrotechnic safety and for its rheoplastic behavior, suitable for the implementation of compaction phases and possible pelletization of the process.
- dry see - - hereinafter
- the manufacture of the compounds by the dry process process comprises up to four main steps (see below), which have been described in particular in the patent application WO 2006/134311.
- Potassium perchlorate is present in the composition of the compounds of the invention at a moderate intermediate level (from 26 to 33% by weight, advantageously from 26 to 30% by weight), particularly with reference to the combustion temperature, "ignitability" and the target high-pressure combustion rate.
- the combustion modifiers selected by the inventors, develop particularly interesting (unexpected) properties with reference to the three improvement points sought (see above).
- Said at least one combustion modifier is selected from transition metal oxides, precursors of such oxides and mixtures thereof.
- a precursor of such an oxide leads to the formation of such an oxide (generates such an oxide) during its decomposition in temperature during the combustion of the pyrotechnic compound.
- the basic copper nitrate (Cu (NO 3 ) 2 '3Cu (OH) 2 ) is decomposed into copper oxide (CuO) (see below).
- Said at least one combustion modifier is present in a sufficient amount (> 2.5% by weight), to be effective (with reference to the three improvement points above), and not excessive ( ⁇ 6% by weight) in order not to harm the gas yield.
- a single combustion modifier is generally present but the presence of at least two such additives is expressly provided for in the context of the present invention.
- said at least one combustion modifier is selected from zinc oxide (ZnO), iron oxide (Fe 2 O 3 ), chromium oxide ( ⁇ 2 ⁇ 3 ), manganese dioxide ( MnO 2 ), copper oxide (CuO), basic copper nitrate (Cu (NO 3 ) 2-3Cu (OH) 2 ) and mixtures thereof.
- the copper oxide and the basic copper nitrate, precursor of said copper oxide are - - particularly powerful.
- the compounds of the invention therefore contain, as a combustion modifier, copper oxide and / or basic nitrate of copper. The use of these combustion modifiers makes it possible to obtain compounds of the invention having a pressure exponent value of less than or equal to 0.1 over the pressure range 6-52 Pa.
- said at least one combustion modifier according to the invention has a specific surface area greater than 3 m 2 / g / advantageously greater than 10 m 2 / g, very advantageously greater than 25 m 2 / g.
- a pressure (relative, that is to say with reference to atmospheric pressure) combustion limit less than or equal to 1.5 MPa, preferably less than 0.2 MPa, very advantageously equal to 0.1 MPa, - -
- the pyrotechnic compounds of the invention may contain, at a low mass level (less than or equal to 6%, generally at least 0.1%), at least one additive, especially at least one additive making it easier to obtain (shaping, when they are obtained), such as calcium or magnesium stearate, graphite and / or at least an additive improving the aggregation of the solid products of their combustion chosen from refractory oxides with a softening or melting temperature adapted to the composition, such as silica or alumina.
- at least one additive especially at least one additive making it easier to obtain (shaping, when they are obtained), such as calcium or magnesium stearate, graphite and / or at least an additive improving the aggregation of the solid products of their combustion chosen from refractory oxides with a softening or melting temperature adapted to the composition, such as silica or alumina.
- silica generally introduced in fine powder form (advantageously of micrometric size, very advantageously of nanometric dimension) having a high specific surface area (Advantageously 100 m 2 / g or more) or in the form of silica fibers of small diameter (1 to 20 microns) and a few tens or hundreds of microns (20 to 500 microns) in length.
- the at least one additive intervenes with the constituent ingredients
- compositions of the compounds of the invention do not contain any explosive ingredient (see the NF standard and the UN recommendations specified above), and this, in particular with reference to the parameters: pyrotechnic safety and combustion temperature. It should also be noted that the masses of pyrotechnic compounds required for the inflation of an airbag, in particular of a lateral airbag, are greater than those required for the inflation of a retractor device according to US Pat. 6,893,517 (said inflations not being of the same type: inflation time greater than 10-20 ms / per pulse).
- the pyrotechnic compounds of the invention can be obtained by a wet process.
- said process comprises the extrusion of a paste containing the constituents of the compound.
- said process includes a step of aqueous dissolution of all (or some) of the main constituents comprising solubilization of at least one of said main constituents (oxidant and / or reducing agent) and then obtaining a powder by spray-drying, the addition to the powder obtained of the constituent (s) which would not have been dissolved, and the shaping of the powder in the form of objects by the usual processes in the dry process.
- the pyrotechnic compounds of the invention may also be obtained in the dry process, for example by simply pelletizing the powder obtained by mixing their constituents.
- the preferred method of obtaining the pyrotechnic compounds of the invention includes a dry compaction step of a mixture of powder constitutive ingredients of said compounds (except for said at least one additive which may be added during the process). Dry compaction is generally carried out, in a manner known per se, in a roller compactor, at a compacting pressure of between 10 8 and 6.10 8 Pa. It can be implemented according to different variants (with a characteristic step compaction "simple" followed by at least one complementary step, with a compaction characteristic step coupled to a shaping step). Thus, the pyrotechnic compounds of the invention are likely to exist in different forms (especially over the manufacturing process leading to the final compounds):
- pellets After dry compaction followed by granulation and then pelletizing (dry compression), pellets are obtained;
- the pyrotechnic compounds of the invention are therefore particularly likely to exist in the form of objects of the type:
- the granules of the invention generally have a particle size (a median diameter) of between 200 and 1400 ⁇ m (and an apparent density of between 0.8 and 1.2 cm 3 / g);
- the pellets of the invention generally have a thickness of between 1 and 3 mm.
- the constitutive ingredients of the compounds of the invention advantageously have a fine particle size, less than or equal to 20 ⁇ m. Said granulometry (value of the median diameter) is generally between 3 and 20 pm.
- the compounds described in the present invention express their full potential if they are obtained by a dry process from powders having a median diameter of between 10 and 20 pm for KCl0 4 and 5 to 15 pm for guanidine nitrate. .
- the present invention relates to a powdery composition (mixture of powders), precursor of a compound of the invention, the composition of which corresponds to that of a compound of the invention (see above ).
- the present invention relates to gas generators containing at least one pyrotechnic compound of the invention.
- Said generators are ideal for airbags, especially side airbags (see above).
- Table 2 gives examples of compositions of compounds of the present invention, as well as the performances of said compounds compared with those of the compound of the prior art of reference 1.
- the compounds were evaluated by means of thermodynamic calculations or from physical measurements on pellets or pellets made from the compositions via the mixing process of . . powders - compaction - granulation - and possibly dry pelletisation.
- the reference compound 1 of the prior art contains guanidine nitrate and potassium perchlorate and does not contain a combustion modifier within the meaning of the invention.
- the compounds of Examples 1 to 7 contain in their composition, in addition to the two constituents of the reference compound 1, such a combustion modifier.
- the levels of the major constituents have been adjusted in order to maintain an oxygen balance value close to -3%, so that the performances of the compounds of Table 1 can be directly compared.
- said addition conjointly leads to a very significant lowering of the pressure exponent, a very low pressure exponent over the entire operating pressure range (beyond 6 MPa), of the combustion limit pressure and a significant increase in the low-pressure combustion rate.
- CuO is the compound which, added to the reference composition
- CuO and BCN allow, when incorporated at a reduced rate (5% in the examples), to retain an advantageous value of gas yield (> 32 g / mol) and ultimately lead to a very significant improvement in the surface flow rate value of inflation (by more than 40%) relative to the reference composition NG / KCIO4 of the reference compound 1.
- Table 3 shows the second surprising effect demonstrated by the inventors, namely the very significant reduction in the combustion limit pressure (measured on granules) when silica is introduced at a moderate rate into the composition of the compounds of the invention.
- This same effect, obtained with another refractory metal oxide such as alumina, is not of sufficient magnitude to be of interest.
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Abstract
Description
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COMPOSES PYROTECHNIQUES GENERATEURS DE GAZ PYROTECHNIC COMPOUNDS GENERATORS OF GAS
La présente invention a pour objet des composés pyrotechniques générateurs de gaz, convenant pour une utilisation dans des systèmes de protection d'occupants de véhicules automobiles, plus spécialement pour le gonflage de coussins amortissants (dits "airbags") et tout particulièrement pour le gonflage de coussins amortissants latéraux (dits "airbags" latéraux (voir ci-dessous)). The present invention relates to pyrotechnic compounds gas generators, suitable for use in protective systems of occupants of motor vehicles, more particularly for the inflation of damping cushions (so-called "airbags") and particularly for the inflation of side damping cushions (so-called "side airbags" (see below)).
Le domaine technique relatif à la protection des occupants de véhicules automobiles a connu un essor très important durant les vingt dernières années. Les véhicules de dernière génération intègrent dorénavant au sein de l'habitacle plusieurs systèmes de sécurité, de type coussin gonflable amortissant (dit "airbag") dont le fonctionnement est assuré par les gaz de combustion de composés pyrotechniques. Parmi les systèmes de type coussin amortissant, on distingue principalement les airbags frontaux pour choc frontal et les airbags latéraux pour choc latéral. The technical field relating to the protection of occupants of motor vehicles has grown considerably over the last twenty years. The latest generation of vehicles now include in the cabin several airbag-type airbag safety systems whose functioning is provided by the combustion gases of pyrotechnic compounds. Among the cushioning type of systems, there are mainly frontal airbags for frontal impact and side airbags for side impact.
Les systèmes airbags latéraux se différencient des systèmes airbags frontaux essentiellement par le temps requis pour le déploiement et la mise en place du coussin gonflable. Typiquement, ce temps est plus court pour un airbag latéral (de l'ordre de 10-20 ms, contre 40-50 ms pour un airbag frontal). Pour un airbag latéral, le besoin fonctionnel de gonflage du sac sur un temps court impose de recourir à une composition pyrotechnique présentant une vitesse de combustion suffisamment élevée (typiquement égale ou supérieure à 30 mm/s, voire 35 mm/s, à 20 MPa) sur la plage de pression de fonctionnement dans la chambre de combustion du générateur, ceci afin d'obtenir une valeur de débit surfacique de gonflage (produit p x n x Te x Vc) suffisante. Par ailleurs, afin d'assurer une mise en régime satisfaisante du système, la composition pyrotechnique doit également présenter de bonnes caractéristiques d'allumabiiité. Aussi, compte tenu du profil de surface généralement dégressif des chargements employés (de type pastille), la composition doit idéalement présenter une vitesse de combustion stable et suffisamment élevée à basse pression. En fait, l'homme du métier n'ignore pas que le . - cahier des charges des airbags latéraux est plus contraignant que celui des airbags frontaux. Bien évidemment, toute avancée technologique dans le domaine desdits airbags latéraux peut aussi avantageusement se décliner dans le domaine des airbags frontaux. Side airbag systems differ from frontal airbag systems primarily in the time required for deployment and placement of the airbag. Typically, this time is shorter for a side airbag (of the order of 10-20 ms, against 40-50 ms for a front airbag). For a side airbag, the functional need for inflation of the bag over a short time requires the use of a pyrotechnic composition having a sufficiently high combustion rate (typically equal to or greater than 30 mm / s, or even 35 mm / s, at 20 MPa ) over the operating pressure range in the generator combustion chamber, in order to obtain an inflated surface flow rate value (product pxnx Te x Vc) sufficient. Moreover, in order to ensure satisfactory system operation, the pyrotechnic composition must also have good reliability characteristics. Also, given the generally decreasing surface profile of the loadings employed (pellet type), the composition should ideally have a stable and sufficiently high combustion rate at low pressure. In fact, those skilled in the art are aware that the . - specifications of the side airbags is more restrictive than that of the front airbags. Of course, any technological advance in the field of said side airbags can also advantageously be declined in the field of frontal airbags.
Dans le présent texte, on définit par basse pression, une pression P telle que : 0,1 < P < 10 MPa, par moyenne pression, une pression P telle que : 10 MPa < P < 30 MPa, par haute pression, une pression P telle que : P > 30 MPa. In the present text, a low pressure is defined as a pressure P such that: 0.1 <P <10 MPa, by medium pressure, a pressure P such that: 10 MPa <P <30 MPa, by high pressure, a pressure P such that: P> 30 MPa.
Il est par ailleurs d'usage de compenser les faibles vitesses de combustion des composés pyrotechniques utilisés dans les générateurs de gaz pour airbag actuels, en ayant recours à des chargements composés de pastilles de très faibles dimensions. Bien que n'étant pas économiquement intéressant du fait du faible débit massique de production des machines de pastillage et des coûts d'outillage induits, ceci permet, dans une certaine mesure, de pallier en partie le manque de vitesse de combustion. Cette solution accentue toutefois deux autres inconvénients : It is also customary to compensate for the low combustion rates of the pyrotechnic compounds used in current airbag gas generators, by using loadings composed of pellets of very small dimensions. Although it is not economically attractive because of the low mass flow rate of pelletizing machines and the resulting tooling costs, this makes it possible, to a certain extent, to overcome part of the lack of combustion speed. This solution, however, highlights two other disadvantages:
- la difficulté d'allumage, qui est augmentée du fait de la forte surface initiale du chargement, ce qui nécessite alors l'emploi d'un allumeur renforcé ou l'ajout d'une charge supplémentaire faisant office de relais d'allumage ; - The difficulty of ignition, which is increased because of the large initial surface of the load, which then requires the use of a reinforced igniter or the addition of an additional load acting ignition relay;
- une forte dégressivité de la surface en combustion du fait de la dimension réduite des pastilles, ce qui induit une longue queue de combustion à basse pression. Cette longue queue de combustion à basse pression est la source de l'émission de la majorité des espèces toxiques présentes dans les gaz servant à gonfler le coussin. - A strong degression of the burning surface due to the reduced size of the pellets, which induces a long tail of combustion at low pressure. This long tail of low pressure combustion is the source of the emission of the majority of the toxic species present in the gases used to inflate the cushion.
Il convient donc de noter que l'augmentation recherchée de la vitesse de combustion du composé pyrotechnique en cause, sur toute la plage de pression, y compris à basse pression, est donc non seulement nécessaire pour accroître le débit de gaz afin d'atteindre les spécifications de délai de gonflage, mais aussi pour assurer l'allumabilité du composé sans recourir à l'emploi d'une charge relais et l'innocuité des produits de combustion. It should therefore be noted that the desired increase in the rate of combustion of the pyrotechnic compound in question over the entire pressure range, including at low pressure, is therefore not only necessary to increase the gas flow to reach the inflation time specifications, but also to ensure the ignitability of the compound without resorting to the use of a relay charge and the safety of the products of combustion.
De surcroit, il existe des contraintes en référence à la température de combustion. . . In addition, there are constraints with reference to the combustion temperature. . .
De façon générale, ladite température de combustion ne doit pas être trop élevée (elle doit a minima rester inférieure à 2400 K, plus favorablement inférieure à 2350 K) afin que la température des gaz dans le coussin amortissant ne porte pas atteinte à l'intégrité physique de l'occupant. Une température de combustion basse permet, d'une part, de limiter l'épaisseur du sac et, d'autre part, de simplifier la conception du générateur de gaz en permettant de diminuer la présence de chicanes et de filtres au sein de celui-ci. In general, said combustion temperature should not be too high (it must at least remain below 2400 K, more favorably below 2350 K) so that the temperature of the gases in the cushioning cushion does not affect the integrity physical of the occupant. A low combustion temperature makes it possible, on the one hand, to limit the thickness of the bag and, on the other hand, to simplify the design of the gas generator by making it possible to reduce the presence of baffles and filters within it. this.
Les systèmes airbags latéraux peuvent faire appel à deux types de générateurs de gaz : ceux dits entièrement pyrotechniques (la génération de gaz étant alors assurée exclusivement par la combustion d'un chargement pyrotechnique) et ceux dits "hybrides" (les gaz provenant alors de façon conjointe de la combustion d'un chargement pyrotechnique et d'un volume de gaz neutre stocké sous pression dans un réservoir étanche). Pour les générateurs de type "hybride", le chargement pyrotechnique ne doit pas présenter une température de combustion trop basse afin que les gaz de combustion soient suffisamment chauds pour compenser la baisse de température engendrée par l'expansion de volume du gaz neutre pré-comprimé. Idéalement, des températures de combustion supérieures à 2000 K sont requises. Side airbag systems can use two types of gas generators: those called fully pyrotechnic (the gas generation being then ensured exclusively by the combustion of a pyrotechnic charge) and those called "hybrids" (the gases then coming from joint combustion of a pyrotechnic charge and a volume of neutral gas stored under pressure in a sealed tank). For "hybrid" type generators, the pyrotechnic charge must not have a low combustion temperature so that the combustion gases are sufficiently hot to compensate for the temperature drop caused by the expansion of the pre-compressed neutral gas volume. . Ideally, combustion temperatures above 2000 K are required.
Ainsi, l'homme du métier est à la recherche de composés pyrotechniques qui conviennent pour une utilisation dans des générateurs de gaz entièrement pyrotechniques ou dans des générateurs hybrides, plus particulièrement destinés à des airbags latéraux, c'est-à-dire présentant simultanément une température de combustion modérée de l'ordre de 2000-2400 K, plus favorablement 2000-2350 K, et une vitesse de combustion élevée sur toute la plage de pression de fonctionnement (notamment supérieure à 30 mm/s à 20 MPa, plus favorablement supérieure à 35 mm/s à 20 MPa . v compris à basse pression. Thus, those skilled in the art are in search of pyrotechnic compounds which are suitable for use in fully pyrotechnic gas generators or in hybrid generators, more particularly intended for side airbags, that is to say simultaneously presenting a moderate combustion temperature of the order of 2000-2400 K, more favorably 2000-2350 K, and a high combustion rate over the entire operating pressure range (especially greater than 30 mm / s at 20 MPa, more favorably higher at 35 mm / s at 20 MPa, v included at low pressure.
En outre, les composés pyrotechniques pour airbags doivent aussi tendre à satisfaire conjointement aux exigences suivantes : In addition, pyrotechnic compounds for airbags must also tend to meet the following requirements together:
- les gaz générés par la combustion du chargement pyrotechnique (comprenant un composé ou n composés) doivent être non toxiques, c'est-à-dire présenter une teneur faible en monoxyde de carbone, en oxydes d'azote et en composés chlorés ; . _ the gases generated by the combustion of the pyrotechnic charge (comprising a compound or n compounds) must be non-toxic, that is to say have a low content of carbon monoxide, oxides of nitrogen and chlorinated compounds; . _
- le rendement gazeux (c'est-à-dire la quantité de gaz généré par la combustion) doit être élevé afin de conduire à un fort pouvoir de gonflage ; the gas yield (ie the quantity of gas generated by the combustion) must be high in order to lead to a high inflation power;
- la quantité de particules solides générées par la combustion, susceptibles de constituer des points chauds pouvant endommager la paroi du coussin gonflable, doit demeurer faible ; the quantity of solid particles generated by the combustion, which may constitute hot spots that can damage the wall of the airbag, must remain low;
- l'exposant de pression doit être le plus faible possible, notamment à moyenne et haute pression (typiquement inférieur à 0,35 ainsi que décrit dans l'art antérieur) mais aussi à basse pression. Un faible exposant de pression permet en effet de réduire de manière très significative la variabilité du fonctionnement entre la température extrême basse (vers -40°C) et la température extrême haute (vers 90°C) requises dans le domaine d'utilisation. La reproductibilité du fonctionnement est de ce fait améliorée et la dimension de la structure métallique du générateur peut être avantageusement réduite ; - The pressure exponent must be as low as possible, especially at medium and high pressure (typically less than 0.35 as described in the prior art) but also at low pressure. A low pressure exponent makes it possible to significantly reduce the variability of operation between the extreme low temperature (around -40 ° C) and the extreme high temperature (around 90 ° C) required in the field of use. The reproducibility of the operation is thereby improved and the size of the metal structure of the generator can be advantageously reduced;
- leur pression limite de combustion doit être aussi proche que possible de la pression atmosphérique. - their limiting combustion pressure must be as close as possible to the atmospheric pressure.
Il est aussi vivement souhaitable que les ingrédients de base des composés soient non dangereux sur le plan pyrotechnique. On évite avantageusement la présence d'ingrédient(s) appartenant à la classe des explosifs tels que la nitroguanidine, l'hexogène (RDX), l'octogène (H X). On entend par ingrédients explosifs les ingrédients classés en division de risque 1.1 selon la norme NF T 70-502 (voir aussi ONU - Recommandations relatives au Transport des marchandises dangereuses - manuel d'épreuves et de critères, Quatrième édition révisée, ST/SG/AC.10/ll/Rev.4, ISBN 92-1-239083-8ISSN 1014-7179 et STANAG 4488). Le nitrate de guanidine et le perchlorate de potassium, pris séparément, ne sont pas des ingrédients classés dans cette division de risque. Ils ne constituent pas des ingrédients explosifs, notamment au sens de l'invention. It is also highly desirable that the basic ingredients of the compounds be pyrotechnically non-hazardous. The presence of ingredient (s) belonging to the class of explosives such as nitroguanidine, hexogen (RDX), octogen (H X) is advantageously avoided. Explosive ingredients are ingredients classified in risk division 1.1 according to standard NF T 70-502 (see also UN - Recommendations on the Transport of Dangerous Goods - Manual of Tests and Criteria, Fourth revised edition, ST / SG / AC.10 / ll / Rev.4, ISBN 92-1-239083-8ISSN 1014-7179 and STANAG 4488). Guanidine nitrate and potassium perchlorate, taken separately, are not ingredients in this risk division. They are not explosive ingredients, especially in the sense of the invention.
Il faut à ce stade signaler que l'incorporation d'ingrédients hautement énergétiques explosifs tels que la nitroguanidine, même à des taux réduits, contribue de façon préjudiciable à augmenter la température de combustion des composés, au-delà du seuil limite de 2350 K fixé par le besoin d'amélioration technique recherché par les inventeurs. Ainsi, des - - composés tels que décrits dans le brevet US 6 893 517, consistant principalement en un mélange d'un dérivé de la guanidine (préférentiellement du nitrate de guanidine), d'un composé azoté explosif (préférentiellement de la nitroguanidine) et d'un oxydant inorganique (tel le perchlorate d'ammonium ou le perchlorate de potassium) ne répondent pas aux exigences du cahier des charges de la présente invention. Ces composés incluent en outre dans leur composition un faible taux d'un catalyseur balistique, constitué d'un composé oxygéné d'un métal de transition, avantageusement à haute surface spécifique, traditionnellement utilisé dans le domaine des propergols pour augmenter la vitesse de combustion à moyenne et haute pression (ce catalyseur accélère la décomposition de la charge oxydante). Les micro-générateurs de gaz pour dispositifs pour rétracteur de ceinture tels que décrits dans ledit brevet US 6 893 517 (et dans sa demande prioritaire EP 1 275 629) fonctionnent par impulsions, ce qui nécessite une forte vitesse de combustion à moyenne et haute pression. Un fort exposant de pression à basse pression et la non combustion à pression atmosphérique des composés en cause ne posent pas de problème, dans la mesure où la pression ne redescend pas, dans le contexte d'utilisation desdits composés, à un niveau bas avant la fin du fonctionnement pyrotechnique. Cette application pour des dispositifs de rétracteur de ceinture ne requiert pas, pour le générateur de gaz, des exigences aussi sévères que celles requises dans le contexte de la présente invention (airbags, et tout particulièrement airbags latéraux), tout particulièrement une vitesse de combustion élevée à basse pression, un abaissement du seuil limite de pression de combustion (au plus proche de la pression atmosphérique) et un faible exposant de pression sur toute la plage de combustion (notamment à basse pression). It should be pointed out at this stage that the incorporation of explosive high energy ingredients such as nitroguanidine, even at reduced levels, contributes detrimentally to increasing the combustion temperature of the compounds, beyond the threshold of 2350 K set by the need for technical improvement sought by the inventors. Thus, compounds as described in US Pat. No. 6,893,517, consisting mainly of a mixture of a guanidine derivative (preferentially guanidine nitrate), an explosive nitrogen compound (preferably nitroguanidine) and a inorganic oxidant (such as ammonium perchlorate or potassium perchlorate) do not meet the requirements of the specification of the present invention. These compounds also include in their composition a low level of a ballistic catalyst, consisting of an oxygen compound of a transition metal, advantageously with a high specific surface area, traditionally used in the field of propellants to increase the combustion rate at medium and high pressure (this catalyst accelerates the decomposition of the oxidizing charge). The micro-gas generators for belt retractor devices as described in said US Pat. No. 6,893,517 (and in its priority application EP 1 275 629) operate in pulses, which requires a high rate of combustion at medium and high pressure. . A high exponent of low-pressure pressure and the non-combustion at atmospheric pressure of the compounds in question are not a problem, since the pressure does not fall back, in the context of use of said compounds, to a low level before the end of pyrotechnic operation. This application for belt retractor devices does not require, for the gas generator, requirements as severe as those required in the context of the present invention (airbags, and especially side airbags), especially a high rate of combustion. at low pressure, a lowering of the limit threshold of combustion pressure (closer to atmospheric pressure) and a low pressure exponent over the entire range of combustion (especially at low pressure).
Actuellement, pour les airbags frontaux, les composés pyrotechniques qui offrent un bon compromis, en termes de température de gaz, de rendement gazeux, de taux de particules émises et de toxicité, contiennent, comme ingrédients principaux, du nitrate de guanidine (NG) en tant que charge réductrice et du nitrate basique de cuivre (BCN) en tant que charge oxydante. Les brevets US 5 608 183 et US 6 143 102 décrivent de tels composés. . _ Currently, for front airbags, pyrotechnic compounds that offer a good compromise, in terms of gas temperature, gas yield, emitted particulate levels and toxicity, contain, as main ingredients, guanidine nitrate (NG) in as a reducing filler and basic copper nitrate (BCN) as an oxidizing filler. US 5,608,183 and US 6,143,102 disclose such compounds. . _
Ces composés présentent toutefois des vitesses de combustion relativement faibles, inférieures ou égales à 20 mm/s à 20 MPa, ainsi qu'un faible rendement gazeux. Ils sont également difficiles à allumer. These compounds, however, have relatively low rates of combustion, less than or equal to 20 mm / s at 20 MPa, and a low gas yield. They are also difficult to light.
Dans l'optique d'améliorer l'allumabilité de ce type de composés, on a proposé, selon l'art antérieur, l'ajout de perchlorate dans leur composition à base de nitrate de guanidine (NG) et de nitrate basique de cuivre (BCN). Ainsi, la demande de brevet EP 1 526 121 décrit l'ajout d'un perchlorate (notamment du perchlorate de potassium), à faible taux (moins de 5 % en masse), pour améliorer l'allumage de ces composés, Toutefois, l'incorporation de perchlorate à un taux aussi faible ne permet pas d'accroître suffisamment la vitesse de combustion du composé pour une utilisation satisfaisante au sein de générateurs de gaz pour airbags latéraux. With a view to improving the ignitability of this type of compounds, it has been proposed, according to the prior art, the addition of perchlorate in their composition based on guanidine nitrate (NG) and basic nitrate of copper ( BCN). Thus, patent application EP 1 526 121 describes the addition of a perchlorate (especially potassium perchlorate), at a low level (less than 5% by weight), to improve the ignition of these compounds, However, The incorporation of perchlorate at such a low rate does not sufficiently increase the rate of combustion of the compound for satisfactory use in gas generators for side airbags.
Les demandes WO 2007/042735 et WO 2009/126702 décrivent des composés présentant des compositions, du même type, qui renferment du nitrate de guanidine (NG), à titre de charge réductrice, du nitrate basique de cuivre (BCN), à titre de charge oxydante principale et, en sus, une seconde charge oxydante, qui consiste avantageusement en du perchlorate de potassium (KCIO4). Ces documents associent les bonnes performances desdits composés, notamment une vitesse de combustion élevée à haute pression, à la composition mais aussi au procédé de fabrication spécifique desdits composés (procédé qui inclut une étape de compactage à rouleaux en voie sèche pour WO 2007/042735 et deux étapes successives de séchage par atomisation et de compression pour WO 2009/126702). Applications WO 2007/042735 and WO 2009/126702 describe compounds having compositions of the same type which contain guanidine nitrate (NG), as a reducing charge, of basic copper nitrate (BCN), as a main oxidizing charge and, in addition, a second oxidizing charge, which advantageously consists of potassium perchlorate (KCIO 4 ). These documents combine the good performances of said compounds, in particular a high combustion rate at high pressure, with the composition but also with the specific manufacturing process of said compounds (process which includes a step of dry roller compaction for WO 2007/042735 and two successive stages of spray drying and compression drying for WO 2009/126702).
Dans l'optique d'améliorer le rendement gazeux et la vitesse de combustion, on a également proposé, selon l'art antérieur, des composés à base d'un (ou plusieurs) réducteur(s) azoté(s) associé(s) à un oxydant fort de type perchlorate. With a view to improving the gas yield and the rate of combustion, it has also been proposed, according to the prior art, compounds based on one or more associated nitrogen reductants. to a strong oxidant perchlorate type.
Dans la demande de brevet US 2006/0137785, il est décrit l'association d'un réducteur de type guanidine (nitroguanidine ou nitrate de guanidine) et de perchlorate d'ammonium, ce dernier étant nécessairement incorporé à un taux significativement élevé (30% à 60% en masse). L'incorporation de perchlorate d'ammonium à un taux aussi élevé conduit à deux inconvénients majeurs qui sont, d'une part, une - augmentation significative de la température de combustion (supérieure à 2800 K) et, d'autre part, la génération de chlorure d'hydrogène (lequel est un gaz toxique et hautement corrosif), ledit chlorure d'hydrogène se retrouvant alors présent dans les effluents gazeux. Pour pallier ce problème, il est décrit dans ledit brevet la nécessité d'adjoindre au mélange de type guanidine + perchlorate d'ammonium un composé métallique de type oxyde de fer afin de neutraliser l'acide chlorhydrique présent dans les gaz de combustion, ce qui a pour conséquence de diminuer la valeur de rendement gazeux du composé. In patent application US 2006/0137785, there is described the combination of a guanidine reducing agent (nitroguanidine or guanidine nitrate) and ammonium perchlorate, the latter necessarily being incorporated at a significantly high level (30% 60% by weight). The incorporation of ammonium perchlorate at such a high rate leads to two major drawbacks which are, on the one hand, a - a significant increase in the combustion temperature (above 2800 K) and, on the other hand, the generation of hydrogen chloride (which is a toxic and highly corrosive gas), said hydrogen chloride being then present in the gaseous effluents. To overcome this problem, it is described in said patent the need to add to the mixture of guanidine + ammonium perchlorate type a metal compound of iron oxide type in order to neutralize the hydrochloric acid present in the combustion gases, which has the consequence of reducing the gas yield value of the compound.
L'incorporation de perchlorate de potassium à la place du perchlorate d'ammonium présenterait l'avantage de conduire à la formation de chlorure de potassium (KCI) à la place de chlorure d'hydrogène (HCI) (mais l'inconvénient de réduire le rendement gazeux). En tout état de cause, l'incorporation de KCI04 à des taux aussi élevés (jusqu'à 60% en masse) produirait une augmentation de la température de combustion rédhibitoire dans le contexte de l'application visée. Incorporation of potassium perchlorate instead of ammonium perchlorate would have the advantage of leading to the formation of potassium chloride (KCl) in place of hydrogen chloride (HCl) (but the disadvantage of reducing the gas yield). In any case, the incorporation of KCl0 4 at such high levels (up to 60% by mass) would produce an increase in the prohibitive combustion temperature in the context of the intended application.
De façon logique, l'homme du métier s'est donc tourné vers des composés consistant en un mélange contenant du nitrate de guanidine (NG, seul ou associé à un co-réducteur) et du perchlorate de potassium (KCI04) à des taux intermédiaires d'environ 25% à 45% en masse, tel que décrit dans la demande de brevet WO 95/25709 et les brevets US 5 854 442, US 5 997 666, ledit mélange permettant d'obtenir des composés répondant partiellement aux exigences essentielles du domaine d'application visé par la présente invention, à savoir : Logically, those skilled in the art therefore turned to compounds consisting of a mixture containing guanidine nitrate (NG, alone or in combination with a co-reductant) and potassium perchlorate (KClO 4 ) at intermediates from about 25% to 45% by weight, as described in the patent application WO 95/25709 and US 5,854,442, US 5,997,666, said mixture to obtain compounds partially meeting the essential requirements scope of application of the present invention, namely:
- un bon rendement gazeux ; - a good gas performance;
- une température de combustion modérée ; - a moderate combustion temperature;
- une non toxicité intrinsèque des effluents particulaires ; et an intrinsic non-toxicity of the particulate effluents; and
- une vitesse de combustion vers 20 MPa légèrement accrue par rapport aux compositions formulées à base nitrate de guanidine (NG) et nitrate basique de cuivre (BCN), mais qui demeure insuffisante pour une utilisation dans des airbags latéraux. - A combustion rate to 20 MPa slightly increased compared to compositions formulated based on guanidine nitrate (NG) and basic copper nitrate (BCN), but which remains insufficient for use in side airbags.
Les caractéristiques thermodynamiques et balistiques d'un tel composé (composé de référence 1), dont la composition ("binaire") renferme uniquement du nitrate de guanidine (NG) et du perchlorate de potassium (KCIO4), sont présentées dans le tableau 1 ci-après. - - The thermodynamic and ballistic characteristics of such a compound (reference compound 1), whose composition ("binary") contains only guanidine nitrate (NG) and potassium perchlorate (KCIO 4 ), are presented in Table 1 below. - -
Tableau 1 Table 1
(1) : la valeur donnée est une pression relative. Une pression limite de combustion nulle correspond à la pression atmosphérique. (1): the given value is a relative pressure. A zero combustion pressure limit corresponds to the atmospheric pressure.
Le composé de référence 1 présente de nombreux avantages parmi ceux attendus d'un composé pour générateur de gaz pour système airbag. Les ingrédients de base sont simples et aisément approvisionnables, peu coûteux, non dangereux sur les aspects pyrotechniques (pas de constituant appartenant à la classe des composés explosifs) et non toxiques. Les performances thermodynamiques (rendement gazeux, taux de particules) sont bonnes et la température de combustion demeure modérée donc acceptable. Les particules émises par la combustion sont non toxiques (essentiellement KCI). Reference compound 1 has many of the advantages expected from a gas generator compound for an airbag system. The basic ingredients are simple and easily available, inexpensive, non-hazardous on the pyrotechnic aspects (no component of the class of explosive compounds) and non-toxic. The thermodynamic performances (gas yield, particle rate) are good and the combustion temperature remains moderate and therefore acceptable. The particles emitted by combustion are non-toxic (essentially KCl).
Toutefois, un tel composé ne présente pas l'ensemble des performances attendues, notamment pour une application airbag latéral. Tout d'abord, la vitesse de combustion de l'ordre de 26 mm/s à 20 MPa, n'est accrue que de 20 à 30% par rapport à celle d'un composé à base de _ _ nitrate de guanidine (NG) et de nitrate basique de cuivre (BCN), et reste faible par rapport au cahier des charges fixé. Ensuite, lors d'essais avec cette formulation de référence, il est apparu que la substitution totale de l'oxydant nitrate basique de cuivre (BCN) par du perchlorate de potassium (KCIO4), si elle permet d'accroître la vitesse de combustion au dessus de 5 MPa et aussi d'améliorer l'allumabilité, induit en contrepartie, et de façon fortement préjudiciable, un très fort exposant de pression à basse pression (supérieur à 0,55 sur la plage 6 à 10 MPa et une non combustion à pression atmosphérique (des essais complémentaires ont montré que la pression limite de fonctionnement se situe vers 1,7 MPa, alors qu'un composé formulé à base de nitrate de guanidine (NG) et de nitrate basique de cuivre (BCN) présente avantageusement une combustion non nulle à pression atmosphérique). However, such a compound does not have all the expected performance, especially for a side airbag application. Firstly, the burning rate of the order of 26 mm / s to 20 MPa is only 20 to 30% higher than that of a compound based on _ Guanidine nitrate (NG) and basic copper nitrate (BCN), and remains low compared to the set specifications. Then, in tests with this reference formulation, it appeared that the total substitution of the basic copper nitrate oxidant (BCN) with potassium perchlorate (KCIO4), if it increases the rate of combustion at above 5 MPa and also improve the ignitability, induced in return, and in a highly detrimental way, a very high pressure exponent at low pressure (greater than 0.55 over the range 6 to 10 MPa and a non-combustion at atmospheric pressure (additional tests have shown that the operating limit pressure is around 1.7 MPa, whereas a compound formulated based on guanidine nitrate (NG) and basic copper nitrate (BCN) advantageously has a combustion non-zero at atmospheric pressure).
En partant des performances connues du mélange nitrate de guanidine (NG) / perchlorate de potassium (KCI04), les inventeurs ont souhaité proposer des composés pyrotechniques générateurs de gaz améliorés, convenant tout particulièrement pour utilisation dans des airbags latéraux. Ils se sont plus particulièrement fixés pour objectif, tout en conservant ou en améliorant les autres caractéristiques, d'améliorer signifïcativement les trois points suivants : Starting from the known performance of the guanidine nitrate (NG) / potassium perchlorate (KClO 4 ) mixture, the inventors wished to propose improved pyrotechnic gas-generating compounds, which are particularly suitable for use in side airbags. In particular, they have set themselves the objective, while maintaining or improving the other features, of significantly improving the following three points:
- diminution de la pression limite de combustion, - reduction of the combustion limit pressure,
- diminution de l'exposant de pression (<0,26), avantageusement une forte diminution (<0,2), très avantageusement une très forte diminution (<0,1) à partir de 6 MPa, - reduction of the pressure exponent (<0.26), advantageously a large decrease (<0.2), very advantageously a very large decrease (<0.1) from 6 MPa,
- accroissement de la vitesse de combustion sur toute la plage de pression, notamment à basse pression. - Increasing the combustion rate over the entire pressure range, especially at low pressure.
De façon totalement inattendue, il s'est avéré que la présence, au sein de la composition des composés de l'invention, d'un faible taux d'(au moins) un composé oxygéné d'un métal de transition (un oxyde d'un métal de transition ou un composé précurseur d'un tel oxyde), avantageusement à haute surface spécifique, (traditionnellement utilisé en tant que catalyseur balistique dans le domaine des propergols pour augmenter la vitesse de combustion à haute pression (en accélérant la décomposition de la charge oxydante)), a (aussi) des effets majeurs sur les trois points d'amélioration recherchés ci-dessus (à savoir, l'augmentation de la vitesse de combustion (aussi) à basse pression, la diminution de la pression limite de combustion et la diminution de l'exposant de pression sur toute la plage de pression). In a totally unexpected manner, it has been found that the presence, within the composition of the compounds of the invention, of a low level of (at least) an oxygen compound of a transition metal (an oxide of a transition metal or a precursor compound for such an oxide), preferably with a high specific surface area (traditionally used as a ballistic catalyst in the field of propellants to increase the rate of combustion at high pressure (by accelerating the decomposition of the oxidizing charge)), has (also) major effects on the three improvement points sought above (i.e., the increase of the combustion rate (also) at low pressure, the reduction of the combustion limit pressure and the decrease of the pressure exponent over the entire pressure range).
Les compositions des composés pyrotechniques générateurs de gaz de l'invention (convenant tout particulièrement pour des applications airbag, notamment latéraux) renferment : The compositions of the pyrotechnic gas-generating compounds of the invention (particularly suitable for airbag applications, especially lateral applications) contain:
- du nitrate de guanidine, et guanidine nitrate, and
- du perchlorate de potassium. potassium perchlorate.
Elles sont caractérisées en ce que, exprimées en pourcentages massiques, elles renferment : They are characterized in that, expressed in mass percentages, they contain:
60 à 70 % de nitrate de guanidine, 60 to 70% of guanidine nitrate,
26 à 33 %, avantageusement 26 à 30 %, de perchlorate de potassium, 26 to 33%, advantageously 26 to 30%, of potassium perchlorate,
2,5 à 6 % d'au moins un modificateur de combustion choisi parmi les oxydes de métal de transition, les précurseurs de tels oxydes et leurs mélanges, 2.5 to 6% of at least one combustion modifier chosen from transition metal oxides, precursors of such oxides and mixtures thereof,
0 à 6 % d'au moins un additif, et 0 to 6% of at least one additive, and
ne renferment pas d'ingrédient explosif. do not contain any explosive ingredient.
Selon une variante, des compositions de composés de l'invention consistent (exclusivement) en les ingrédients listés ci-dessus (NG + KCI04 + au moins un modificateur de combustion + éventuellement au moins un additif), pris en les teneurs indiquées ci-dessus. According to one variant, compositions of compounds of the invention consist (exclusively) in the ingredients listed above (NG + KCI0 4 + at least one combustion modifier + optionally at least one additive) taken at the levels indicated below. above.
Les ingrédients des trois premiers types ci-dessus (nitrate de guanidine, perchlorate de potassium et modificateur de combustion spécifique) représentent généralement plus de 90% en masse de la masse totale (de la composition) des composés de l'invention, très généralement au moins 94 % en masse, voire plus de 98% en masse. L'éventuelle présence d'additif(s), tels des auxiliaires de fabrication (stéarate de calcium, silice par exemple), est expressément prévue. Les ingrédients des trois types ci-dessus peuvent tout à fait représenter 100% en masse de la masse totale des composés de l'invention. The ingredients of the first three types above (guanidine nitrate, potassium perchlorate and specific combustion modifier) generally represent more than 90% by weight of the total mass (of the composition) of the compounds of the invention, very generally at less than 94% by weight, or even more than 98% by weight. The possible presence of additive (s), such as production auxiliaries (calcium stearate, silica, for example), is expressly provided for. The ingredients of the three types above can be quite 100% by weight of the total mass of the compounds of the invention.
Le nitrate de guanidine, représentant de 60 à 70 % de la masse totale, est en autres retenu pour des raisons de sécurité pyrotechnique et pour son comportement rhéo-plastique, adapté à la mise en uvre des phases de compactage et éventuel pastillage du procédé voie sèche (voir - - ci-après), assurant une bonne densification de la composition pyrotechnique pulvérulente de départ tout en limitant l'effort de compression à appliquer. La fabrication des composés par le procédé voie sèche comprend jusqu'à quatre étapes principales (voir ci-après), qui ont notamment été décrites dans la demande brevet WO 2006/134311. Guanidine nitrate, representing 60 to 70% of the total mass, is also selected for reasons of pyrotechnic safety and for its rheoplastic behavior, suitable for the implementation of compaction phases and possible pelletization of the process. dry (see - - hereinafter), ensuring a good densification of the starting pulverulent pyrotechnic composition while limiting the compressive force to be applied. The manufacture of the compounds by the dry process process comprises up to four main steps (see below), which have been described in particular in the patent application WO 2006/134311.
Le perchlorate de potassium est présent, dans la composition des composés de l'invention, à une teneur intermédiaire, modérée (de 26 à 33 % massique, avantageusement de 26 à 30 % massique), tout particulièrement en référence à la température de combustion, "l'allumabilité" et la vitesse de combustion à haute pression visées. Potassium perchlorate is present in the composition of the compounds of the invention at a moderate intermediate level (from 26 to 33% by weight, advantageously from 26 to 30% by weight), particularly with reference to the combustion temperature, "ignitability" and the target high-pressure combustion rate.
Au sein des mélanges NG + KCIO4, les modificateurs de combustion, sélectionnés par les inventeurs, développent des propriétés particulièrement intéressantes (inattendues) en référence aux trois points d'amélioration recherchés (voir ci-dessus). Within the NG + KCIO 4 mixtures, the combustion modifiers, selected by the inventors, develop particularly interesting (unexpected) properties with reference to the three improvement points sought (see above).
Ledit au moins un modificateur de combustion est choisi parmi les oxydes de métal de transition, les précurseurs de tels oxydes et leurs mélanges. Un précurseur d'un tel oxyde conduit à la formation d'un tel oxyde (génère un tel oxyde) lors de sa décomposition en température au cours de la combustion du composé pyrotechnique. Ainsi le nitrate basique de cuivre (Cu(NO3)2'3Cu(OH)2) se décompose-t-il en oxyde de cuivre (CuO) (voir ci-après). Said at least one combustion modifier is selected from transition metal oxides, precursors of such oxides and mixtures thereof. A precursor of such an oxide leads to the formation of such an oxide (generates such an oxide) during its decomposition in temperature during the combustion of the pyrotechnic compound. Thus, the basic copper nitrate (Cu (NO 3 ) 2 '3Cu (OH) 2 ) is decomposed into copper oxide (CuO) (see below).
Ledit au moins un modificateur de combustion est présent en une quantité suffisante (> 2,5 % en masse), pour être efficace (en référence aux trois points d'amélioration ci-dessus), et non excessive (< 6 % en masse) pour ne pas nuire au rendement gazeux. Un seul modificateur de combustion est généralement présent mais la présence d'au moins deux tels additifs est expressément prévue dans le cadre de la présente invention. Said at least one combustion modifier is present in a sufficient amount (> 2.5% by weight), to be effective (with reference to the three improvement points above), and not excessive (<6% by weight) in order not to harm the gas yield. A single combustion modifier is generally present but the presence of at least two such additives is expressly provided for in the context of the present invention.
De façon préférée, ledit au moins un modificateur de combustion est choisi parmi l'oxyde de zinc (ZnO), l'oxyde de fer (Fe2O3), l'oxyde de chrome (Ο2Ο3), le dioxyde de manganèse (MnO2), l'oxyde de cuivre (CuO), le nitrate basique de cuivre (Cu(NO3)2-3Cu(OH)2) et leurs mélanges. L'oxyde de cuivre et le nitrate basique de cuivre, précurseur dudit oxyde de cuivre (en ce sens que le BCN conduit à la formation d'oxyde de cuivre CuO lors de sa décomposition en température), sont - - particulièrement performants. De façon particulièrement préférée, les composés de l'invention renferment donc, à titre de modificateur de combustion, l'oxyde de cuivre et/ou le nitrate basique de cuivre. L'utilisation de ces modificateurs de combustion permet d'obtenir des composés de l'invention présentant une valeur d'exposant de pression inférieure ou égale à 0,1 sur la plage de pression 6-52 Pa. Preferably, said at least one combustion modifier is selected from zinc oxide (ZnO), iron oxide (Fe 2 O 3 ), chromium oxide (Ο 2Ο 3 ), manganese dioxide ( MnO 2 ), copper oxide (CuO), basic copper nitrate (Cu (NO 3 ) 2-3Cu (OH) 2 ) and mixtures thereof. The copper oxide and the basic copper nitrate, precursor of said copper oxide (in that the BCN leads to the formation of copper oxide CuO during its decomposition in temperature), are - - particularly powerful. In a particularly preferred manner, the compounds of the invention therefore contain, as a combustion modifier, copper oxide and / or basic nitrate of copper. The use of these combustion modifiers makes it possible to obtain compounds of the invention having a pressure exponent value of less than or equal to 0.1 over the pressure range 6-52 Pa.
De façon préférée, ledit au moins un modificateur de combustion selon l'invention présente une surface spécifique supérieure à 3 m2/g/ avantageusement supérieure à 10 m2/g, très avantageusement supérieure à 25 m2/g. Preferably, said at least one combustion modifier according to the invention has a specific surface area greater than 3 m 2 / g / advantageously greater than 10 m 2 / g, very advantageously greater than 25 m 2 / g.
On comprend que la fonction dudit au moins un modificateur de combustion spécifique (choisi parmi les oxydes de métal de transition, leurs précurseurs et leurs mélanges) au sein de la composition des composés de l'invention est, non seulement, comme dans l'art antérieur (voir notamment l'enseignement du brevet US 6 893 517 rappelé ci- dessus) d'augmenter la vitesse de combustion à haute et moyenne pression, mais aussi, de façon surprenante, de conférer aux composés pyrotechniques : It is understood that the function of said at least one specific combustion modifier (selected from transition metal oxides, their precursors and mixtures thereof) within the composition of the compounds of the invention is not only as in the art previous (see in particular the teaching of US Patent 6,893,517 mentioned above) to increase the combustion rate at high and medium pressure, but also, surprisingly, to give the pyrotechnic compounds:
- une combustion stable et auto-entretenue à basse pression (voire à une pression quasi égale à la pression atmosphérique), a stable and self-sustaining combustion at low pressure (or at a pressure almost equal to atmospheric pressure),
- une vitesse de combustion à basse pression plus élevée que celle des compositions de l'art antérieur, a lower combustion rate at a lower pressure than that of the compositions of the prior art,
- un exposant de pression faible, voire quasi nul, à basse, moyenne et haute pression, significativement plus faible que celui des compositions de l'art antérieur ; a low or almost no pressure exponent at low, medium and high pressure, significantly lower than that of the compositions of the prior art;
et ce, avec une "bonne" allumabilité" desdits composés, sans générer trop de particules solides à la combustion, et une température de combustion avoisinant les 2300 K. and this, with a "good" ignitability "of said compounds, without generating too much solid particles for combustion, and a combustion temperature of around 2300 K.
On peut indiquer ici que les composés de l'invention, dont la composition a été précisée ci-dessus, présentent : It can be stated here that the compounds of the invention, the composition of which has been specified above, exhibit:
une température de combustion inférieure à 2350 K, a combustion temperature below 2350 K,
une pression (relative, c'est-à-dire en référence à la pression atmosphérique) limite de combustion inférieure ou égale à 1,5 MPa, avantageusement inférieure à 0,2 MPa, très avantageusement égale à 0,1 MPa, - - a pressure (relative, that is to say with reference to atmospheric pressure) combustion limit less than or equal to 1.5 MPa, preferably less than 0.2 MPa, very advantageously equal to 0.1 MPa, - -
- un exposant de pression inférieur ou égal à 0,25, avantageusement inférieur ou égal à 0,2, très avantageusement inférieur ou égal à 0,1, pour une pression entre 6 et 52 MPa, an exponent of pressure less than or equal to 0.25, advantageously less than or equal to 0.2, very advantageously less than or equal to 0.1, for a pressure between 6 and 52 MPa,
- une vitesse de combustion : - a burning speed:
+ supérieure à 24 mm/s, avantageusement supérieure à 36 mm/s, à basse pression, + greater than 24 mm / s, advantageously greater than 36 mm / s, at low pressure,
+ supérieure à 30 mm/s, avantageusement supérieure à 35 mm/s, à moyenne pression, + greater than 30 mm / s, advantageously greater than 35 mm / s, at medium pressure,
+ supérieure à 37 mm/s, avantageusement supérieure à 45 mm/s, à haute pression. + greater than 37 mm / s, advantageously greater than 45 mm / s, at high pressure.
On se doit d'insister ici sur les valeurs d'exposant de pression, basses, voire très basses, des composés de l'invention. It is necessary to insist here on the low or even very low pressure exponent values of the compounds of the invention.
Les meilleurs résultats indiqués ci-dessus (variantes avantageuses et variantes très avantageuses) ont notamment été obtenus avec l'oxyde de cuivre et le nitrate basique de cuivre comme modificateur de combustion. A l'appui de cette affirmation, on peut se référer aux exemples ci-après. The best results indicated above (advantageous variants and very advantageous variants) have been obtained in particular with copper oxide and basic copper nitrate as a combustion modifier. In support of this statement, reference may be made to the following examples.
Dans le cadre de la présente invention, au sein de la composition des composés de l'invention, il est donc proposé une utilisation originale (tout particulièrement en référence aux paramètres ci-dessus) aux oxydes et précurseurs d'oxydes en cause (originale, par rapport à celle classique de catalyseur balistique connue, au sein de compositions différentes). In the context of the present invention, in the composition of the compounds of the invention, it is therefore proposed an original use (particularly with reference to the above parameters) to the oxides and precursors of oxides in question (original, compared to that conventional known ballistic catalyst, in different compositions).
En sus des constituants ci-dessus (NG + KCIO4 + au moins un modificateur de combustion du type précisé), les composés pyrotechniques de l'invention peuvent renfermer, à un faible taux massique (inférieur ou égal à 6 %, généralement d'au moins 0,1 %), au moins un additif, notamment au moins un additif facilitant leur obtention (la mise en forme, lors de leur obtention), tel que le stéarate de calcium ou de magnésium, le graphite et/ou au moins un additif améliorant l'agrégation des produits solides de leur combustion choisi parmi les oxydes réfractaires à température de ramollissement ou de fusion adaptée à la composition tels que la silice ou l'alumine. Il s'agit avantageusement de la silice, généralement introduite sous forme pulvérulente fine (avantageusement de dimension micrométrique, très avantageusement de dimension nanométrique) présentant une haute surface spécifique (avantageusement de 100 m2/g ou plus) ou sous forme de fibres de silice de faible diamètre (1 à 20 microns) et de quelques dizaines ou centaines de microns (20 à 500 microns) de longueur. De façon surprenante, il s'est avéré que la présence, au sein des composés pyrotechniques de l'invention, de silice, à des taux compris entre 0,5 et 6 % en masse, avantageusement entre 0,5 et 3,5 % en masse, a aussi un effet très significatif d'abaissement de la pression limite de combustion. In addition to the above constituents (NG + KCIO 4 + at least one combustion modifier of the specified type), the pyrotechnic compounds of the invention may contain, at a low mass level (less than or equal to 6%, generally at least 0.1%), at least one additive, especially at least one additive making it easier to obtain (shaping, when they are obtained), such as calcium or magnesium stearate, graphite and / or at least an additive improving the aggregation of the solid products of their combustion chosen from refractory oxides with a softening or melting temperature adapted to the composition, such as silica or alumina. It is advantageously silica, generally introduced in fine powder form (advantageously of micrometric size, very advantageously of nanometric dimension) having a high specific surface area (Advantageously 100 m 2 / g or more) or in the form of silica fibers of small diameter (1 to 20 microns) and a few tens or hundreds of microns (20 to 500 microns) in length. Surprisingly, it has been found that the presence, within the pyrotechnic compounds of the invention, of silica, at levels of between 0.5 and 6% by weight, advantageously between 0.5 and 3.5% in mass, also has a very significant effect of lowering the combustion limit pressure.
Il est donc aussi du mérite des inventeurs d'avoir mis en évidence cet effet de la silice au sein de compositions type NG + KCIO4 (voir le tableau 3 ci-après), et donc au sein des compositions de l'invention (type NG + KCI04 + au moins un modificateur de combustion) où ledit effet se cumule avec ceux (englobant celui de l'abaissement de la pression limite de combustion) du au moins un modificateur de combustion présent. It is therefore also the merit of the inventors to have demonstrated this effect of the silica within compositions of NG + KCIO 4 type (see Table 3 below), and therefore within the compositions of the invention (type NG + KCI0 4 + at least one combustion modifier) wherein said effect is cumulative with those (including that of lowering the combustion limit pressure) of the at least one combustion modifier present.
Le au moins un additif intervient avec les ingrédients constitutifs The at least one additive intervenes with the constituent ingredients
(NG, KCI04 + au moins un modificateur de combustion du type précité) (au début du procédé de fabrication) ou est ajouté, plus en aval, dans le procédé de fabrication des composés de l'invention. (NG, KCI0 4 + at least one combustion modifier of the aforementioned type) (at the beginning of the manufacturing process) or is added, further downstream, in the manufacturing process of the compounds of the invention.
On rappelle que les compositions des composés de l'invention ne renferment pas d'ingrédient explosif (voir la norme NF et les recommandations ONU précisées ci-dessus), et ce, notamment en référence aux paramètres : sécurité pyrotechnique et température de combustion. On note par ailleurs que les masses de composés pyrotechniques requises pour le gonflage d'un air-bag, notamment d'un air-bag latéral, sont plus importantes que celles requises pour le gonflage d'un dispositif rétracteur de ceinture selon le brevet US 6 893 517 (lesdits gonflages n'étant pas du même type : temps de gonflage supérieur à 10-20 ms / par impulsion). It is recalled that the compositions of the compounds of the invention do not contain any explosive ingredient (see the NF standard and the UN recommendations specified above), and this, in particular with reference to the parameters: pyrotechnic safety and combustion temperature. It should also be noted that the masses of pyrotechnic compounds required for the inflation of an airbag, in particular of a lateral airbag, are greater than those required for the inflation of a retractor device according to US Pat. 6,893,517 (said inflations not being of the same type: inflation time greater than 10-20 ms / per pulse).
Les composés pyrotechniques de l'invention peuvent être obtenus suivant un procédé voie humide. Selon une variante, ledit procédé comprend l'extrusion d'une pâte contenant les constituants du composé. Selon une autre variante, ledit procédé inclut une étape de mise en solution aqueuse de tous les (ou certains des) constituants principaux comprenant une solubilisation d'au moins l'un desdits constituants principaux (oxydant et/ou réducteur) puis l'obtention d'une poudre par - - séchage par atomisation, l'ajout à la poudre obtenue du ou des constituants qui n'auraient pas été mis en solution, puis la mise en forme de la poudre sous la forme d'objets par les procédés usuels en voie sèche. The pyrotechnic compounds of the invention can be obtained by a wet process. According to one variant, said process comprises the extrusion of a paste containing the constituents of the compound. According to another variant, said process includes a step of aqueous dissolution of all (or some) of the main constituents comprising solubilization of at least one of said main constituents (oxidant and / or reducing agent) and then obtaining a powder by spray-drying, the addition to the powder obtained of the constituent (s) which would not have been dissolved, and the shaping of the powder in the form of objects by the usual processes in the dry process.
Les composés pyrotechniques de l'invention peuvent aussi être obtenus en voie sèche, par exemple par simple pastillage de la poudre obtenue par mélange de leurs constituants. The pyrotechnic compounds of the invention may also be obtained in the dry process, for example by simply pelletizing the powder obtained by mixing their constituents.
Le procédé d'obtention préférentiel des composés pyrotechniques de l'invention inclut une étape de compactage à sec d'un mélange des ingrédients constitutifs en poudre desdits composés (excepté pour ledit au moins un additif qui peut être ajouté au cours du procédé). Le compactage à sec est généralement mis en œuvre, de façon connue per se, dans un compacteur à cylindres, à une pression de compactage comprise entre 108 et 6.108 Pa. Il peut être mis en œuvre selon différentes variantes (avec une étape caractéristique de compactage "simple" suivie d'au moins une étape complémentaire, avec une étape caractéristique de compactage couplée à une étape de mise en forme). Ainsi, les composés pyrotechniques de l'invention sont susceptibles d'exister sous différentes formes (notamment au fil du procédé de fabrication conduisant aux composés finaux): The preferred method of obtaining the pyrotechnic compounds of the invention includes a dry compaction step of a mixture of powder constitutive ingredients of said compounds (except for said at least one additive which may be added during the process). Dry compaction is generally carried out, in a manner known per se, in a roller compactor, at a compacting pressure of between 10 8 and 6.10 8 Pa. It can be implemented according to different variants (with a characteristic step compaction "simple" followed by at least one complementary step, with a compaction characteristic step coupled to a shaping step). Thus, the pyrotechnic compounds of the invention are likely to exist in different forms (especially over the manufacturing process leading to the final compounds):
- à l'issue d'un compactage à sec couplé à une mise en forme - after dry compaction coupled with a shaping
(par utilisation d'au moins un cylindre de compactage, dont la surface externe présente des alvéoles), on obtient des plaques avec motifs en relief que l'on peut casser pour l'obtention directe d'objets pyrotechniques formés ; (By use of at least one compacting cylinder, the outer surface of which has cavities), plates with relief patterns are obtained which can be broken in order to directly obtain pyrotechnic objects formed;
- à l'issue d'un compactage à sec suivi d'une granulation, on obtient des granulés ; - After dry compaction followed by granulation, granules are obtained;
- à l'issue d'un compactage à sec suivi d'une granulation puis d'un pastillage (compression à sec), on obtient des pastilles ; - After dry compaction followed by granulation and then pelletizing (dry compression), pellets are obtained;
- à l'issue d'un compactage à sec suivi d'une granulation puis du mélange des granulés obtenus avec un liant extrudable et de l'extrusion dudit liant chargé en lesdits granulés, on obtient des blocs monolithiques extrudés (chargés avec lesdits granulés). - After dry compaction followed by granulation and then mixing the granules obtained with an extrudable binder and the extrusion of said binder loaded into said granules, we obtain extruded monolithic blocks (loaded with said granules) .
Les composés pyrotechniques de l'invention sont donc notamment susceptibles d'exister sous la forme d'objets de type: The pyrotechnic compounds of the invention are therefore particularly likely to exist in the form of objects of the type:
- granulés, - . - granules, -.
- pastilles, - lozenges,
- blocs monolithes. - monolithic blocks.
De façon nullement limitative, on peut indiquer ici que: In no way limiting, we can indicate here that:
- les granulés de l'invention présentent généralement une granulométrie (un diamètre médian) comprise entre 200 et 1400 pm (ainsi qu'une masse volumique apparente comprise entre 0,8 et 1,2 cm3/g) ; the granules of the invention generally have a particle size (a median diameter) of between 200 and 1400 μm (and an apparent density of between 0.8 and 1.2 cm 3 / g);
- les pastilles de l'invention présentent généralement une épaisseur comprise entre 1 et 3 mm. the pellets of the invention generally have a thickness of between 1 and 3 mm.
Lorsque les composés de l'invention sont obtenus par un procédé en voie sèche, les ingrédients constitutifs des composés de l'invention présentent avantageusement une granulométrie fine, inférieure ou égale à 20 pm. Ladite granulométrie (valeur du diamètre médian) est généralement comprise entre 3 et 20 pm. Les composés décrits dans la présente invention expriment tout leur potentiel s'ils sont obtenus par un procédé en voie sèche à partir de poudres présentant un diamètre médian compris entre 10 et 20 pm pour le KCI04 et 5 à 15 pm pour le nitrate de guanidine. When the compounds of the invention are obtained by a dry process, the constitutive ingredients of the compounds of the invention advantageously have a fine particle size, less than or equal to 20 μm. Said granulometry (value of the median diameter) is generally between 3 and 20 pm. The compounds described in the present invention express their full potential if they are obtained by a dry process from powders having a median diameter of between 10 and 20 pm for KCl0 4 and 5 to 15 pm for guanidine nitrate. .
Selon un autre de ses objets, la présente invention concerne une composition pulvérulente (mélange de poudres), précurseur d'un composé de l'invention, dont la composition correspond donc à celle d'un composé de l'invention (voir ci-dessus). According to another of its objects, the present invention relates to a powdery composition (mixture of powders), precursor of a compound of the invention, the composition of which corresponds to that of a compound of the invention (see above ).
Selon un autre de ses objets, la présente invention concerne les générateurs de gaz contenant au moins un composé pyrotechnique de l'invention. Lesdits générateurs conviennent parfaitement pour les airbags, notamment latéraux (voir ci-dessus). According to another of its objects, the present invention relates to gas generators containing at least one pyrotechnic compound of the invention. Said generators are ideal for airbags, especially side airbags (see above).
On se propose maintenant d'illustrer, de façon nullement limitative, l'invention. It is now proposed to illustrate, in a non-limiting way, the invention.
Le tableau 2 ci-après présente des exemples de compositions de composés de la présente invention, ainsi que les performances desdits composés comparées à celles du composé de l'art antérieur de référence 1. Les composés ont été évalués au moyen de calculs thermodynamiques ou à partir de mesures physiques menées sur des granulés ou des pastilles fabriqués à partir des compositions via le procédé de mélange de . . poudres - compactage - granulation - et éventuellement pastillage en voie sèche. Table 2 below gives examples of compositions of compounds of the present invention, as well as the performances of said compounds compared with those of the compound of the prior art of reference 1. The compounds were evaluated by means of thermodynamic calculations or from physical measurements on pellets or pellets made from the compositions via the mixing process of . . powders - compaction - granulation - and possibly dry pelletisation.
Le composé de référence 1 de l'art antérieur (voir le tableau 1 ci-dessus) renferme du nitrate de guanidine et du perchlorate de potassium et ne contient pas de modificateur de combustion au sens de l'invention. Les composés des exemples 1 à 7 renferment dans leur composition, en plus des deux constituants du composé de référence 1, un tel modificateur de combustion. The reference compound 1 of the prior art (see Table 1 above) contains guanidine nitrate and potassium perchlorate and does not contain a combustion modifier within the meaning of the invention. The compounds of Examples 1 to 7 contain in their composition, in addition to the two constituents of the reference compound 1, such a combustion modifier.
Les taux des constituants majeurs ont été ajustés afin de conserver une valeur de balance en oxygène proche de -3%, de manière à pouvoir directement comparer les performances des composés du tableau 1. The levels of the major constituents have been adjusted in order to maintain an oxygen balance value close to -3%, so that the performances of the compounds of Table 1 can be directly compared.
Les résultats du tableau 2 montrent, comme attendu selon l'enseignement de l'art antérieur (enseignement du brevet US 6 893 517 et celui du domaine des propergols), que l'ajout d'un modificateur de combustion au sens de l'invention dans une composition du type de celle du composé de référence 1 conduit à une augmentation de la vitesse de combustion à moyenne et haute pression sans modification significative de la température de combustion. The results in Table 2 show, as expected according to the teaching of the prior art (teaching of US Pat. No. 6,893,517 and that of the field of propellants), that the addition of a combustion modifier within the meaning of the invention in a composition of the type of that of the reference compound 1 leads to an increase in the combustion rate at medium and high pressure without significant modification of the combustion temperature.
De façon surprenante, ledit ajout conduit de manière conjointe à un abaissement très important de l'exposant de pression, exposant de pression très faible sur toute la plage de pression de fonctionnement (au delà de 6 MPa), de la pression limite de combustion et à une augmentation importante de la vitesse de combustion à basse pression. Surprisingly, said addition conjointly leads to a very significant lowering of the pressure exponent, a very low pressure exponent over the entire operating pressure range (beyond 6 MPa), of the combustion limit pressure and a significant increase in the low-pressure combustion rate.
Le CuO est le composé qui, ajouté à la composition de référence CuO is the compound which, added to the reference composition
1, apporte les améliorations les plus significatives (voir l'exemple 2). L'exposant de pression est quasi nul sur l'ensemble de la plage de fonctionnement, la pression limite de fonctionnement est quasiment égale à la pression atmosphérique. 1, provides the most significant improvements (see Example 2). The pressure exponent is almost zero over the entire operating range, the operating limit pressure is almost equal to the atmospheric pressure.
Dans la mesure où un complexe de métal tel que le BCN se décompose au cours des réactions exothermiques de combustion en générant in situ du CuO de haute surface spécifique (ce qui a été vérifié expérimentalement), le CuO peut donc être remplacé par du BCN comme modificateur de combustion avec des résultats qui sont équivalents à ceux du CuO (voir l'exemple 7). - - Since a metal complex such as BCN decomposes during exothermic combustion reactions by generating in situ high surface area CuO (which has been verified experimentally), CuO can therefore be replaced by BCN as burn modifier with results that are equivalent to those of CuO (see Example 7). - -
Le CuO et le BCN, permettent, lorsqu'ils sont incorporés à un taux réduit (5% dans les exemples), de conserver une valeur avantageuse de rendement gazeux (>32 g/mol) et conduisent au final à une amélioration très significative de la valeur de débit surfacique de gonflage (de plus de 40%) par rapport à la composition de référence NG / KCIO4 du composé de référence 1. CuO and BCN allow, when incorporated at a reduced rate (5% in the examples), to retain an advantageous value of gas yield (> 32 g / mol) and ultimately lead to a very significant improvement in the surface flow rate value of inflation (by more than 40%) relative to the reference composition NG / KCIO4 of the reference compound 1.
Tableau 2 Table 2
Tableau 2 (suite) Table 2 (continued)
Le tableau 3 ci-après montre le deuxième effet surprenant mis en évidence par les inventeurs, à savoir la diminution très significative de la pression limite de combustion (mesurée sur des granulés) lorsque l'on introduit de la silice à un taux modéré dans la composition des composés de l'invention. Ce même effet, obtenu avec un autre oxyde réfractaire de métal tel que l'alumine, n'est pas d'une ampleur suffisante pour présenter un intérêt. Table 3 below shows the second surprising effect demonstrated by the inventors, namely the very significant reduction in the combustion limit pressure (measured on granules) when silica is introduced at a moderate rate into the composition of the compounds of the invention. This same effect, obtained with another refractory metal oxide such as alumina, is not of sufficient magnitude to be of interest.
TABLEAU 3 TABLE 3
Claims
Applications Claiming Priority (2)
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|---|---|---|---|
| FR1057353A FR2964656B1 (en) | 2010-09-15 | 2010-09-15 | PYROTECHNIC COMPOUNDS GENERATORS OF GAS |
| PCT/FR2011/052125 WO2012035271A2 (en) | 2010-09-15 | 2011-09-15 | Pyrotechnic gas generator compounds |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP2616413A2 true EP2616413A2 (en) | 2013-07-24 |
| EP2616413B1 EP2616413B1 (en) | 2021-11-03 |
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| EP (1) | EP2616413B8 (en) |
| JP (1) | JP2013541487A (en) |
| KR (1) | KR20140135087A (en) |
| CN (1) | CN103180271A (en) |
| BR (1) | BR112013006065A2 (en) |
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| WO (1) | WO2012035271A2 (en) |
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| FR3007659B1 (en) | 2013-06-28 | 2017-03-24 | Herakles | METHOD FOR DELIVERING A PRESSURIZED LIQUID FROM THE COMBUSTION GASES OF AT LEAST ONE PYROTECHNIC LOAD |
| CN106458784A (en) * | 2014-06-05 | 2017-02-22 | Tk控股公司 | Improved booster composition |
| WO2015188167A1 (en) * | 2014-06-05 | 2015-12-10 | Tk Holdings Inc. | Improved booster composition |
| FR3037812B1 (en) | 2015-06-29 | 2017-08-04 | Herakles | FIRE EXTINGUISHER |
| CN107573199A (en) * | 2016-11-03 | 2018-01-12 | 湖北航天化学技术研究所 | A kind of voltage-controlled heat production gas generating agent of high security |
| FR3077989B1 (en) | 2018-02-20 | 2021-11-19 | Arianegroup Sas | FIRE EXTINGUISHER |
| CN108752154B (en) * | 2018-06-08 | 2020-08-28 | 中国科学技术大学 | A kind of composite gas generating agent with mash burning effect and preparation method thereof |
| CN110317120B (en) * | 2019-05-30 | 2020-10-20 | 湖北航鹏化学动力科技有限责任公司 | Ignition powder, preparation method and application thereof and safety airbag gas generator |
| JP2024037522A (en) * | 2022-09-07 | 2024-03-19 | 株式会社ダイセル | Gas generant composition |
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| US5538567A (en) * | 1994-03-18 | 1996-07-23 | Olin Corporation | Gas generating propellant |
| JPH08151288A (en) * | 1994-11-25 | 1996-06-11 | Otsuka Chem Co Ltd | Gas generating agent for air bag |
| DE19581542T1 (en) * | 1994-12-21 | 1999-04-01 | Daicel Chem | Gas generating composition |
| US5854442A (en) * | 1995-03-31 | 1998-12-29 | Atlantic Research Corporation | Gas generator compositions |
| US5608183A (en) | 1996-03-15 | 1997-03-04 | Morton International, Inc. | Gas generant compositions containing amine nitrates plus basic copper (II) nitrate and/or cobalt(III) triammine trinitrate |
| US5997666A (en) | 1996-09-30 | 1999-12-07 | Atlantic Research Corporation | GN, AGN and KP gas generator composition |
| JP2000086376A (en) * | 1998-09-14 | 2000-03-28 | Daicel Chem Ind Ltd | Gas generating composition |
| DE29821541U1 (en) * | 1998-12-02 | 1999-02-18 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azide-free, gas generating composition |
| US6143102A (en) | 1999-05-06 | 2000-11-07 | Autoliv Asp, Inc. | Burn rate-enhanced basic copper nitrate-containing gas generant compositions and methods |
| CZ20014668A3 (en) * | 1999-06-25 | 2002-09-11 | Nippon Kayaku Kabushiki-Kaisha | Gas-producing composition |
| DE20111410U1 (en) * | 2001-07-10 | 2001-08-30 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Nitrocellulose free gas generating composition |
| US8101033B2 (en) * | 2004-07-26 | 2012-01-24 | Autoliv Asp, Inc. | Alkali metal perchlorate-containing gas generants |
| JP4767487B2 (en) | 2003-10-20 | 2011-09-07 | ダイセル化学工業株式会社 | Gas generant composition |
| DE102004059992A1 (en) | 2004-12-13 | 2006-06-14 | Trw Airbag Systems Gmbh | Gas generating composition consists of 20-65wt% organic fuel, 30-60wt% ammonium perchlorate, 5-30wt% of a chloride catcher, and 0-10wt% working material |
| FR2887247B1 (en) | 2005-06-15 | 2007-10-12 | Snpe Materiaux Energetiques | PROCESS FOR MANUFACTURING GAS GENERATOR PELLETS COMPRISING A DRY GRANULATION STEP |
| FR2892117B1 (en) * | 2005-10-13 | 2008-05-02 | Snpe Materiaux Energetiques Sa | FAST GAS GENERATING PYROTECHNIC COMPOSITION AND PROCESS FOR OBTAINING THE SAME |
| FR2899227B1 (en) * | 2006-04-04 | 2008-10-24 | Snpe Materiaux Energetiques Sa | LARGE-SIZE MONOLITH PYROTECHNIC OBJECTS, OBTAINING AND USING |
| JP5277428B2 (en) * | 2006-05-02 | 2013-08-28 | 日本化薬株式会社 | Gas actuator composition for gas actuator for operating safety parts and gas generator for gas actuator using the same |
| US8815029B2 (en) * | 2008-04-10 | 2014-08-26 | Autoliv Asp, Inc. | High performance gas generating compositions |
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2010
- 2010-09-15 FR FR1057353A patent/FR2964656B1/en active Active
-
2011
- 2011-09-15 CN CN2011800515939A patent/CN103180271A/en active Pending
- 2011-09-15 WO PCT/FR2011/052125 patent/WO2012035271A2/en active Application Filing
- 2011-09-15 US US13/821,525 patent/US20130228254A1/en not_active Abandoned
- 2011-09-15 MX MX2013002988A patent/MX2013002988A/en not_active Application Discontinuation
- 2011-09-15 JP JP2013528747A patent/JP2013541487A/en active Pending
- 2011-09-15 BR BR112013006065A patent/BR112013006065A2/en not_active IP Right Cessation
- 2011-09-15 EP EP11773097.8A patent/EP2616413B8/en active Active
- 2011-09-15 KR KR1020137009591A patent/KR20140135087A/en not_active Withdrawn
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| Title |
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| None * |
| See also references of WO2012035271A2 * |
Also Published As
| Publication number | Publication date |
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| EP2616413B1 (en) | 2021-11-03 |
| FR2964656B1 (en) | 2012-10-12 |
| FR2964656A1 (en) | 2012-03-16 |
| KR20140135087A (en) | 2014-11-25 |
| JP2013541487A (en) | 2013-11-14 |
| WO2012035271A3 (en) | 2012-05-10 |
| BR112013006065A2 (en) | 2016-06-07 |
| WO2012035271A2 (en) | 2012-03-22 |
| CN103180271A (en) | 2013-06-26 |
| EP2616413B8 (en) | 2021-12-08 |
| US20130228254A1 (en) | 2013-09-05 |
| MX2013002988A (en) | 2013-06-24 |
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