EP3558900B1 - Gas-generating pyrotechnic solid objects - Google Patents
Gas-generating pyrotechnic solid objects Download PDFInfo
- Publication number
- EP3558900B1 EP3558900B1 EP17829259.5A EP17829259A EP3558900B1 EP 3558900 B1 EP3558900 B1 EP 3558900B1 EP 17829259 A EP17829259 A EP 17829259A EP 3558900 B1 EP3558900 B1 EP 3558900B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oxalate
- inorganic
- composition
- nitrate
- advantageously
- 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.)
- Active
Links
- 239000007787 solid Substances 0.000 title claims description 22
- 239000000203 mixture Substances 0.000 claims description 81
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 39
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 35
- 229940039748 oxalate Drugs 0.000 claims description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 31
- 239000004615 ingredient Substances 0.000 claims description 29
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims description 28
- 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 26
- 239000008188 pellet Substances 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 15
- 229940039790 sodium oxalate Drugs 0.000 claims description 15
- 239000000470 constituent Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000002360 explosive Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- KQAGKTURZUKUCH-UHFFFAOYSA-L strontium oxalate Chemical compound [Sr+2].[O-]C(=O)C([O-])=O KQAGKTURZUKUCH-UHFFFAOYSA-L 0.000 claims description 10
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 8
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 claims description 7
- 238000005453 pelletization Methods 0.000 claims description 7
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 3
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 claims description 2
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 description 67
- 239000007789 gas Substances 0.000 description 18
- 239000011734 sodium Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000002585 base Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- 238000005056 compaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 150000003891 oxalate salts Chemical class 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- -1 alkaline earth metal formates Chemical class 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 239000002826 coolant Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 4
- 239000000028 HMX Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000013016 damping Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000002075 main ingredient Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 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 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 3
- 239000003826 tablet Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HIGRAKVNKLCVCA-UHFFFAOYSA-N alumine Chemical compound C1=CC=[Al]C=C1 HIGRAKVNKLCVCA-UHFFFAOYSA-N 0.000 description 2
- WEUCVIBPSSMHJG-UHFFFAOYSA-N calcium titanate Chemical compound [O-2].[O-2].[O-2].[Ca+2].[Ti+4] WEUCVIBPSSMHJG-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007937 lozenge Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 235000010603 pastilles Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000904 FeC2O4 Inorganic materials 0.000 description 1
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003416 augmentation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229940044172 calcium formate Drugs 0.000 description 1
- 235000019255 calcium formate Nutrition 0.000 description 1
- 239000004281 calcium formate Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 210000000038 chest Anatomy 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007907 direct compression Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
-
- 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
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/001—Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
-
- 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
- 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
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
Definitions
- the present invention relates to novel pyrotechnic solid objects which generate gas. Said new objects are particularly interesting with regard to their combustion temperature (low), their generation of combustion residues (in small quantity, in agglomerated form) and their obtaining (easy to use by dry process). They are suitable for use in gas generators with optimized architecture. This optimization is detailed below.
- Said pyrotechnic solid objects which generate gas are particularly suitable for use in systems for protecting the occupants of motor vehicles, more especially for inflating front damping cushions (called “airbags").
- the technical field relating to the protection of occupants of motor vehicles has experienced a very significant development during the last twenty years.
- the vehicles integrate within their passenger compartment several safety systems of the damping airbag type (called "airbags").
- airbags a distinction is made between the front airbags (driver or passenger) and the side airbags (curtain, thorax protection).
- Front airbags differ from side airbags primarily in the time required for deployment and installation of the airbag. Typically, this time is higher for a front airbag (of the order of 40-50 ms, against 10-20 ms for a side airbag).
- Front airbags essentially use so-called fully pyrotechnic gas generators, including at least one pyrotechnic charge consisting of at least one solid pyrotechnic object.
- This type of design requires in return that said at least one solid pyrotechnic object jointly satisfies numerous requirements. (relating to its gas yield, to its surface inflation rate, to its ignitability, to its temperature and combustion rate, to its pressure exponent, to the non-toxicity of the gases generated by its combustion, to the quantity of solid particles generated by its combustion and pyrotechnic safety when obtaining and using it).
- Said objects have a low combustion temperature, due to the presence of said complex of low enthalpy of formation in their composition.
- the pyrotechnic solid objects which seem to offer the best compromise with reference to the many requirements to be satisfied (see above) contain, in their composition, as main ingredients, guanidine nitrate (NG; as reducing charge) and basic copper nitrate (BCN; as oxidizing charge).
- NG guanidine nitrate
- BCN basic copper nitrate
- Their composition (of NG / BCN type, therefore) is moreover capable of containing at least one additive, acting on the agglomeration of combustion residues and / or, advantageously, on the combustion rate.
- the Applicant has in fact considered the technical problem of the size and weight (and therefore of the cost) of gas generators operating with a pyrotechnic solid charge that generates gas. It wished to optimize the architecture of said generators by minimizing the volume and mass of the devices required, within the structure of said generators, for the filtration and cooling of the combustion gases generated. It can be indicated, for illustration, that the mass of the filtration device employed, for a gas-generating composition with a combustion temperature of 1900 K, is generally equivalent to the mass of the gas-generating charge. For all practical purposes, it can also be specified that the filtration device constitutes per se a cooling device (which combines its cooling effect with that of the cooling device).
- the Applicant proposes new pyrotechnic solid objects which generate gas, having an NG / BCN type composition, which can be obtained by the dry route, without the presence of a binder in their composition, and whose combustion temperature (below 1800 K) is lower than that (below 2200 K) of the objects described in the patent application WO 2012/153062 .
- Said combustion temperature is lowered by the presence, within the composition of the articles, of at least one specific cooling agent (see below); said presence of said at least one specific cooling agent, in a relatively limited quantity ( ⁇ 18% by mass, in particular ⁇ 15% by mass mass, and even ⁇ 13% by mass), within a specific base (see its composition specified below), being effective (therefore with regard to the lowering of the combustion temperature) while inducing only effects limited on other parameters such as combustion rate (the presence of an explosive ingredient is not required), gas yield and temperature stability of the objects in question.
- Said composition is therefore of the NG (reducing charge) / BCN (oxidizing charge) type.
- Guanidine nitrate (NG) was chosen as a reducing agent, among other things, for its ability to generate a lot of gas, for its rheo-plastic behavior adapted to the implementation of the pelletizing phase (direct) or the compaction phases and pelletizing of a dry process (its presence allows in particular a good densification of the starting powdery pyrotechnic composition while limiting the compressive force to be applied: see below), and for pyrotechnic safety reasons.
- the composition of the pyrotechnic articles of the invention contains from 35 to 50% by mass of guanidine nitrate (NG), advantageously from 40 to 50% by mass of guanidine nitrate (NG).
- Basic copper nitrate was chosen as an oxidant, particularly for its impact on the combustion rate, for its ductility and its “slaggant” effect (presence of copper).
- Said basic copper nitrate is present in an amount of 35 to 50% by mass, generally in an amount of 35 to 45% by mass.
- Said composition therefore contains, in an NG / BCN type base (as specified above, with particular reference to the desired oxygen balance value, close to -3%), a small amount (from 0.5 to 6 %, often from 1 to 6%, advantageously from 3 to 5%, by mass) of at least one compound chosen from alumina (Al 2 O 3 ), inorganic titanates whose melting point is greater than 2100 K and their mixtures.
- alumina Al 2 O 3
- inorganic titanates whose melting point is greater than 2100 K and their mixtures.
- the presence of said at least one compound is appropriate with regard to the agglomeration of the combustion residues (for all practical purposes, it can be noted here that the alumina has a “slaggant” power greater than that of the titanates) and the speed of combustion.
- Said composition advantageously contains alumina (Al 2 O 3 ) or at least one titanate as specified above. It very advantageously contains alumina (Al 2 O 3 ) or such a titan
- Said composition of the objects of the invention contains, in a base of NG / BCN type as specified above, in addition to said at least one inorganic titanate and / or alumina, a relatively limited amount (from 5 to 18%, in particular from 5 to 15%, advantageously from 5 to 13%, very advantageously from 7 to 13%, by mass) of at least one specific cooling agent, ie of at least one chosen inorganic oxalate from sodium oxalate (Na 2 C 2 O 4 ), tin oxalate (SnC 2 O 4 ), strontium oxalate (SrC 2 O 4 ), iron oxalate (FeC 2 O 4) ), copper oxalate (CuC 2 O 4 ) and their mixtures.
- a specific cooling agent ie of at least one chosen inorganic oxalate from sodium oxalate (Na 2 C 2 O 4 ), tin oxalate (SnC 2 O 4 ), str
- the presence, within the specified NG / BCN base (containing said at least one inorganic titanate and / or alumina), of at least one such oxalate, in said relatively limited amount indicated, has occurred. proved to be opportune, with reference to the lowering of the combustion temperature of the objects, without inducing significant effects on the other parameters such as the combustion rate (the presence of an explosive ingredient is not required), the gas yield (the oxalates were preferred to the formates) and the stability over time (the oxalates selected being not very hygroscopic) and in temperature (the melting point and / or decomposition of the oxalates selected is not less than 200 ° C (the those skilled in the art have understood that said retained oxalates are in anhydrous form)) of said objects.
- the selected oxalates are, moreover, non-toxic and inexpensive.
- Said composition of the objects of the invention does not contain a binder.
- NG guanidine nitrate
- the rheoplastic behavior of guanidine nitrate (NG) entering in a significant amount in said composition, makes the presence of any binder superfluous (in particular for obtaining, by dry process, pyrotechnic objects formed, granules, pellets and compressed monolith blocks (see below)).
- NG guanidine nitrate
- a person skilled in the art understands the advantage of being able to obtain, by the dry route, the objects of the invention without the intervention of a binder (which would have a significant impact on the oxygen balance of the composition); the absence of any binder being moreover particularly advisable with reference to the desired objective of low combustion temperature and high gas yield of said objects.
- Said composition of the objects of the invention does not contain an explosive ingredient. It thus contains neither nitroguanidine nor hexogen (RDX), neither octogen (HMX) ...
- explosive ingredient is understood to mean ingredients classified in risk division 1.1 according to standard NF T 70-502 (see also UN - Recommendations relating to Transport Dangerous Goods - Manual of Tests and Criteria, Fourth Revised Edition, ST / SG / AC.10 / 11 / Rev.4, ISBN 92-1-239083-8ISSN 1014-7179 and STANAG 4488).
- guanidine nitrate NG
- the absence of any explosive ingredient in the composition of the objects of the invention is particularly appropriate with reference to the safety and to the combustion temperature of said objects. It is incidentally recalled that a low combustion temperature is desired.
- the at least one inorganic oxalate present in the composition of the objects of the invention is advantageously chosen from sodium oxalate (Na 2 C 2 O 4 ), strontium oxalate (SrC 2 O 4 ) and oxalate of copper (CuC 2 O 4 ).
- the composition of the objects of the invention which contains at least one titanate as specified, contains strontium titanate (SrTiO 3 ) and / or calcium titanate (CaTiO 3 ) and / or titanate of aluminum (Al 2 TiO 5 ).
- it contains strontium titanate (SrTiO 3 ), calcium titanate (CaTiO 3 ) or aluminum titanate (Al 2 TiO 5 ).
- titanates respectively exhibit melting temperatures of 2353 K, 2248 K and 2133 K, ie melting temperatures significantly higher than the combustion temperature of the NG / BCN base (the combustion temperature of any NG / BCN base being in fact always less than 1950 K), which, in addition, contains the at least one inorganic oxalate.
- the at least one inorganic oxalate advantageously consists of sodium oxalate.
- ingredients of the above four types (guanidine nitrate (NG), basic copper nitrate (BCN), alumina and / or inorganic titanate (s) with a melting point above 2100 K, and oxalate ( s) inorganic (s), as specified) (constituent ingredients of the objects of the invention in general and of the above subfamily in particular) generally represent at least 98% by mass of the composition pyrotechnic objects of the invention.
- the ingredients of the four types above can quite represent at least 99.5% by mass, or even 100% by mass of the total mass of the objects of the invention.
- At least one “other” additive alumina and / or the at least one inorganic titanate as well as the at least one inorganic oxalate which can be completely assimilated to additives
- the processing aids calcium stearate, graphite, silica in particular
- the constitutive (main) ingredients of the objects of the invention guanidine nitrate + basic copper nitrate + alumina and / or at least one inorganic titanate as specified + at least one oxalate inorganic as specified - are known products. They are in the form of powders with a narrow particle size distribution (around their median diameter (d 50 )). Throughout this text (including in the examples), the median diameters indicated are median diameters by volume.
- Said (main) constituent ingredients of the objects of the invention advantageously exhibit, very particularly with reference to the obtaining of said objects by the dry process and to the rate of combustion of said objects, a fine, or even very fine, particle size. They generally have median diameter values (d 50 ) less than or equal to 20 ⁇ m.
- the median diameter of one of said guanidine nitrate (NG) and Basic copper nitrate (BCN) is substantially greater than the median diameter of the other of said guanidine nitrate (NG) and basic copper nitrate (BCN), said substantially (significantly) larger median diameter generally remaining less than or equal to 20 ⁇ m (see above).
- substantially higher is meant “at least 1.8 times higher”, advantageously “at least double of”, very advantageously “at least 5 times higher”, or even “at least 10 times higher”.
- the median diameter of one of said guanidine nitrate and basic copper nitrate is less than or equal to 1 ⁇ m while the median diameter of the other of said nitrate of copper.
- guanidine and basic copper nitrate for example therefore that of said guanidine nitrate, is at least 5 ⁇ m, advantageously at least 10 ⁇ m (while generally remaining less than or equal to 20 ⁇ m (see above)).
- alumina When alumina (also intervening in the pulverulent state) is present, it is advantageously present with a fine grain size, or even very fine; it then has a high specific surface, or even very high.
- Median diameter values generally less than or equal to 20 ⁇ m have been mentioned for all the constituent ingredients.
- median diameter values generally less than or equal to 10 ⁇ m, advantageously less than or equal to 5 ⁇ m, very advantageously less than or equal to 1 ⁇ m, or even as low as 100 nm, and even 10 nm.
- said at least one inorganic titanate is present, it is also advantageously present at the smallest possible particle size.
- said at least one inorganic titanate present is present in a fine pulverulent form, of micrometric dimension, or even of nanometric dimension, ie with a median diameter (d 50 ) of less than 6 ⁇ m, or even less than 1 ⁇ m. (generally in the context of this advantageous variant, we have: 0.5 ⁇ m ⁇ d 50 ⁇ 6 ⁇ m).
- Said at least one inorganic titanate present advantageously has a specific surface area greater than 1 m 2 / g (very advantageously greater than 5 m 2 / g or more).
- the particle size of at least one inorganic oxalate it is also suitably the finest possible.
- good results have been obtained with commercial products of “large particle size”, in particular with sodium oxalate having a median diameter greater than 40 ⁇ m (60 ⁇ m in particular).
- the good results obtained would be even better with (at least) one oxalate of the invention, which is thinner (in particular having a median diameter of less than 20 ⁇ m (see above)).
- the objects of the invention are in particular likely to exist in the form of formed pyrotechnic objects, granules, pellets or monolithic blocks (tablets) (see below).
- the manufacturing processes in question are processes by analogy, the dry route or the wet route, advantageously the dry route.
- the pyrotechnic solid objects of the invention can be manufactured (by the dry process) by simple pelletizing (compression) of the powder mixtures obtained by mixing their constituent ingredients (it has been understood that said ingredients are used in the pulverulent state, with a more or less fine particle size, suitably as fine as possible (see above), and that it is essentially, or even exclusively, NG, BCN, alumina and / or inorganic titanate (s) such as ) as specified, and oxalate (s) as specified).
- the pyrotechnic objects of the invention can also be manufactured (by the dry process) according to a process capable of comprising up to four main stages. Such a method is familiar to those skilled in the art. It has in particular been described in the patent application WO 2006/134311 .
- Alumina or (and) at least one inorganic titanate (whose melting point is greater than 2100 K) and at least one inorganic oxalate (chosen from sodium oxalate, tin oxalate, strontium oxalate, iron oxalate, copper oxalate and their mixtures) are advantageously involved with the other constituent ingredients, NG + BCN mainly, or even NG + BCN exclusively, at the start of the manufacturing process.
- said alumina or (and) said at least one inorganic titanate (the melting point of which is greater than 2100 K) or (and) said at least one inorganic oxalate (chosen from sodium oxalate, tin oxalate, strontium oxalate, iron oxalate, copper oxalate and mixtures thereof), quite particularly said at least one inorganic oxalate, itself (s) added, further downstream, in the method of manufacturing the objects of the invention.
- the preferential dry manufacturing process (preparation) of the pyrotechnic objects of the invention includes a dry compacting step of a mixture of the powdered constituent ingredients of said objects (except, optionally, said at least one inorganic oxalate which can be added later). Dry compaction is generally carried out, in a manner known per se, in a roller compactor, at a compaction pressure (p) of between 10 8 and 6.10 8 Pa (10 8 Pa ⁇ p ⁇ 6.10 8 Pa). It can be implemented according to different variants (with a characteristic "simple" compacting step followed by at least one complementary step or with a characteristic compacting step coupled with a shaping step).
- the objects of the invention - formed pyrotechnic objects, granules, pellets and monolithic blocks - obtained at the end of one or other of the steps specified above, it being understood that pellets can also be obtained. by direct pelletizing (see above).
- the solid pyrotechnic objects of the invention can also be obtained by a wet process.
- a method includes 1) a step of dissolving all or (generally rather) some of the main ingredients in aqueous solution (said step of dissolving in water generally comprises dissolving at least one of the main ingredients (and more particularly that of guanidine nitrate (NG))), 2) obtaining a powder by spray drying, 3) adding to the powder obtained the ingredient (s) which have not been put into solution, then 4) the shaping (in the form of objects) of the pulverulent mixture obtained by the usual dry process.
- NG guanidine nitrate
- the objects of the invention advantageously exist in the form of granules, pellets or monolithic blocks.
- Said granules and pellets are ideally suited for the main intended application (that of front airbags, in the field of motor vehicle safety).
- the formed pyrotechnic objects and monolithic blocks are intended for other uses.
- the present invention relates to a pulverulent composition (mixture of powders), a precursor of an object of the invention, the composition of which therefore corresponds to that of an object of the invention (see above ).
- the present invention relates to gas generators containing a pyrotechnic solid charge which generates gas; said charge containing at least one solid pyrotechnic object of the invention.
- Said generators, loaded in particular with pellets of the invention, are perfectly suitable for airbags, in particular front airbags (see above).
- Table 1 below shows five examples (Ex.1, Ex.2, Ex.3, Ex.4 and Ex.5) of composition of objects (pellets) of the present invention, as well as the characteristics (calculated performance or measured) of said objects (pellets) compared to those of an object (pellet) of the prior art (Ref. 1, according to the patent application WO 2012/153062 ); said objects (lozenges) of the invention and of the prior art having been manufactured, from the above ingredients, as indicated above.
- Table 1 below also shows two other examples (Ex. A and Ref. 2) of the composition of pellets as well as the performance of said pellets (obtained in a similar manner). These examples show the advantage of using BCN of very fine particle size (with NG of substantially higher particle size).
- pellets were evaluated by means of thermodynamic calculations and from physical measurements therefore carried out on the lozenges.
- the combustion rates and pressure exponents of said pellets were obtained after several shots in a manometric chamber (volume 40 cm 3 ). The values indicated are therefore average values.
- the reference pellets of the prior art contained, in their composition, guanidine nitrate (NG), basic copper nitrate (BCN) and strontium titanate (SrTiO 3 ), in percentages by weight indicated.
- NG guanidine nitrate
- BCN basic copper nitrate
- SrTiO 3 strontium titanate
- the tablets of Examples 1 to 5 contained, in their composition, in addition to the three constituents guanidine nitrate (NG), basic copper nitrate (BCN) and strontium titanate (SrTiO 3 ) for examples 1 and 2, alumina for examples 3, 4 and 5, an agent for lowering the combustion temperature according to the present invention: sodium oxalate (Na 2 C 2 O 4 ) for examples 1 to 3, strontium oxalate (SrC 2 O 4 ) for example 4 and copper oxalate (CuC 2 O 4 ) for example 5.
- the four constituents were present in the compositions in the weight percentages indicated.
- compositions (objects) of Examples 1 and 2 showed that the addition, at a variable rate (mass content of, respectively 7.5 and 10%), of sodium oxalate (Na 2 C 2 O 4 ), in a composition of the type of that of reference 1 (Ref. 1), led to a significant lowering of the combustion temperature (respectively -144 and -190 ° C).
- the value of the pressure exponent remained acceptable for the intended application (front airbags).
- the characteristics (performance) of the composition (of the article) of Example 3 showed that the presence of alumina contributed to obtaining good performance (lowering of the combustion temperature (from -155 ° C compared to using the example of Ref. 1) with an increase in the value of the combustion speed to 20 MPa by compared to Example 2, and a parallel increase in the quality of agglomeration of the combustion residues compared to Example 2).
- BCN basic copper nitrate
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Description
La présente invention concerne de nouveaux objets solides pyrotechniques générateurs de gaz. Lesdits nouveaux objets sont particulièrement intéressants au regard de leur température de combustion (basse), de leur génération de résidus de combustion (en faible quantité, sous forme agglomérés) et de leur obtention (de mise en œuvre aisée par voie sèche). Ils conviennent pour utilisation dans des générateurs de gaz dont l'architecture est optimisée. Cette optimisation est précisée ci-après.The present invention relates to novel pyrotechnic solid objects which generate gas. Said new objects are particularly interesting with regard to their combustion temperature (low), their generation of combustion residues (in small quantity, in agglomerated form) and their obtaining (easy to use by dry process). They are suitable for use in gas generators with optimized architecture. This optimization is detailed below.
Lesdits objets solides pyrotechniques générateurs de gaz conviennent particulièrement pour une utilisation dans des systèmes de protection d'occupants de véhicules automobiles, plus spécialement pour le gonflage des coussins amortissants (dits "airbags") frontaux.Said pyrotechnic solid objects which generate gas are particularly suitable for use in systems for protecting the occupants of motor vehicles, more especially for inflating front damping cushions (called "airbags").
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 intègrent au sein de leur habitacle plusieurs systèmes de sécurité de type coussin gonflable amortissant (dits "airbags"). Parmi les systèmes de sécurité de type coussin gonflable amortissant, on distingue les airbags frontaux (conducteur ou passager) et les airbags latéraux (rideau, protection thorax). Les airbags frontaux se différencient des airbags latéraux essentiellement par le temps requis pour le déploiement et la mise en place du coussin gonflable. Typiquement, ce temps est plus élevé pour un airbag frontal (de l'ordre de 40-50 ms, contre 10-20 ms pour un airbag latéral).The technical field relating to the protection of occupants of motor vehicles has experienced a very significant development during the last twenty years. The vehicles integrate within their passenger compartment several safety systems of the damping airbag type (called "airbags"). Among the safety systems of the damping airbag type, a distinction is made between the front airbags (driver or passenger) and the side airbags (curtain, thorax protection). Front airbags differ from side airbags primarily in the time required for deployment and installation of the airbag. Typically, this time is higher for a front airbag (of the order of 40-50 ms, against 10-20 ms for a side airbag).
Les airbags frontaux font pour l'essentiel appel à des générateurs de gaz dits entièrement pyrotechniques, incluant au moins un chargement pyrotechnique constitué d'au moins un objet solide pyrotechnique. Ce type de conception impose en retour que ledit au moins un objet solide pyrotechnique satisfasse conjointement à de nombreuses exigences (relatives à son rendement gazeux, à son débit surfacique de gonflage, à son allumabilité, à ses température et vitesse de combustion, à son exposant de pression, à la non toxicité des gaz générés par sa combustion, à la quantité de particules solides générées par sa combustion et à la sécurité pyrotechnique lors de son obtention et de son utilisation).Front airbags essentially use so-called fully pyrotechnic gas generators, including at least one pyrotechnic charge consisting of at least one solid pyrotechnic object. This type of design requires in return that said at least one solid pyrotechnic object jointly satisfies numerous requirements. (relating to its gas yield, to its surface inflation rate, to its ignitability, to its temperature and combustion rate, to its pressure exponent, to the non-toxicity of the gases generated by its combustion, to the quantity of solid particles generated by its combustion and pyrotechnic safety when obtaining and using it).
Divers types de compositions pyrotechniques, pour des objets solides pyrotechniques générateurs de gaz convenant particulièrement pour une utilisation dans des systèmes de protection d'occupants de véhicules automobiles, ont déjà été proposés à ce jour.Various types of pyrotechnic compositions, for solid pyrotechnic gas-generating objects particularly suitable for use in systems for protecting the occupants of motor vehicles, have already been proposed to date.
Le brevet
Le brevet
- un complexe de nitrate de guanyl urée avec un métal (Cu, Zn, Mn, par exemple), tel celui de formule CuGuN,
- un oxydant (tel le nitrate basique de cuivre (BCN)), et
- un autre réducteur (tel le nitrate de guanidine (NG)).
- a complex of guanyl urea nitrate with a metal (Cu, Zn, Mn, for example), such as that of formula CuGuN,
- an oxidant (such as basic copper nitrate (BCN)), and
- another reducing agent (such as guanidine nitrate (NG)).
Lesdits objets ont une température de combustion basse, de par la présence dudit complexe de faible enthalpie de formation dans leur composition.Said objects have a low combustion temperature, due to the presence of said complex of low enthalpy of formation in their composition.
Actuellement, pour les airbags frontaux, les objet solides pyrotechniques qui semblent offrir le meilleur compromis en référence aux nombreuses exigences à satisfaire (voir ci-dessus) contiennent, dans leur composition, 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). Leur composition (de type NG/BCN, donc) est par ailleurs susceptible de renfermer au moins un additif, agissant sur l'agglomération des résidus de combustion et/ou, avantageusement et, sur la vitesse de combustion.Currently, for front airbags, the pyrotechnic solid objects which seem to offer the best compromise with reference to the many requirements to be satisfied (see above) contain, in their composition, as main ingredients, guanidine nitrate (NG; as reducing charge) and basic copper nitrate (BCN; as oxidizing charge). Their composition (of NG / BCN type, therefore) is moreover capable of containing at least one additive, acting on the agglomeration of combustion residues and / or, advantageously, on the combustion rate.
La Demanderesse a plus particulièrement décrit, dans la demande de brevet
- il agit comme agent « slaggant » ou agent agglomérant (ledit au moins un titanate inorganique est un composé réfractaire, dont la température de fusion (voir ci-dessus) est significativement supérieure aux températures de combustion des bases (NG/BCN) dans lesquelles il est présent. Ainsi, il conserve son état physique de solide pulvérulent (il intervient évidemment sous cette forme) à la température de combustion, caractéristique nécessaire à l'obtention d'un effet d'agglomération des résidus liquides de cuivre (à une augmentation de la viscosité de la phase condensée constituée de cuivre liquide). La filtrabilité des résidus de combustion ainsi facilitée, il est possible de réduire les systèmes de filtration des générateurs de gaz) ; et,
- il agit positivement sur la vitesse de combustion (les objets renfermant ledit au moins un titanate inorganique dans leur composition présentent simultanément une vitesse de combustion élevée (≥ 20 mm/s à 20 MPa) et une température de combustion modérée (< 2200 K), avec exposant de pression faible et combustion non nulle et auto-entretenue à pression atmosphérique).
- it acts as a “slaggant” or agglomerating agent (said at least one inorganic titanate is a refractory compound, the melting point of which (see above) is significantly higher than the combustion temperatures of the bases (NG / BCN) in which it is is present. Thus, it retains its physical state as a pulverulent solid (it obviously occurs in this form) at the combustion temperature, a characteristic necessary to obtain an agglomeration effect of the liquid copper residues (at an increase of the viscosity of the condensed phase consisting of liquid copper). The filterability of the combustion residues thus facilitated, it is possible to reduce the filtration systems of the gas generators); and,
- it acts positively on the combustion rate (objects containing said at least one inorganic titanate in their composition simultaneously exhibit a high combustion rate (≥ 20 mm / s at 20 MPa) and a moderate combustion temperature (<2200 K), with low pressure exponent and non-zero, self-sustaining combustion at atmospheric pressure).
La Demanderesse a en fait considéré le problème technique de l'encombrement et de la masse (et donc du coût) des générateurs de gaz fonctionnant avec chargement solide pyrotechnique générateur de gaz. Elle a souhaité optimiser l'architecture desdits générateurs en minimisant le volume et la masse des dispositifs requis, au sein de la structure desdits générateurs, pour la filtration et le refroidissement des gaz de combustion générés. On peut indiquer, pour illustration, que la masse du dispositif de filtration employé, pour une composition génératrice de gaz dont la température de combustion est de 1900 K, est généralement équivalente à la masse du chargement générateur de gaz. A toutes fins utiles, on peut aussi préciser que le dispositif de filtration constitue per se un dispositif de refroidissement (qui cumule son effet de refroidissement avec celui du dispositif de refroidissement).The Applicant has in fact considered the technical problem of the size and weight (and therefore of the cost) of gas generators operating with a pyrotechnic solid charge that generates gas. It wished to optimize the architecture of said generators by minimizing the volume and mass of the devices required, within the structure of said generators, for the filtration and cooling of the combustion gases generated. It can be indicated, for illustration, that the mass of the filtration device employed, for a gas-generating composition with a combustion temperature of 1900 K, is generally equivalent to the mass of the gas-generating charge. For all practical purposes, it can also be specified that the filtration device constitutes per se a cooling device (which combines its cooling effect with that of the cooling device).
Dans cette optique d'optimisation de l'architecture desdits générateurs, la Demanderesse propose de nouveaux objets solides pyrotechniques générateurs de gaz, présentant une composition de type NG/BCN, pouvant être obtenus par voie sèche, sans présence de liant dans leur composition, et dont la température de combustion (inférieure à 1800 K) est plus faible que celle (inférieure à 2200 K) des objets décrits dans la demande de brevet
Selon son premier objet, la présente invention concerne donc des objets solides pyrotechniques générateurs de gaz. De façon caractéristique, la composition desdits objets, exprimée en pourcentages massiques, renferme :
- de 35 à 50 %, avantageusement de 40 à 50 %, de nitrate de guanidine (NG),
- de 35 à 50 % de nitrate basique de cuivre (BCN),
- de 0,5 à 6 % d'au moins un composé choisi parmi l'alumine (Al2O3), les titanates inorganiques dont la température de fusion est supérieure à 2100 K et leurs mélanges, et
- de 5 à 18 % d'au moins un oxalate inorganique choisi parmi l'oxalate de sodium (Na2C2O4), l'oxalate d'étain (SnC2O4), l'oxalate de strontium (SrC2O4), l'oxalate de fer (FeC2O4), l'oxalate de cuivre (CuC2O4) et leurs mélanges ;
- from 35 to 50%, advantageously from 40 to 50%, of guanidine nitrate (NG),
- from 35 to 50% basic copper nitrate (BCN),
- from 0.5 to 6% of at least one compound chosen from alumina (Al 2 O 3 ), inorganic titanates whose melting point is greater than 2100 K and mixtures thereof, and
- from 5 to 18% of at least one inorganic oxalate chosen from sodium oxalate (Na 2 C 2 O 4 ), tin oxalate (SnC 2 O 4 ), strontium oxalate (SrC 2 O 4 ), iron oxalate (FeC 2 O 4 ), copper oxalate (CuC 2 O 4 ) and their mixtures;
Ladite composition est donc de type NG (charge réductrice)/BCN (charge oxydante).Said composition is therefore of the NG (reducing charge) / BCN (oxidizing charge) type.
Le nitrate de guanidine (NG) a été retenu comme réducteur, entre autre, pour sa capacité à générer beaucoup de gaz, pour son comportement rhéo-plastique adapté à la mise en œuvre de la phase de pastillage (direct) ou des phases de compactage et de pastillage d'un procédé voie sèche (sa présence permet notamment une bonne densification de la composition pyrotechnique pulvérulente de départ tout en limitant l'effort de compression à appliquer : voir ci-après), et pour des raisons de sécurité pyrotechnique. La composition des objets pyrotechniques de l'invention renferme de 35 à 50 % en masse de nitrate de guanidine (NG), avantageusement de 40 à 50 % en masse de nitrate de guanidine (NG).Guanidine nitrate (NG) was chosen as a reducing agent, among other things, for its ability to generate a lot of gas, for its rheo-plastic behavior adapted to the implementation of the pelletizing phase (direct) or the compaction phases and pelletizing of a dry process (its presence allows in particular a good densification of the starting powdery pyrotechnic composition while limiting the compressive force to be applied: see below), and for pyrotechnic safety reasons. The composition of the pyrotechnic articles of the invention contains from 35 to 50% by mass of guanidine nitrate (NG), advantageously from 40 to 50% by mass of guanidine nitrate (NG).
Le nitrate basique de cuivre (BCN) a été retenu comme oxydant, et ce, tout particulièrement, pour son impact sur la vitesse de combustion, pour sa ductibilité et son effet « slaggant » (présence du cuivre). Ledit nitrate basique de cuivre est présent à raison de 35 à 50 % en masse, généralement à raison de 35 à 45 % en masse.Basic copper nitrate (BCN) was chosen as an oxidant, particularly for its impact on the combustion rate, for its ductility and its “slaggant” effect (presence of copper). Said basic copper nitrate is present in an amount of 35 to 50% by mass, generally in an amount of 35 to 45% by mass.
Ladite composition renferme donc, dans une base de type NG/BCN (telle que précisée ci-dessus, en référence notamment à la valeur de balance en oxygène souhaitée, proche de -3 %), une faible quantité (de 0,5 à 6 %, souvent de 1 à 6 %, avantageusement de 3 à 5 %, en masse) d'au moins un composé choisi parmi l'alumine (Al2O3), les titanates inorganiques dont la température de fusion est supérieure à 2100 K et leurs mélanges. La présence dudit au moins un composé est opportune au regard de l'agglomération des résidus de combustion (à toutes fins utiles, on peut noter ici que l'alumine a un pouvoir « slaggant » supérieur à celui des titanates) et de la vitesse de combustion. Ladite composition renferme avantageusement de l'alumine (Al2O3) ou au moins un titanate tel que précisé ci-dessus. Elle renferme très avantageusement de l'alumine (Al2O3) ou un tel titanate.Said composition therefore contains, in an NG / BCN type base (as specified above, with particular reference to the desired oxygen balance value, close to -3%), a small amount (from 0.5 to 6 %, often from 1 to 6%, advantageously from 3 to 5%, by mass) of at least one compound chosen from alumina (Al 2 O 3 ), inorganic titanates whose melting point is greater than 2100 K and their mixtures. The presence of said at least one compound is appropriate with regard to the agglomeration of the combustion residues (for all practical purposes, it can be noted here that the alumina has a “slaggant” power greater than that of the titanates) and the speed of combustion. Said composition advantageously contains alumina (Al 2 O 3 ) or at least one titanate as specified above. It very advantageously contains alumina (Al 2 O 3 ) or such a titanate.
Ladite composition des objets de l'invention renferme, dans une base de type NG/BCN telle que précisée ci-dessus, en sus dudit au moins un titanate inorganique et/ou alumine, une quantité relativement limitée (de 5 à 18 %, notamment de 5 à 15 %, avantageusement de 5 à 13 %, très avantageusement de 7 à 13 %, en masse) d'au moins un agent de refroidissement spécifique, i.e. d'au moins un oxalate inorganique choisi parmi l'oxalate de sodium (Na2C2O4), l'oxalate d'étain (SnC2O4), l'oxalate de strontium (SrC2O4), l'oxalate de fer (FeC2O4), l'oxalate de cuivre (CuC2O4) et leurs mélanges. Comme indiqué ci-dessus, la présence, au sein de la base NG/BCN spécifiée (renfermant ledit au moins un titanate inorganique et/ou alumine), d'au moins un tel oxalate, en ladite quantité relativement limitée indiquée, s'est révélée opportune, en référence à l'abaissement de la température de combustion des objets, sans induire d'effets significatifs sur les autres paramètres tels la vitesse de combustion (la présence d'un ingrédient explosif n'est pas requise), le rendement gazeux (les oxalates ont été préférés aux formiates) et les stabilités dans le temps (les oxalates sélectionnés étant peu hygroscopiques) et en température (la température de fusion et/ou décomposition des oxalates retenus n'est pas inférieure à 200 °C (l'homme du métier a compris que lesdits oxalates retenus sont sous forme anhydre)) desdits objets. Les oxalates sélectionnés sont par ailleurs non toxiques et de coûts raisonnables.Said composition of the objects of the invention contains, in a base of NG / BCN type as specified above, in addition to said at least one inorganic titanate and / or alumina, a relatively limited amount (from 5 to 18%, in particular from 5 to 15%, advantageously from 5 to 13%, very advantageously from 7 to 13%, by mass) of at least one specific cooling agent, ie of at least one chosen inorganic oxalate from sodium oxalate (Na 2 C 2 O 4 ), tin oxalate (SnC 2 O 4 ), strontium oxalate (SrC 2 O 4 ), iron oxalate (FeC 2 O 4) ), copper oxalate (CuC 2 O 4 ) and their mixtures. As indicated above, the presence, within the specified NG / BCN base (containing said at least one inorganic titanate and / or alumina), of at least one such oxalate, in said relatively limited amount indicated, has occurred. proved to be opportune, with reference to the lowering of the combustion temperature of the objects, without inducing significant effects on the other parameters such as the combustion rate (the presence of an explosive ingredient is not required), the gas yield (the oxalates were preferred to the formates) and the stability over time (the oxalates selected being not very hygroscopic) and in temperature (the melting point and / or decomposition of the oxalates selected is not less than 200 ° C (the those skilled in the art have understood that said retained oxalates are in anhydrous form)) of said objects. The selected oxalates are, moreover, non-toxic and inexpensive.
Ladite composition des objets de l'invention ne renferme pas de liant. En effet, le comportement rhéo-plastique du nitrate de guanidine (NG), entrant en quantité significative dans ladite composition, rend la présence d'un quelconque liant superflu (notamment pour l'obtention, par voie sèche, d'objets pyrotechniques formés, de granulés, de pastilles et de blocs monolithes comprimés (voir ci-après)). L'homme du métier conçoit l'intérêt de pouvoir obtenir, par voie sèche, les objets de l'invention et ce, sans intervention d'un liant (qui aurait un impact significatif sur l'oxygène balance de la composition) ; l'absence d'un quelconque liant étant par ailleurs particulièrement opportune en référence à l'objectif visé de température de combustion basse et de rendement gazeux élevé desdits objets.Said composition of the objects of the invention does not contain a binder. Indeed, the rheoplastic behavior of guanidine nitrate (NG), entering in a significant amount in said composition, makes the presence of any binder superfluous (in particular for obtaining, by dry process, pyrotechnic objects formed, granules, pellets and compressed monolith blocks (see below)). A person skilled in the art understands the advantage of being able to obtain, by the dry route, the objects of the invention without the intervention of a binder (which would have a significant impact on the oxygen balance of the composition); the absence of any binder being moreover particularly advisable with reference to the desired objective of low combustion temperature and high gas yield of said objects.
Ladite composition des objets de l'invention ne renferme pas d'ingrédient explosif. Elle ne renferme ainsi, ni nitroguanidine, ni hexogène (RDX), ni octogène (HMX)... On entend, présentement et de façon conventionnelle, par ingrédient explosif, 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.10/11/Rev.4, ISBN 92-1-239083-8ISSN 1014-7179 et STANAG 4488). A toutes fins utiles, on rappelle que le nitrate de guanidine (NG) n'est pas un ingrédient classé dans cette division de risque. L'absence d'un quelconque ingrédient explosif au sein de la composition des objets de l'invention est particulièrement opportune en référence à la sécurité et à la température de combustion desdits objets. On rappelle incidemment qu'une basse température de combustion est recherchée.Said composition of the objects of the invention does not contain an explosive ingredient. It thus contains neither nitroguanidine nor hexogen (RDX), neither octogen (HMX) ... Currently and conventionally, explosive ingredient is understood to mean ingredients classified in risk division 1.1 according to standard NF T 70-502 (see also UN - Recommendations relating to Transport Dangerous Goods - Manual of Tests and Criteria, Fourth Revised Edition, ST / SG / AC.10 / 11 / Rev.4, ISBN 92-1-239083-8ISSN 1014-7179 and STANAG 4488). For all practical purposes, it is recalled that guanidine nitrate (NG) is not an ingredient classified in this risk division. The absence of any explosive ingredient in the composition of the objects of the invention is particularly appropriate with reference to the safety and to the combustion temperature of said objects. It is incidentally recalled that a low combustion temperature is desired.
Les objets de l'invention, présentant la composition telle que précisée ci-dessus, se sont donc révélés particulièrement intéressants au regard :
- 1) de leur température de combustion (basse : inférieure à 1800 K ; température de combustion basse qui reste associée à une vitesse de combustion de plus de 15 mm/s à 20 MPa (en référence à ladite vitesse de combustion, on peut d'ores et déjà indiquer ici qu'elle est opportunément augmentée en utilisant les ingrédients sous des granulométries fines, adaptées (voir ci-après)),
- 2) de leur génération de résidus de combustion (en faible quantité, sous forme agglomérés), et
- 3) de leur obtention (de mise en œuvre aisée par voie sèche).
- 1) their combustion temperature (low: less than 1800 K; low combustion temperature which remains associated with a combustion rate of more than 15 mm / s at 20 MPa (with reference to said combustion rate, it is possible to ores and already indicate here that it is suitably increased by using the ingredients in fine grain sizes, adapted (see below)),
- 2) their generation of combustion residues (in small quantities, in agglomerated form), and
- 3) their obtaining (easy to apply by dry process).
Le au moins un oxalate inorganique présent dans la composition des objets de l'invention est avantageusement choisi parmi l'oxalate de sodium (Na2C2O4), l'oxalate de strontium (SrC2O4) et l'oxalate de cuivre (CuC2O4).The at least one inorganic oxalate present in the composition of the objects of the invention is advantageously chosen from sodium oxalate (Na 2 C 2 O 4 ), strontium oxalate (SrC 2 O 4 ) and oxalate of copper (CuC 2 O 4 ).
Le au moins un titanate inorganique, dont la température de fusion est supérieure à 2100 K, éventuellement présent dans la composition des objets de l'invention (on rappelle à toutes fins utiles que ladite composition renferme de 0,5 à 6 %, souvent de 1 à 6 %, avantageusement de 3 à 5 %, d'au moins un composé choisi parmi l'alumine (Al2O3), les titanates inorganiques dont la température de fusion est supérieure à 2100 K et leurs mélanges), est avantageusement choisi parmi les titanates métalliques, les titanates d'alcalino-terreux et leurs mélanges. Il consiste très avantageusement en un titanate métallique ou un titanate d'alcalino-terreux. De façon préférée, la composition des objets de l'invention, qui renferme au moins un titanate tel que précisé, renferme du titanate de strontium (SrTiO3) et/ou du titanate de calcium (CaTiO3) et/ou du titanate d'aluminium (Al2TiO5). De façon particulièrement préférée, elle renferme du titanate de strontium (SrTiO3), du titanate de calcium (CaTiO3) ou du titanate d'aluminium (Al2TiO5). Ces titanates présentent respectivement des températures de fusion de 2353 K, 2248 K et 2133 K, i.e. des températures de fusion significativement supérieure à la température de combustion de la base NG/BCN (la température de combustion d'une quelconque base NG/BCN étant en effet toujours inférieure à 1950 K), qui, de surcroit renferme le au moins un oxalate inorganique.The at least one inorganic titanate, the melting point of which is greater than 2100 K, optionally present in the composition of objects of the invention (it is recalled for all useful purposes that said composition contains from 0.5 to 6%, often from 1 to 6%, advantageously from 3 to 5%, of at least one compound chosen from alumina ( Al 2 O 3 ), inorganic titanates whose melting point is greater than 2100 K and their mixtures), is advantageously chosen from metal titanates, alkaline earth titanates and their mixtures. It very advantageously consists of a metal titanate or an alkaline earth titanate. Preferably, the composition of the objects of the invention, which contains at least one titanate as specified, contains strontium titanate (SrTiO 3 ) and / or calcium titanate (CaTiO 3 ) and / or titanate of aluminum (Al 2 TiO 5 ). Particularly preferably, it contains strontium titanate (SrTiO 3 ), calcium titanate (CaTiO 3 ) or aluminum titanate (Al 2 TiO 5 ). These titanates respectively exhibit melting temperatures of 2353 K, 2248 K and 2133 K, ie melting temperatures significantly higher than the combustion temperature of the NG / BCN base (the combustion temperature of any NG / BCN base being in fact always less than 1950 K), which, in addition, contains the at least one inorganic oxalate.
Dans le cadre de son premier objet, la présente invention concerne la sous-famille des objets solides pyrotechniques générateurs de gaz, dont la composition, exprimée en pourcentages massiques, renferme :
- de 35 à 50 %, avantageusement de 40 à 50 %, de nitrate de guanidine (NG),
- de 35 à 45 % de nitrate basique de cuivre (BCN),
- de 1 à 6 %, avantageusement de 3 à 5 %, d'au moins un composé choisi parmi l'alumine (Al2O3), les titanates inorganiques dont la température de fusion est supérieure à 2100 K et leurs mélanges, et
- de 5 à 15 %, avantageusement de 5 à 13 %, très avantageusement de 7 à 13 %, d'au moins un oxalate inorganique choisi parmi l'oxalate de sodium (Na2C2O4), l'oxalate d'étain (SnC2O4) et leurs mélanges ;
- from 35 to 50%, advantageously from 40 to 50%, of guanidine nitrate (NG),
- from 35 to 45% basic copper nitrate (BCN),
- from 1 to 6%, advantageously from 3 to 5%, of at least one compound chosen from alumina (Al 2 O 3 ), inorganic titanates whose melting point is greater than 2100 K and their mixtures, and
- from 5 to 15%, advantageously from 5 to 13%, very advantageously from 7 to 13%, of at least one inorganic oxalate chosen from sodium oxalate (Na 2 C 2 O 4 ), tin oxalate (SnC 2 O 4 ) and mixtures thereof;
Dans la composition des objets de cette sous-famille, le au moins un oxalate inorganique consiste avantageusement en l'oxalate de sodium.In the composition of the objects of this subfamily, the at least one inorganic oxalate advantageously consists of sodium oxalate.
A propos des objets de ladite sous-famille, on peut reprendre ce qui a été dit ci-dessus et qui bien évidemment s'y applique.With regard to the objects of said sub-family, we can take up what was said above and which obviously applies to it.
Les ingrédients des quatre types ci-dessus (nitrate de guanidine (NG), nitrate basique de cuivre (BCN), alumine et/ou titanate(s) inorganique(s) dont la température de fusion est supérieure à 2100 K, et oxalate(s) inorganique(s), tel(s) que précisé(s)) (ingrédients constitutifs des objets de l'invention en général et de la sous famille ci-dessus en particulier) représentent généralement au moins 98 % en masse de la composition des objets pyrotechniques de l'invention. Les ingrédients des quatre types ci-dessus peuvent tout à fait représenter au moins 99,5 % en masse, voire même 100 % en masse de la masse totale des objets de l'invention. L'éventuelle présence d'au moins un « autre » additif (l'alumine et/ou le au moins un titanate inorganique ainsi que le au moins un oxalate inorganique pouvant tout à fait être assimilés à des additifs), choisi, par exemple, parmi les auxiliaires de fabrication (stéarate de calcium, graphite, silice notamment), est expressément prévue, à un taux inférieur ou égal à 2 % en masse. On a compris, au vu des propos ci-dessus, qu'un tel au moins un « autre » additif ne saurait en aucune façon consister en un liant ou en un ingrédient explosif.The ingredients of the above four types (guanidine nitrate (NG), basic copper nitrate (BCN), alumina and / or inorganic titanate (s) with a melting point above 2100 K, and oxalate ( s) inorganic (s), as specified) (constituent ingredients of the objects of the invention in general and of the above subfamily in particular) generally represent at least 98% by mass of the composition pyrotechnic objects of the invention. The ingredients of the four types above can quite represent at least 99.5% by mass, or even 100% by mass of the total mass of the objects of the invention. The possible presence of at least one “other” additive (alumina and / or the at least one inorganic titanate as well as the at least one inorganic oxalate which can be completely assimilated to additives), chosen, for example, among the processing aids (calcium stearate, graphite, silica in particular), is expressly provided, at a rate less than or equal to 2% by mass. It has been understood, in view of the above remarks, that such at least one "other" additive can in no way consist of a binder or of an explosive ingredient.
Les ingrédients constitutifs (principaux) des objets de l'invention - nitrate de guanidine + nitrate basique de cuivre + alumine et/ou au moins un titanate inorganique tel que précisé + au moins un oxalate inorganique tel que précisé - sont des produits connus. Ils se présentent sous la forme de poudres dont la distribution granulométrique est resserrée (autour de leur diamètre médian (d50)). Tout au long du présent texte (y compris dans les exemples), les diamètres médians indiqués sont des diamètres médians en volume.The constitutive (main) ingredients of the objects of the invention - guanidine nitrate + basic copper nitrate + alumina and / or at least one inorganic titanate as specified + at least one oxalate inorganic as specified - are known products. They are in the form of powders with a narrow particle size distribution (around their median diameter (d 50 )). Throughout this text (including in the examples), the median diameters indicated are median diameters by volume.
Lesdits ingrédients constitutifs (principaux) des objets de l'invention présentent avantageusement, tout particulièrement en référence à l'obtention desdits objets par voie sèche et à la vitesse de combustion desdits objets, une granulométrie fine, voire très fine. Ils présentent généralement des valeurs de diamètre médian (d50) inférieures ou égales à 20 µm.Said (main) constituent ingredients of the objects of the invention advantageously exhibit, very particularly with reference to the obtaining of said objects by the dry process and to the rate of combustion of said objects, a fine, or even very fine, particle size. They generally have median diameter values (d 50 ) less than or equal to 20 μm.
Pour un parfait mélange des poudres de la base NG/BCN (ingrédients constitutifs principaux des objets de l'invention, intervenant conventionnellement à l'état pulvérulent), on préconise que le diamètre médian de l'un desdits nitrate de guanidine (NG) et nitrate basique de cuivre (BCN) soit substantiellement plus élevé que le diamètre médian de l'autre desdits nitrate de guanidine (NG) et nitrate basique de cuivre (BCN), ledit diamètre médian substantiellement (significativement) plus élevé demeurant généralement inférieur ou égal à 20 µm (voir ci-dessus). Par « substantiellement plus élevé », on entend « au moins 1,8 fois plus élevé », avantageusement « au moins le double de », très avantageusement « au moins 5 fois plus élevé », voire « au moins 10 fois plus élevé ». Des résultats très intéressants ont notamment été obtenus avec des poudres de NG présentant un diamètre médian de 12 µm et des poudres de BCN présentant un diamètre médian inférieur à 6 µm. Selon une variante avantageuse, le diamètre médian de l'un desdits nitrate de guanidine et nitrate basique de cuivre, par exemple celui dudit nitrate basique de cuivre, est inférieur ou égal à 1 µm tandis que le diamètre médian de l'autre desdits nitrate de guanidine et nitrate basique de cuivre, par exemple donc celui dudit nitrate de guanidine, est d'au moins 5 µm, avantageusement d'au moins 10 µm (tout en demeurant généralement inférieur ou égal à 20 µm (voir ci-dessus)). Des résultats très intéressants ont notamment été obtenus avec des poudres de NG présentant un diamètre médian entre 10 et 14 µm et des poudres de BCN présentant un diamètre médian de 1 µm. L'intervention d'une poudre très fine (d50 ≤ 1 µm) et d'une poudre « substantiellement plus grosse », est préconisée tout particulièrement en vue de la réalisation d'un parfait mélange et de l'obtention d'une vitesse de combustion élevée. Cet effet (positif) de la granulométrie sur la vitesse de combustion est opportunément mis à profit pour compenser l'effet limité de la présence de l'oxalate sur ladite vitesse de combustion.For a perfect mixture of the powders of the NG / BCN base (main constituent ingredients of the objects of the invention, conventionally occurring in the pulverulent state), it is recommended that the median diameter of one of said guanidine nitrate (NG) and Basic copper nitrate (BCN) is substantially greater than the median diameter of the other of said guanidine nitrate (NG) and basic copper nitrate (BCN), said substantially (significantly) larger median diameter generally remaining less than or equal to 20 µm (see above). By “substantially higher” is meant “at least 1.8 times higher”, advantageously “at least double of”, very advantageously “at least 5 times higher”, or even “at least 10 times higher”. Very interesting results have in particular been obtained with NG powders having a median diameter of 12 μm and BCN powders having a median diameter of less than 6 μm. According to an advantageous variant, the median diameter of one of said guanidine nitrate and basic copper nitrate, for example that of said basic copper nitrate, is less than or equal to 1 μm while the median diameter of the other of said nitrate of copper. guanidine and basic copper nitrate, for example therefore that of said guanidine nitrate, is at least 5 μm, advantageously at least 10 μm (while generally remaining less than or equal to 20 μm (see above)). Very interesting results have in particular been obtained with NG powders having a median diameter between 10 and 14 μm and BCN powders having a median diameter of 1 μm. The use of a very fine powder (d 50 ≤ 1 µm) and of a “substantially larger” powder is particularly recommended for achieving a perfect mixing and obtaining a speed high combustion. This (positive) effect of the particle size on the combustion rate is advantageously taken advantage of to compensate for the limited effect of the presence of the oxalate on said combustion rate.
Lorsque de l'alumine (intervenant elle aussi à l'état pulvérulent) est présente, elle l'est avantageusement à une granulométrie fine, voire très fine ; elle présente alors une surface spécifique élevée, voire très élevée. On a mentionné pour tous les ingrédients constitutifs des valeurs de diamètre médian généralement inférieures ou égales à 20 µm. Pour l'alumine, on peut mentionner des valeurs de diamètre médian généralement inférieures ou égales à 10 µm, avantageusement inférieures ou égales à 5 µm, très avantageusement inférieures ou égales à 1 µm, voire aussi faibles que 100 nm, et même 10 nm.When alumina (also intervening in the pulverulent state) is present, it is advantageously present with a fine grain size, or even very fine; it then has a high specific surface, or even very high. Median diameter values generally less than or equal to 20 μm have been mentioned for all the constituent ingredients. For alumina, there may be mentioned median diameter values generally less than or equal to 10 μm, advantageously less than or equal to 5 μm, very advantageously less than or equal to 1 μm, or even as low as 100 nm, and even 10 nm.
Lorsqu'au moins un titanate inorganique (intervenant lui-aussi à l'état pulvérulent) est présent, il l'est aussi avantageusement à une granulométrie la plus faible possible. Ainsi, de façon avantageuse, ledit au moins un titanate inorganique présent l'est sous une forme pulvérulente fine, de dimension micrométrique, voire de dimension nanométrique, i.e. avec un diamètre médian (d50) inférieur à 6 µm, voire inférieur à 1 µm (généralement dans le cadre de cette variante avantageuse, on a : 0,5 µm ≤ d50 ≤ 6 µm). Ledit au moins un titanate inorganique présent a avantageusement une surface spécifique supérieure à 1 m2/g (très avantageusement supérieure à 5 m2/g ou plus).When at least one inorganic titanate (itself involved in the pulverulent state) is present, it is also advantageously present at the smallest possible particle size. Thus, advantageously, said at least one inorganic titanate present is present in a fine pulverulent form, of micrometric dimension, or even of nanometric dimension, ie with a median diameter (d 50 ) of less than 6 μm, or even less than 1 μm. (generally in the context of this advantageous variant, we have: 0.5 μm ≤ d 50 ≤ 6 μm). Said at least one inorganic titanate present advantageously has a specific surface area greater than 1 m 2 / g (very advantageously greater than 5 m 2 / g or more).
Pour ce qui concerne la granulométrie du au moins un oxalate inorganique, elle est elle aussi opportunément la plus fine possible. Toutefois, de bons résultats ont été obtenus avec des produits commerciaux « de grosse granulométrie », notamment avec de l'oxalate de sodium présentant un diamètre médian supérieur à 40 µm (de 60 µm notamment). Nul doute que les bons résultats obtenus seraient encore meilleurs avec (au moins) un oxalate de l'invention, plus fin (présentant notamment un diamètre médian inférieur à 20 µm (voir ci-dessus)).As regards the particle size of at least one inorganic oxalate, it is also suitably the finest possible. However, good results have been obtained with commercial products of “large particle size”, in particular with sodium oxalate having a median diameter greater than 40 μm (60 μm in particular). There is no doubt that the good results obtained would be even better with (at least) one oxalate of the invention, which is thinner (in particular having a median diameter of less than 20 μm (see above)).
Les objets de l'invention sont notamment susceptibles d'exister sous la forme d'objets pyrotechniques formés, de granulés, de pastilles ou de blocs (comprimés) monolithes (voir ci-après).The objects of the invention are in particular likely to exist in the form of formed pyrotechnic objects, granules, pellets or monolithic blocks (tablets) (see below).
On en vient maintenant à la fabrication des objets solides pyrotechniques de l'invention. Les procédés de fabrication en cause sont des procédés par analogie, voie sèche ou voie humide, avantageusement voie sèche.We now come to the manufacture of the solid pyrotechnic objects of the invention. The manufacturing processes in question are processes by analogy, the dry route or the wet route, advantageously the dry route.
Les objets solides pyrotechniques de l'invention peuvent être fabriqués (par voie sèche) par simple pastillage (compression) des mélanges de poudres obtenus par mélange de leurs ingrédients constitutifs (on a compris que lesdits ingrédients sont utilisés à l'état pulvérulent, avec une granulométrie plus ou moins fine, opportunément la plus fine possible (voir ci-dessus), et qu'il s'agit essentiellement, voire exclusivement, de NG, BCN, alumine et/ou titanate(s) inorganique(s) tel(s) que précisé(s), et oxalate(s) tel(s) que précisé(s)).The pyrotechnic solid objects of the invention can be manufactured (by the dry process) by simple pelletizing (compression) of the powder mixtures obtained by mixing their constituent ingredients (it has been understood that said ingredients are used in the pulverulent state, with a more or less fine particle size, suitably as fine as possible (see above), and that it is essentially, or even exclusively, NG, BCN, alumina and / or inorganic titanate (s) such as ) as specified, and oxalate (s) as specified).
Les objets pyrotechniques de l'invention peuvent aussi être fabriqués (par voie sèche) selon un procédé susceptible de comprendre jusqu'à quatre étapes principales. Un tel procédé est familier à l'homme de l'art. Il a notamment été décrit dans la demande de brevet
L'alumine ou(et) le au moins un titanate inorganique (dont la température de fusion est supérieure à 2100 K) et le au moins un oxalate inorganique (choisi parmi l'oxalate de sodium, l'oxalate d'étain, l'oxalate de strontium, l'oxalate de fer, l'oxalate de cuivre et leurs mélanges) interviennent avantageusement avec les autres ingrédients constitutifs, NG + BCN principalement, voire NG + BCN exclusivement, au début du procédé de fabrication. Il est toutefois possible que ledit alumine ou(et) ledit au moins un titanate inorganique (dont la température de fusion est supérieure à 2100 K) ou(et) ledit au moins un oxalate inorganique (choisi parmi l'oxalate de sodium, l'oxalate d'étain, l'oxalate de strontium, l'oxalate de fer, l'oxalate de cuivre et leurs mélanges), tout particulièrement ledit au moins un oxalate inorganique, soi(en)t ajouté(s), plus en aval, dans le procédé de fabrication des objets de l'invention. On comprend que plusieurs alternatives existent. On peut incidemment noter qu'il n'est pas exclu de faire intervenir l'un et/ou l'autre desdits alumine, au moins un titanate inorganique et au moins un oxalate inorganique en plusieurs fois au cours dudit procédé.Alumina or (and) at least one inorganic titanate (whose melting point is greater than 2100 K) and at least one inorganic oxalate (chosen from sodium oxalate, tin oxalate, strontium oxalate, iron oxalate, copper oxalate and their mixtures) are advantageously involved with the other constituent ingredients, NG + BCN mainly, or even NG + BCN exclusively, at the start of the manufacturing process. It is however possible that said alumina or (and) said at least one inorganic titanate (the melting point of which is greater than 2100 K) or (and) said at least one inorganic oxalate (chosen from sodium oxalate, tin oxalate, strontium oxalate, iron oxalate, copper oxalate and mixtures thereof), quite particularly said at least one inorganic oxalate, itself (s) added, further downstream, in the method of manufacturing the objects of the invention. We understand that several alternatives exist. It may incidentally be noted that it is not excluded to involve one and / or the other of said alumina, at least one inorganic titanate and at least one inorganic oxalate in several stages during said process.
Le procédé de fabrication (préparation) voie sèche préférentiel des objets pyrotechniques de l'invention inclut une étape de compactage à sec d'un mélange des ingrédients constitutifs en poudre desdits objets (excepté, éventuellement, ledit au moins un oxalate inorganique qui peut être ajouté plus tard). Le compactage à sec est généralement mis en œuvre, de façon connue per se, dans un compacteur à cylindres, à une pression de compactage (p) comprise entre 108 et 6.108 Pa (108 Pa ≤ p ≤ 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 ou avec une étape caractéristique de compactage couplée à une étape de mise en forme).The preferential dry manufacturing process (preparation) of the pyrotechnic objects of the invention includes a dry compacting step of a mixture of the powdered constituent ingredients of said objects (except, optionally, said at least one inorganic oxalate which can be added later). Dry compaction is generally carried out, in a manner known per se, in a roller compactor, at a compaction pressure (p) of between 10 8 and 6.10 8 Pa (10 8 Pa ≤ p ≤ 6.10 8 Pa). It can be implemented according to different variants (with a characteristic "simple" compacting step followed by at least one complementary step or with a characteristic compacting step coupled with a shaping step).
Ainsi, les objets solides pyrotechniques de l'invention sont susceptibles d'exister sous différentes formes (notamment au fil du procédé de fabrication conduisant à des objets finaux) :
- à l'issue d'un compactage à sec couplé à une mise en forme (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 ;
- à l'issue d'un compactage à sec (compactage "simple" qui génère une plaque plane) suivi d'une granulation, on obtient des granulés ;
- à l'issue d'un compactage à sec (compactage "simple" qui génère une plaque plane) suivi d'une granulation puis d'un pastillage (compression à sec), on obtient des pastilles ou des blocs monolithiques (comprimés).
- after dry compaction coupled with shaping (by using at least one compacting cylinder, the outer surface of which has cells), plates are obtained with relief patterns that can be breaking for the direct obtaining of formed pyrotechnic objects;
- after dry compaction ("simple" compaction which generates a flat plate) followed by granulation, granules are obtained;
- after dry compaction ("simple" compaction which generates a flat plate) followed by granulation and then pelletizing (dry compression), monolithic pellets or blocks (tablets) are obtained.
Sont particulièrement préférés les objets de l'invention - objets pyrotechniques formés, granulés, pastilles et blocs monolithiques - obtenus à l'issue de l'une ou l'autre des étapes précisées ci-dessus, étant entendu que des pastilles peuvent aussi être obtenues par un pastillage direct (voir ci-dessus).Particularly preferred are the objects of the invention - formed pyrotechnic objects, granules, pellets and monolithic blocks - obtained at the end of one or other of the steps specified above, it being understood that pellets can also be obtained. by direct pelletizing (see above).
Les objets solides pyrotechniques de l'invention peuvent aussi être obtenus par un procédé voie humide. Un tel procédé inclut 1) une étape de mise en solution aqueuse de tous les ou (généralement plutôt) de certains des ingrédients principaux (ladite étape de mise en solution aqueuse comprend généralement la dissolution d'au moins l'un des ingrédients principaux (et plus particulièrement celle du nitrate de guanidine (NG))), 2) l'obtention d'une poudre par séchage par atomisation, 3) l'ajout à la poudre obtenue du ou des ingrédients qui n'ont pas été mis en solution, puis 4) la mise en forme (sous la forme d'objets) du mélange pulvérulent obtenu par les procédés usuels voie sèche.The solid pyrotechnic objects of the invention can also be obtained by a wet process. Such a method includes 1) a step of dissolving all or (generally rather) some of the main ingredients in aqueous solution (said step of dissolving in water generally comprises dissolving at least one of the main ingredients (and more particularly that of guanidine nitrate (NG))), 2) obtaining a powder by spray drying, 3) adding to the powder obtained the ingredient (s) which have not been put into solution, then 4) the shaping (in the form of objects) of the pulverulent mixture obtained by the usual dry process.
Les objets de l'invention existent avantageusement sous la forme de granulés, de pastilles ou de blocs monolithes.The objects of the invention advantageously exist in the form of granules, pellets or monolithic blocks.
De façon nullement limitative, on peut indiquer ici :
- que les granulés de l'invention présentent généralement un diamètre médian (d50) compris entre 200 et 1000 µm (ainsi qu'une masse volumique apparente comprise entre 0,8 et 1,2 g/cm3) ; et
- que les pastilles de l'invention présentent généralement une épaisseur comprise entre 1 et 6 mm pour un diamètre de 3 à 15 mm.
- that the granules of the invention generally have a median diameter (d 50 ) of between 200 and 1000 μm (as well as an apparent density of between 0.8 and 1.2 g / cm 3 ); and
- that the pellets of the invention generally have a thickness of between 1 and 6 mm for a diameter of 3 to 15 mm.
Lesdits granulés et pastilles conviennent parfaitement pour la principale application visée (celle des airbags frontaux, dans le domaine de la sécurité automobile). Les objets pyrotechniques formés et blocs monolithiques sont destinés à d'autres utilisations.Said granules and pellets are ideally suited for the main intended application (that of front airbags, in the field of motor vehicle safety). The formed pyrotechnic objects and monolithic blocks are intended for other uses.
Selon un autre de ses objets, la présente invention concerne une composition pulvérulente (mélange de poudres), précurseur d'un objet de l'invention, dont la composition correspond donc à celle d'un objet de l'invention (voir ci-dessus).According to another of its subjects, the present invention relates to a pulverulent composition (mixture of powders), a precursor of an object of the invention, the composition of which therefore corresponds to that of an object of the invention (see above ).
Selon un autre de ses objets, la présente invention concerne les générateurs de gaz renfermant un chargement solide pyrotechnique générateur de gaz ; ledit chargement contenant au moins un objet solide pyrotechnique de l'invention. Lesdits générateurs, chargés notamment en pastilles de l'invention, conviennent parfaitement pour les airbags, notamment frontaux (voir ci-dessus).According to another of its objects, the present invention relates to gas generators containing a pyrotechnic solid charge which generates gas; said charge containing at least one solid pyrotechnic object of the invention. Said generators, loaded in particular with pellets of the invention, are perfectly suitable for airbags, in particular front airbags (see above).
On se propose maintenant d'illustrer, de façon nullement limitative, l'invention.It is now proposed to illustrate, in no way limiting, the invention.
Des pastilles (pastilles de diamètre 11 mm et d'épaisseur 3 mm) ont été réalisées à partir des ingrédients ci-après :
- NG (commercialisé par la société Alzchem AG (DE), de grade 10 - 14 µm), (d50 ≈ 12 µm),
- BCN (commercialisé par la société Shepherd Chemical Company (US), de grade 4 - 6 µm), (d50 ≈ 5 µm),
- BCN (d50 ≈ 1 µm),
- SrTiO3 (commercialisé par la société Thermograde Process Technology Ltd (US), de grade 4 - 6 µm), (d50 ≈ 5,5 µm),
- Al2O3 (commercialisé par la société Evonik Industries AG (DE), de grade 10 - 100 nm), (de surface spécifique : 100 m2/g),
- Na2C2O4 (commercialisé par la société Alfa Aesar (US) de grade 40 - 70 µm, (d50 ≈ 55 µm),
- SrC2O4 (commercialisé par la société Isaltis (FR), (d50 ≈ 4 µm)
- CuC2O4 (commercialisé par la société Bernardy (FR), (d50 ≈ 5 µm), via un procédé, voie sèche, de compression directe (= simple pastillage mis en œuvre avec une pression de 45. 106 Pa (450 bar)).
- NG (marketed by Alzchem AG (DE), grade 10 - 14 µm), (d 50 ≈ 12 µm),
- BCN (marketed by Shepherd Chemical Company (US), grade 4 - 6 µm), (d 50 ≈ 5 µm),
- BCN (d 50 ≈ 1 µm),
- SrTiO 3 (marketed by Thermograde Process Technology Ltd (US), grade 4 - 6 µm), (d 50 ≈ 5.5 µm),
- Al 2 O 3 (marketed by Evonik Industries AG (DE), grade 10 - 100 nm), (specific surface area: 100 m 2 / g),
- Na 2 C 2 O 4 (marketed by the company Alfa Aesar (US) of grade 40 - 70 µm, (d 50 ≈ 55 µm),
- SrC 2 O 4 (marketed by the company Isaltis (FR), (d 50 ≈ 4 µm)
- CuC 2 O 4 (marketed by the Bernardy company (FR), (d 50 ≈ 5 µm), via a dry process, of direct compression (= simple pelletizing implemented with a pressure of 45. 10 6 Pa (450 bar)).
Le tableau 1 ci-après présente cinq exemples (Ex.1, Ex.2, Ex.3, Ex.4 et Ex.5) de composition d'objets (pastilles) de la présente invention, ainsi que les caractéristiques (performances calculées ou mesurées) desdits objets (pastilles) comparées à celles d'un objet (pastille) de l'art antérieur (Réf.1, selon la demande de brevet
Le tableau 1 ci-après présente aussi deux autres exemples (Ex. A et Réf. 2) de composition de pastilles ainsi que les performances desdites pastilles (obtenues de façon similaire). Ces exemples font ressortir l'intérêt d'utiliser du BCN de granulométrie très fine (avec du NG de granulométrie substantiellement plus élevée).Table 1 below also shows two other examples (Ex. A and Ref. 2) of the composition of pellets as well as the performance of said pellets (obtained in a similar manner). These examples show the advantage of using BCN of very fine particle size (with NG of substantially higher particle size).
Les objets (pastilles) ont été évalué(e)s au moyen de calculs thermodynamiques et à partir de mesures physiques menées donc sur les pastilles. Les vitesses de combustion et exposants de pression desdites pastilles ont été obtenus à la suite de plusieurs tirs en enceinte manométrique (volume 40 cm3). Les valeurs indiquées sont donc des valeurs moyennes.The objects (pellets) were evaluated by means of thermodynamic calculations and from physical measurements therefore carried out on the lozenges. The combustion rates and pressure exponents of said pellets were obtained after several shots in a manometric chamber (volume 40 cm 3 ). The values indicated are therefore average values.
Les pastilles de référence de l'art antérieur (Réf.1) renfermaient, dans leur composition, du nitrate de guanidine (NG), du nitrate basique de cuivre (BCN) ainsi du titanate de strontium (SrTiO3), en les pourcentages massiques indiqués.The reference pellets of the prior art (Ref. 1) contained, in their composition, guanidine nitrate (NG), basic copper nitrate (BCN) and strontium titanate (SrTiO 3 ), in percentages by weight indicated.
Les pastilles des exemples 1 à 5 (Ex.1, Ex.2, Ex.3, Ex.4 et Ex.5) renfermaient, dans leur composition, en sus des trois constituants nitrate de guanidine (NG), nitrate basique de cuivre (BCN) et titanate de strontium (SrTiO3) pour les exemples 1 et 2, alumine pour les exemples 3, 4 et 5, un agent d'abaissement de la température de combustion selon la présente invention : l'oxalate de sodium (Na2C2O4) pour les exemples 1 à 3, l'oxalate de strontium (SrC2O4) pour l'exemple 4 et l'oxalate de cuivre (CuC2O4) pour l'exemple 5. Les quatre constituants étaient présents dans les compositions en les pourcentages massiques indiqués.The tablets of Examples 1 to 5 (Ex.1, Ex.2, Ex.3, Ex.4 and Ex.5) contained, in their composition, in addition to the three constituents guanidine nitrate (NG), basic copper nitrate (BCN) and strontium titanate (SrTiO 3 ) for examples 1 and 2, alumina for examples 3, 4 and 5, an agent for lowering the combustion temperature according to the present invention: sodium oxalate (Na 2 C 2 O 4 ) for examples 1 to 3, strontium oxalate (SrC 2 O 4 ) for example 4 and copper oxalate (CuC 2 O 4 ) for example 5. The four constituents were present in the compositions in the weight percentages indicated.
Les caractéristiques (performances) des compositions (objets) des exemples 1 et 2 ont montré que l'ajout, à un taux variable (teneur massique de, respectivement 7,5 et 10 %), d'oxalate de sodium (Na2C2O4), dans une composition du type de celle de la référence 1 (Réf. 1), a conduit à un abaissement de la température de combustion significatif (de respectivement -144 et -190 °C). La valeur de l'exposant de pression est demeurée acceptable pour l'application visée (airbags frontaux).The characteristics (performances) of the compositions (objects) of Examples 1 and 2 showed that the addition, at a variable rate (mass content of, respectively 7.5 and 10%), of sodium oxalate (Na 2 C 2 O 4 ), in a composition of the type of that of reference 1 (Ref. 1), led to a significant lowering of the combustion temperature (respectively -144 and -190 ° C). The value of the pressure exponent remained acceptable for the intended application (front airbags).
Les caractéristiques (performances) de la composition (de l'objet) de l'exemple 3 ont montré que la présence d'alumine contribuait à l'obtention de bonnes performances (abaissement de la température de combustion (de -155 °C par rapport à l'exemple de Réf.1) avec accroissement de la valeur de la vitesse de combustion à 20 MPa par rapport à l'exemple 2, et augmentation parallèle de la qualité d'agglomération des résidus de combustion par rapport à l'exemple 2).The characteristics (performance) of the composition (of the article) of Example 3 showed that the presence of alumina contributed to obtaining good performance (lowering of the combustion temperature (from -155 ° C compared to using the example of Ref. 1) with an increase in the value of the combustion speed to 20 MPa by compared to Example 2, and a parallel increase in the quality of agglomeration of the combustion residues compared to Example 2).
Les caractéristiques (performances) de la composition (objet) de l'exemple 4 ont montré que l'ajout conjoint d'alumine et d'oxalate de strontium (SrC2O4) dans une composition du type de celle de la référence 1 (Réf. 1), a conduit à un abaissement de la température de combustion significatif (de -156 °C). La valeur de l'exposant de pression est demeurée acceptable pour l'application visée (airbags frontaux). La très bonne qualité d'agglomération des résidus de combustion est à souligner.The characteristics (performance) of the composition (object) of Example 4 showed that the joint addition of alumina and strontium oxalate (SrC 2 O 4 ) in a composition of the type of that of reference 1 ( Ref. 1), led to a significant lowering of the combustion temperature (-156 ° C). The value of the pressure exponent remained acceptable for the intended application (front airbags). The very good quality of agglomeration of combustion residues should be emphasized.
Les caractéristiques (performances) indiquées pour la composition (objet) de l'exemple 5 ont montré que l'ajout conjoint d'alumine et d'oxalate de cuivre (CuC2O4) dans une composition du type de celle de la référence 1 (Réf. 1), a conduit à un abaissement de la température de combustion significatif (de -146 °C).The characteristics (performances) indicated for the composition (object) of Example 5 showed that the joint addition of alumina and copper oxalate (CuC 2 O 4 ) in a composition of the type of that of reference 1 (Ref. 1), led to a significant lowering of the combustion temperature (-146 ° C).
L'exemple A, à considérer donc en parallèle avec l'exemple de référence 2 (Réf. 2), illustre l'intervention de nitrate basique de cuivre (BCN) de grade fin (d50 = 1 µm) dans une composition de type NG (de granulométrie substantiellement plus élevée) + BCN + Al2O3 (2,7 %), en absence d'oxalate (plus particulièrement d'oxalate de sodium, d'oxalate de strontium et d'oxalate de cuivre). L'impact sur la vitesse de combustion est significative : augmentation de plus de 20 % (en comparaison avec la vitesse de combustion des pastilles de l'exemple de référence 2 (Réf. 2)). Ainsi se confirme-t-il qu'il est possible, dans le cadre de la présente invention, d'abaisser la température de combustion tout en optimisant la vitesse de combustion par la faible granulométrie du BCN présent (en fait par la faible granulométrie de l'un des constituants NG ou BCN, l'autre desdits constituants ayant alors une granulométrie substantiellement plus élevée).
Claims (14)
- A gas-generating pyrotechnic solid object, the composition of which, expressed as weight percentages, contains:- from 35 to 50%, advantageously from 40 to 50%, of guanidine nitrate,- from 35 to 50% of basic copper nitrate,- from 0.5 to 6% of at least one compound chosen from alumina and inorganic titanates, the melting point of which is above 2100 K, and- from 5 to 18%, advantageously from 5 to 13%, of at least one inorganic oxalate chosen from sodium oxalate, tin oxalate, strontium oxalate, iron oxalate, copper oxalate and mixtures thereof;said composition being free of binder and of explosive ingredient.
- The object as claimed in claim 1, characterized in that said at least one inorganic oxalate consists of sodium oxalate, strontium oxalate or copper oxalate.
- The object as claimed in claim 1 or 2, the composition of which, expressed as weight percentages, contains:- from 35 to 50%, advantageously from 40 to 50%, of guanidine nitrate,- from 35 to 45% of basic copper nitrate,- from 1 to 6%, advantageously 3 to 5%, of at least one compound chosen from alumina and inorganic titanates, the melting point of which is above 2100 K, and- from 5 to 15%, advantageously from 5 to 13%, very advantageously from 7 to 13%, of at least one inorganic oxalate chosen from sodium oxalate, tin oxalate and mixtures thereof.
- The object as claimed in any one of claims 1 to 3, characterized in that its composition contains at least one inorganic titanate chosen from strontium titanate, calcium titanate, aluminum titanate and mixtures thereof.
- The object as claimed in any one of claims 1 to 4, characterized in that its composition consists, for at least 98% by weight, or even at least 99.5% by weight, or even 100% by weight, of said guanidine nitrate, basic copper nitrate, alumina and/or inorganic titanate(s), and inorganic oxalate(s).
- The object as claimed in any one of claims 1 to 5, characterized in that said guanidine nitrate, basic copper nitrate, alumina and/or inorganic titanate(s), and inorganic oxalate(s) have median diameters of less than or equal to 20 µm.
- The object as claimed in any one of claims 1 to 6, characterized in that the median diameter of one of said guanidine nitrate and basic copper nitrate is substantially higher than the median diameter of the other of said guanidine nitrate and basic copper nitrate.
- The object as claimed in any one of claims 1 to 7, characterized in that the median diameter of one of said guanidine nitrate and basic copper nitrate is less than or equal to 1 µm whereas the median diameter of the other of said guanidine nitrate and basic copper nitrate is at least 5 µm, advantageously at least 10 µm.
- The object as claimed in any one of claims 1 to 8, characterized in that its composition contains alumina, the median diameter of which is less than or equal to 5 µm.
- The object as claimed in any one of claims 1 to 9, characterized in that its composition contains at least one inorganic titanate, the median diameter of which is less than 6 µm, advantageously less than 1 µm.
- The object as claimed in any one of claims 1 to 10, characterized in that it is obtained by a dry-route process, which comprises a step of compacting a pulverulent mixture containing the powdered constituent ingredients of said object, optionally followed by a step of granulation, itself followed, optionally, by a step of forming by pelletizing.
- The object as claimed in any one of claims 1 to 11, characterized in that it is in the form of granules, pellets or monolithic blocks.
- A pulverulent composition, which is a precursor of an object as claimed in any one of claims 1 to 12, the composition of which corresponds to that of an object as claimed in any one of claims 1 to 10.
- A gas generator, containing a gas-generating pyrotechnic solid charge, characterized in that said charge contains at least one object as claimed in any one of claims 1 to 12.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1663229A FR3061174B1 (en) | 2016-12-22 | 2016-12-22 | SOLID PYROTECHNIC OBJECTS GENERATORS OF GAS |
| PCT/FR2017/053727 WO2018115735A1 (en) | 2016-12-22 | 2017-12-20 | Gas-generating pyrotechnic solid objects |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP3558900A1 EP3558900A1 (en) | 2019-10-30 |
| EP3558900B1 true EP3558900B1 (en) | 2021-11-17 |
| EP3558900B8 EP3558900B8 (en) | 2021-12-29 |
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| EP17829259.5A Active EP3558900B8 (en) | 2016-12-22 | 2017-12-20 | Gas-generating pyrotechnic solid objects |
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| US (1) | US20200002243A1 (en) |
| EP (1) | EP3558900B8 (en) |
| JP (1) | JP2020514218A (en) |
| KR (1) | KR20190101995A (en) |
| CN (1) | CN110325492A (en) |
| FR (1) | FR3061174B1 (en) |
| WO (1) | WO2018115735A1 (en) |
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| CN111978136B (en) * | 2020-09-01 | 2021-11-23 | 湖北航天化学技术研究所 | Improved gas generating agent and preparation method thereof |
| EP4223728A1 (en) * | 2020-10-01 | 2023-08-09 | Daicel Corporation | Gas-generating agent composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6361630B2 (en) * | 1999-08-17 | 2002-03-26 | Trw Inc. | Cool burning gas generating composition |
| US6602365B1 (en) | 2000-11-17 | 2003-08-05 | Autoliv Asp, Inc. | Gas generation via metal complexes of guanylurea nitrate |
| US6589375B2 (en) * | 2001-03-02 | 2003-07-08 | Talley Defense Systems, Inc. | Low solids gas generant having a low flame temperature |
| FR2866022B1 (en) * | 2004-02-10 | 2006-07-28 | Snpe Materiaux Energetiques | GAS GENERATING PYROTECHNIC COMPOSITION FOR MOTOR VEHICLE SAFETY |
| CN1331827C (en) * | 2004-12-16 | 2007-08-15 | 中国航天科技集团公司第四研究院第四十二研究所 | Non-nitrine gas generating agent and production thereof |
| FR2887247B1 (en) | 2005-06-15 | 2007-10-12 | Snpe Materiaux Energetiques | PROCESS FOR MANUFACTURING GAS GENERATOR PELLETS COMPRISING A DRY GRANULATION STEP |
| JP5275862B2 (en) * | 2008-04-11 | 2013-08-28 | 株式会社ダイセル | Gas generant composition |
| FR2975097B1 (en) * | 2011-05-09 | 2015-11-20 | Sme | PYROTECHNIC COMPOUNDS GENERATORS OF GAS |
| CN104744185B (en) * | 2013-12-30 | 2017-11-17 | 比亚迪股份有限公司 | A kind of gas generant composition and preparation method thereof |
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2016
- 2016-12-22 FR FR1663229A patent/FR3061174B1/en active Active
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2017
- 2017-12-20 CN CN201780087086.8A patent/CN110325492A/en active Pending
- 2017-12-20 WO PCT/FR2017/053727 patent/WO2018115735A1/en unknown
- 2017-12-20 JP JP2019534212A patent/JP2020514218A/en active Pending
- 2017-12-20 EP EP17829259.5A patent/EP3558900B8/en active Active
- 2017-12-20 US US16/472,297 patent/US20200002243A1/en not_active Abandoned
- 2017-12-20 KR KR1020197019861A patent/KR20190101995A/en unknown
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| FR3061174A1 (en) | 2018-06-29 |
| EP3558900B8 (en) | 2021-12-29 |
| KR20190101995A (en) | 2019-09-02 |
| JP2020514218A (en) | 2020-05-21 |
| WO2018115735A1 (en) | 2018-06-28 |
| EP3558900A1 (en) | 2019-10-30 |
| FR3061174B1 (en) | 2019-05-31 |
| CN110325492A (en) | 2019-10-11 |
| US20200002243A1 (en) | 2020-01-02 |
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