EP3160922B1 - Gaserzeugende pyrotechnische monolithische blöcke - Google Patents
Gaserzeugende pyrotechnische monolithische blöcke Download PDFInfo
- Publication number
- EP3160922B1 EP3160922B1 EP15736572.7A EP15736572A EP3160922B1 EP 3160922 B1 EP3160922 B1 EP 3160922B1 EP 15736572 A EP15736572 A EP 15736572A EP 3160922 B1 EP3160922 B1 EP 3160922B1
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- EP
- European Patent Office
- Prior art keywords
- nitrate
- titanate
- basic copper
- blocks
- combustion
- 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.)
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- 239000000203 mixture Substances 0.000 claims description 100
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 37
- 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 26
- 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 20
- 238000000034 method Methods 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 14
- 239000000470 constituent Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 8
- 239000008187 granular material Substances 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 7
- WEUCVIBPSSMHJG-UHFFFAOYSA-N calcium titanate Chemical compound [O-2].[O-2].[O-2].[Ca+2].[Ti+4] WEUCVIBPSSMHJG-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 230000000295 complement effect Effects 0.000 claims description 3
- 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 3
- 230000004907 flux Effects 0.000 claims 4
- 239000007864 aqueous solution Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 claims 2
- 238000002485 combustion reaction Methods 0.000 description 80
- 239000007789 gas Substances 0.000 description 35
- 239000004615 ingredient Substances 0.000 description 24
- 238000007906 compression Methods 0.000 description 21
- 230000006835 compression Effects 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 16
- 229910002651 NO3 Inorganic materials 0.000 description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 11
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 10
- 239000008188 pellet Substances 0.000 description 9
- 238000000280 densification Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 238000005056 compaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 5
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 5
- 240000008042 Zea mays Species 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241001080024 Telles Species 0.000 description 2
- HIGRAKVNKLCVCA-UHFFFAOYSA-N alumine Chemical compound C1=CC=[Al]C=C1 HIGRAKVNKLCVCA-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 235000010603 pastilles Nutrition 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 206010000372 Accident at work Diseases 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000006677 Appel reaction Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium 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
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 239000007937 lozenge Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003860 storage 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- 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
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
Definitions
- the present invention relates to pyrotechnic monolithic blocks ("large" pyrotechnic objects) gas generators; said blocks being adapted to be integrated within devices dedicated to the pressurization of volume structures to a greater or lesser extent, depending on the intended application. Said blocks are more particularly adapted to be integrated within devices requiring for their operation that pressurization is provided over a relatively long period, very significantly greater than the time required for the operation of gas generators for airbags (durations of up to milliseconds) and even gas generators for lift cylinders (durations of about 100 milliseconds).
- the pyrotechnic monolithic blocks of the invention by their intrinsic characteristics of size, porosity and composition, are particularly effective (with reference to specifications with many stringent stipulations). They are particularly efficient, especially with regard to their speed and temperature of combustion (low), their ease of obtaining and their gas yield (see below).
- the devices in question are, for example, extinguishers (the gases useful for their operation are used as a propellant, used to expel a quenching liquid through a nozzle), actuators of cylinders for opening doors in emergency situation (the gases useful for their operation are used to mechanically actuate a jack), devices for inflating flexible structures (gases that are useful for their operation ensure the deployment and pressurization of a flexible and watertight envelope ).
- Inflation of such flexible structures can meet different needs: need obstruction of a pipeline (for example, for anti-effusion systems, aimed at limiting the risk of pollution in the event of an industrial accident), need for the generation of buoyancy cushions (for example for emergency ditching, including a helicopter), need to deploy a flexible slide (eg for the emergency evacuation of passengers from an aircraft), for example.
- need obstruction of a pipeline for example, for anti-effusion systems, aimed at limiting the risk of pollution in the event of an industrial accident
- need for the generation of buoyancy cushions for example for emergency ditching, including a helicopter
- need to deploy a flexible slide eg for the emergency evacuation of passengers from an aircraft
- volume of gas, of a moderate temperature be generated, from the pyrotechnic objects in question, in a relatively slow and constant manner, over a relatively long specified time, to thereby pressurize a volume structure more or less consistent (we can indicate, in no way limiting, volumes of about 1 L (cylinders for opening doors, for example), about 3000 L (helicopter flotation tanks, for example), or even about 20,000 L (escape slide, for example)).
- the patent application WO 2007/113299 thus describes pyrotechnic objects, intended for gas generation over a relatively long period of time (durations of 50 ms to 1 min are indicated), whose composition, free of binder, contains guanidine nitrate (NG: as a charge reducing agent) and basic copper nitrate (BCN: as oxidizing charge), in an NG / NCB ratio close to stoichiometric equilibrium. Said composition therefore has a near equilibrium oxygen balance (close to zero). This confers on said pyrotechnic objects too high temperature and burn rate with reference to the specifications currently in question (see below).
- NG guanidine nitrate
- BCN basic copper nitrate
- the objects described in the said application WO 2007/113299 are of substantially cylindrical shape and have a thickness greater than 5 mm, a diameter greater than or equal to 10 mm (generally a thickness and / or a diameter between 10 and 60 mm) and a porosity of between 1 and 8%.
- low porosities ⁇ 5%, and more preferably ⁇ 3%
- the skilled person does not ignore the criticality of this parameter porosity.
- a "high" porosity value (in this case greater than 4 - 5%) is, in general, such as to increase the ballistic dispersion of the pyrotechnic object, to confer on the pyrotechnic object insufficient resistance to severe vibratory environments over extended periods of time and, for this family of pyrotechnic compounds ( ie based on a NG + BCN mixture), to increase the value of the combustion rate.
- the inventors propose pyrotechnic monolithic gas generators whose combustion gases replace the pressurized gases of the prior art, to ensure the operation of emergency or emergency devices (for, more generally, to ensure the pressurization of structures) .
- This substitution advantageous per se (see above the disadvantages of the use of pressurized gas), is all the more so that said blocks of the invention are particularly effective, with reference to a severe specification. In any case, they perform better than the objects described in the application WO 2007/113299 .
- the inventors propose pyrotechnic monolithic blocks generating original gases, particularly powerful, which are characterized by their size, their porosity and their composition.
- the blocks in question consist of large objects.
- they generally have a thickness between 10 and 100 mm (10 mm ⁇ e ⁇ 100 mm) and / or, very generally and, an equivalent diameter between 10 and 100 mm (10 mm ⁇ ⁇ ⁇ 100 mm).
- they have a thickness between 20 and 80 mm (20 mm ⁇ e ⁇ 80 mm) and / or, preferably, and an equivalent diameter between 20 and 80 mm (20 mm ⁇ ⁇ ⁇ 80 mm).
- the blocks in question are dense blocks.
- the porosity of said blocks is less than or equal to 3%.
- the porosity of said blocks is less than or equal to 2%, even less than or equal to 1% (a low porosity value ( ⁇ 2%), or even very low ( ⁇ 1%), is obtained (with the compositions of the blocks of the invention) via the application of a nominally high compressive force and a lower but already low porosity value (> 2% and ⁇ 5%) is obtained via the application of an effort reduced compression compared to that required to obtain equivalent porosity with the compositions according to the teaching of WO 2007/113299 (see attached figure)).
- the composition of the blocks of the invention thus very advantageously contains a metal titanate or a titanate of (a) alkaline earth.
- the composition of the blocks of the invention contains strontium titanate (SrTiO 3 , whose melting point is 2353 K) and / or calcium titanate (CaTiO 3 , whose melting point is 2248 ° C.). K) and / or aluminum titanate (Al 2 TiO 5 , whose melting temperature is 2133 K).
- it contains strontium titanate (SrTiO 3 ), calcium titanate (CaTiO 3 ) or aluminum titanate (Al 2 TiO 5 ).
- titanates act as agglomerating agent for the combustion residues (because of their refractory nature (melting temperature> 2100 K), they retain their physical state of solid powder (they obviously intervene in this form) at the temperature of combustion of the block, from which the agglomeration of the copper residues (residues in liquid form (in whole or in part at the combustion temperature of the composition) generated during the combustion of the NCB) and present within the a NG + BCN base strongly unbalanced in oxygen balance, they make it possible to obtain, surprisingly, the specific combustion properties sought (a combustion temperature less than or equal to 1415 K, a moderate combustion rate, less than or equal to 6 mm / s, low pressure (between 1 and 10 MPa) and a non-zero combustion rate at atmospheric pressure), combustion properties necessary for the intended functional need for pressurization, over a long time (it has been indicated above times of 500 ms to 2 min. ), more
- the three essential constitutive ingredients of the blocks of the invention identified above - NG + BCN + at least one inorganic titanate whose melting temperature is greater than 2100 K - thus represent at least 94% by mass of the total mass of said blocks . They are quite likely to represent at least 97% of it, at least 99% of it, or even 100% of it.
- composition of said blocks may contain other ingredients. It is understood that said other ingredients are likely to be present at most at the rate of 6% by weight and, of course, only insofar as their presence does not significantly affect the properties. particularly of combustion, required. Said other ingredients are, not exclusively, but generally, selected from processing additives (processing aids), binders and fluxing agents (see below).
- the composition of the blocks of the invention contains, in addition to said three essential constitutive ingredients, at least one processing additive (manufacturing aid, consisting for example of calcium stearate or graphite).
- processing additive consisting for example of calcium stearate or graphite.
- Such an additive for use is generally present in a content not exceeding 1% by weight. It is conventionally present in a content not exceeding 0.5% by weight. Its presence is particularly suitable for obtaining the blocks of the invention by the dry route (see below).
- the composition of the blocks of the invention is advantageously composed of 100% by weight of said guanidine nitrate, basic copper nitrate, at least one inorganic titanate and at least one processing additive.
- the blocks of the invention, having this advantageous composition are generally obtained by the dry route. However, they can also be obtained by wet process, particularly by a wet process comprising an atomization step (see below).
- composition of the blocks of the invention contains, in addition to said three essential constitutive ingredients (and, optionally, in addition, said at least one processing additive), at least one binder (for example of cellulosic type). or acrylic) or at least one fluxing agent (for example of the alkaline chloride salt type, such as NaCl or KCl).
- at least one binder for example of cellulosic type. or acrylic
- at least one fluxing agent for example of the alkaline chloride salt type, such as NaCl or KCl.
- the presence of at least one such binder may be particularly suitable for obtaining blocks of the invention by extrusion, possibly wet (the binder then contributing to the formation of a gel in contact with the solvent used (the water being the preferred "solvent” (see below)); the presence of at least one such melting agent may be particularly suitable for obtaining blocks of the invention by the dry route (see below), particularly for obtaining blocks formulated from compositions characterized by a very low combustion temperature.
- Said at least one such binder or at least one such melting agent is generally present in a content not exceeding 5% by weight, very generally present in a content not exceeding 3% by weight.
- the composition of the blocks of the invention advantageously consists of 100% by weight of said guanidine nitrate, basic copper nitrate, at least one inorganic titanate, at least one processing additive and at least one binder or at least one fluxing agent. It is very advantageously composed of 100% by weight of said guanidine nitrate, basic copper nitrate, at least one inorganic titanate, at least one processing additive and at least one fluxing agent.
- the blocks of the invention, having this very advantageous composition are generally obtained by the dry route.
- porosity less than 5% and composition consisting of at least 94% by mass of guanidine nitrate, basic nitrate of copper and at least one inorganic titanate (refractory), present in the proportions indicated - the blocks of the invention can be, on at least part of their surface, inhibited in combustion (covered with a layer of suitable material (combustion inhibitor material), generally in the form of a varnish (non-combustible)).
- suitable material combustion inhibitor material
- Such inhibition is a conventional means (especially described in the patent application FR 2,275,425 and the patent US 5,682,013 ) which makes it possible to slow down their combustion (already “intrinsically” slow) and thus to obtain very long periods of combustion (see the 2 min indicated above).
- Blocks of the invention can be obtained by conventional, wet or dry methods. It is understood that the original composition of said blocks is at the source of their properties advantageous, and also allows them to be obtained under advantageous conditions.
- the blocks of the invention are advantageously obtained by a dry process.
- the high guanidine nitrate content of their composition has previously been emphasized.
- Such a dry process can almost be reduced to a compression of the pulverulent mixture obtained by mixing the constituent ingredients of the blocks (three essential constitutive ingredients and optionally, in addition, at least one other ingredient, advantageously, three essential constitutive ingredients + at least one processing additive and optionally at least one fluxing agent), said ingredients being used, in a conventional manner, in the pulverulent state.
- the pressure applied to the powder mixture placed in a suitable mold is generally between 10 8 and 6.5 ⁇ 10 8 Pa.
- the first step is a compaction step (dry) of a mixture of (constituents) powder constituents of the blocks (all the constituent ingredients (advantageously, the three ingredients constituting essential + at least one additive for implementation and optionally at least one fluxing agent) may be mixed or all but the at least one titanate (advantageously, NG + BCN + at least one processing additive and optionally at least one fluxing agent) (see below)).
- Dry compaction is generally carried out, in a manner known per se, in a roller compactor, at a compacting pressure of between 10 8 and 6 ⁇ 10 8 Pa.
- the second step is a step of granulation of the compacted material obtained (generally a flat plate or plate with reliefs).
- the granules obtained generally have a particle size (a median diameter) of between 200 and 1000 ⁇ m (and an apparent density of between 0.7 and 1.2 g / cm 3 ).
- the pressure applied is generally between 10 8 Pa and 6,5.10 8
- the at least one titanate interact with the other constituent ingredients of the blocks of the invention.
- BCN mainly, if not exclusively - ie at the beginning of the manufacturing process blocks of the invention or is added, further downstream in the manufacturing process, to the granules, before the implementation of the compression. It can not be totally ruled out that it should be added several times at the beginning (to the powder mixture) and further downstream (to the granules).
- dry process methods are, in the context of the present invention, used to obtain blocks that have the characteristics of composition, size and porosity explained above (ie in particular a thickness to burn greater than or equal to 10 mm, generally between 10 and 100 mm, advantageously between 20 and 80 mm).
- the guanidine nitrate (NG) and the basic copper nitrate (BCN) used advantageously have a particle size (value median diameter) fine, less than or equal to 20 ⁇ m. Said particle size is generally between 1 and 20 microns. It is actually conventional particle size.
- the blocks of the invention can also be obtained by a wet process.
- such a wet process comprises the extrusion of a paste containing all the constituent ingredients of the block (advantageously, guanidine nitrate, basic nitrate of copper, the at least one titanate, at least one additive containing at least one binder) and a solvent (water being the preferred "solvent").
- the shaping of the powder mixture is generally a conventional compression (by a known method of dry compression). As indicated above, in no way limiting, compression pressures of 10 8 to 6.5.10 8 Pa.
- the wet process methods are, in the context of the present invention, used to obtain blocks which have the characteristics of composition, size and porosity explained above (ie in particular a thickness to burn greater than or equal to 10 mm, generally between 10 and 100 mm, advantageously between 20 and 80 mm).
- the present invention relates to gas generators containing a pyrotechnic solid charge gas generator.
- the gas generators of the invention contain a charge which contains at least one block (pyrotechnic monolithic gas generator, of substantially cylindrical shape) of the invention and / or as obtained by the methods mentioned below. above.
- Such generators incorporating a pyrotechnic charge containing several blocks of the invention, in an ordered configuration (for example in the form of a stack of several blocks), as opposed to a bulk load, said (stacks of) blocks being able to Moreover, being inhibited on their lateral surface, they are particularly suitable for the pressurization of structures over long or very long durations (remember the 500 ms to 2 min indicated above).
- compositions of said Examples A, B and C have combustion temperatures above 1415 K.
- the combustion temperature of the composition of Example C (1438 K) remains greater than 1415 K.
- compositions of Examples 1 to 8 of the invention typically contain guanidine nitrate (NG) and basic copper nitrate (NCB) in an unbalanced mass ratio (greater than or equal to 8.5) and an inorganic titanate at a mass ratio greater than or equal to 3% and less than or equal to 12.5%.
- NG guanidine nitrate
- NCB basic copper nitrate
- compositions of Examples 1 to 8 of Table 1 show that the addition of strontium titanate (SrTiO 3 ) or Calcium titanate (CaTiO 3 ), in a composition based on NG + BCN strongly unbalanced in oxygen balance (of the type of Example C), makes it possible to obtain a low combustion temperature value (below the threshold of 1415 K fixed in the specifications (see above)) while maintaining a high gas yield (greater than or equal to 39.5 mol / kg).
- the blocks and pellets were obtained by the same dry process (compaction + granulation + compression), implemented under the same conditions (same compaction and compression pressure, in particular), so that the measured combustion rates are comparable. .
- Table 2 Examples Ex. A Ex. 8 Characteristics Burning rate at 10 MPa mm / s 16 5 Burning rate at 2 MPa mm / s 8 2 Burning rate at 0.1 MPa mm / s 1 0.4 Agglomerated appearance of combustion residues (in the form of a skeleton of the pyrotechnic block) - Yes Yes
- the block according to the invention despite the significant imbalance of the NG / NCB ratio of its composition, advantageously has a self-sustaining combustion up to the desired minimum value (ie up to the pressure atmospheric).
- the figure 1 annexed presents the densification curves (ie the evolution of the porosity value as a function of the pressure applied to the material during a compression step), measured compared with the composition of Example 1 (Ex. 1) according to the invention and with the composition of Comparative Example A (Ex. A) (according to the teaching of WO 2007/113299 ).
- These densification curves were established in a pellet manufacturing context (dry process: compaction + granulation + compression), with different values of compressive stress.
- the porosity value (ordinate) is calculated from the measurement of the dimensions (thickness, diameter) and mass of the tablet (compressed) obtained (it is expressed as a percentage and corresponds to the difference between the mass value theoretical volume and the measured density value, reduced to the theoretical density value (see above)).
- the composition according to Example 1 of the invention makes it possible to obtain pellets characterized by a porosity value of less than or equal to 1%, ie very close to densification. Max.
- the measured porosity value for pellets according to the prior art is significantly higher (of the order of 5%).
- obtaining a porosity value of 4% or less for the composition according to Comparative Example A requires a high material pressure value, of the order of 4000 bar, ie an equivalent compression force of order of 45 tons.
- obtaining a porosity value less than or equal to 4% (or preferably less than or equal to 3%) for the composition according to the invention (Example 1) is obtained for a significantly lower material pressure value, of the order of 1000 bar (1500 bar), an equivalent compressive force of the order of 11 tons (17 tons).
- the composition according to Example 1 of the present invention advantageously allows either to significantly reduce the compression force (for the same level of targeted porosity), or to obtain a lower porosity value (for the same level compressive force applied).
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Claims (15)
- Monolithischer pyrotechnischer gaserzeugender Block von im Wesentlichen zylindrischer Form, dadurch gekennzeichnet, dass:- er aufweist: eine Dicke größer oder gleich 10 mm,einen äquivalenten Durchmesser größer oder gleich 10 mm, undeine Porosität unter 5 %, und
dass- seine Zusammensetzung, ausgedrückt in Massenprozent, für mindestens 94 % seiner Masse enthält:+ 77,5 bis 92,5 % Guanidinnitrat,+ 5 bis 10 % basisches Kupfernitrat und+ 2,5 bis 12,5 % mindestens eines anorganischen Titanats mit einer Schmelztemperatur über 2100 K. - Block gemäß Anspruch 1, dessen Dicke zwischen 10 und 100 mm und/oder dessen äquivalenter Durchmesser zwischen 10 und 100 mm liegt.
- Block gemäß Anspruch 1 oder 2, dessen Porosität kleiner oder gleich 2 % ist.
- Block gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass seine Zusammensetzung das Guanidinnitrat und das basische Kupfernitrat in einem Verhältnis R zwischen 8,5 und 15 (8,5 ≤ R ≤ 15), vorzugsweise zwischen 8,5 und 12 (8,5 ≤ R ≤ 12), enthält.
- Block gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das mindestens eine anorganische Titanat aus mindestens einem anorganischen Titanat, ausgewählt aus Metalltitanaten und Erdalkalititanaten, besteht.
- Block gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das mindestens eine anorganische Titanat aus Strontiumtitanat (SrTiO3) und/oder Calciumtitanat (CaTiO3) und/oder Aluminiumtitanat (Al2TiO5) besteht,
- Block gemäß einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Guanidinnitrat, das basische Kupfernitrat und das mindestens eine anorganische Titanat mindestens 97 Masse-%, vorzugsweise mindestens 99 Masse-%, seiner Masse ausmachen.
- Block gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass seine Zusammensetzung neben dem Guanidinnitrat, dem basischen Kupfernitrat und dem mindestens einen anorganischen Titanat mindestens ein Verarbeitungsadditiv mit einem Massengehalt von höchstens 1 % enthält.
- Block gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass seine Zusammensetzung neben dem Guanidinnitrat, dem basischen Kupfernitrat und dem mindestens einen anorganischen Titanat, mindestens ein Bindemittel oder mindestens ein Flussmittel mit einem Massengehalt von höchstens 5 % enthält.
- Block gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass seine Zusammensetzung für 100 % seiner Masse enthält:- das Guanidinnitrat,- das basische Kupfernitrat,- das mindestens eine anorganische Titanat und- mindestens ein Verarbeitungsadditiv.
- Block gemäß einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass seine Zusammensetzung für 100 % seiner Masse enthält:- das Guanidinnitrat,- das basische Kupfernitrat,- das mindestens eine anorganische Titanat,- mindestens ein Verarbeitungsadditiv und- mindestens ein Bindemittel oder mindestens ein Flussmittel.
- Verfahren zur Herstellung eines im Wesentlichen zylindrischen monolithischen pyrotechnischen gaserzeugenden Blocks gemäß einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass es entweder aus einem Trockenverfahren oder einem Nassverfahren besteht, vorzugsweise einem Trockenverfahren.
- Verfahren gemäß Anspruch 12, dadurch gekennzeichnet, dass es aus einem Trockenverfahren besteht, das vorzugsweise umfasst:Komprimieren einer Pulvermischung, die das Guanidinnitrat, das basische Kupfernitrat, das mindestens eine anorganische Titanat, mindestens ein Verarbeitungsadditiv und gegebenenfalls mindestens ein Flussmittel enthält, oderKompaktieren einer Pulvermischung, die das Guanidinnitrat, das basische Kupfernitrat, mindestens ein Verarbeitungsadditiv und gegebenenfalls mindestens ein Flussmittel enthält, um ein komprimiertes Material zu erhalten, gefolgt vom Granulieren des komprimierten Materials, um Granulat zu erhalten, weiterhin gefolgt vom Verdichten des Granulats, wobei das mindestens eine anorganische Titanat dem zu komprimierenden Pulvergemisch und/oder dem zu verdichtenden Granulat zugesetzt wird.
- Verfahren gemäß Anspruch 12, dadurch gekennzeichnet, dass es aus einem Nassverfahren besteht, das vorzugsweise umfasst:Extrudieren einer Paste, die das Guanidinnitrat, das basische Kupfernitrat, das mindestens eine anorganische Titanat, mindestens ein Verarbeitungsadditiv, mindestens ein Bindemittel und ein Lösungsmittel enthält, oderHerstellen einer wässrigen Lösung, die mindestens das Guanidinnitrat enthält, gegebenenfalls Suspendieren mindestens des basischen Kupfernitrats in der wässrigen Lösung, Erhalten eines Pulvers durch Sprühtrocknen der Lösung oder Suspension, falls erforderlich, Zugeben eines oder mehrerer komplementärer(/en) Bestandteile(/s) des Blocks zu dem Pulver und Formen des Pulvers, gegebenenfalls unter Zusatz des (der) komplementären Bestandteile(/s), sodass alle Bestandteile des Blocks enthalten sind, wobei das mindestens eine anorganische Titanat der zu zerstäubenden Lösung oder Suspension und/oder dem zerstäubten Pulver zugesetzt wird.
- Gasgenerator, der eine pyrotechnische feste gaserzeugende Ladung enthält, dadurch gekennzeichnet, dass die Ladung mindestens einen Block gemäß einem der Ansprüche 1 bis 11 enthält und/oder gemäß dem Verfahren eines der Ansprüche 12 bis 14 erhalten wird.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1456162A FR3022906B1 (fr) | 2014-06-30 | 2014-06-30 | Blocs monolithiques pyrotechniques generateurs de gaz |
PCT/FR2015/051753 WO2016001549A1 (fr) | 2014-06-30 | 2015-06-29 | Blocs monolithiques pyrotechniques generateurs de gaz |
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EP3160922A1 EP3160922A1 (de) | 2017-05-03 |
EP3160922B1 true EP3160922B1 (de) | 2018-08-29 |
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US (1) | US9868678B2 (de) |
EP (1) | EP3160922B1 (de) |
JP (1) | JP6657128B2 (de) |
CN (1) | CN107074673B (de) |
FR (1) | FR3022906B1 (de) |
WO (1) | WO2016001549A1 (de) |
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CN107698415A (zh) * | 2017-10-24 | 2018-02-16 | 湖北航鹏化学动力科技有限责任公司 | 一种气体发生剂组合物、制备方法、应用及气体发生器 |
CN107698414B (zh) * | 2017-10-24 | 2019-08-09 | 湖北航鹏化学动力科技有限责任公司 | 气体发生剂组合物、制备方法、应用及气体发生器 |
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CH602519A5 (de) | 1974-06-21 | 1978-07-31 | Oerlikon Buehrle Ag | |
CA2094888A1 (en) | 1992-08-24 | 1994-02-25 | Bradley W. Smith | Gas generant body having pressed-on burn inhibitor layer |
FR2887247B1 (fr) | 2005-06-15 | 2007-10-12 | Snpe Materiaux Energetiques | Procede de fabrication de pastilles generatrices de gaz comportant une etape de granulation par voie seche |
FR2899227B1 (fr) * | 2006-04-04 | 2008-10-24 | Snpe Materiaux Energetiques Sa | Objets pyrotechniques monolithes de grandes dimensions, obtention et utilisation |
FR2905454B1 (fr) * | 2006-09-01 | 2011-03-18 | Pyroalliance | Generateur de gaz pyrotechnique a regulation de pression et dispositif de propulsion de liquide l'incorporant dans sa structure |
US9193639B2 (en) * | 2007-03-27 | 2015-11-24 | Autoliv Asp, Inc. | Methods of manufacturing monolithic generant grains |
FR2975097B1 (fr) * | 2011-05-09 | 2015-11-20 | Sme | Composes pyrotechniques generateurs de gaz |
FR2998174B1 (fr) * | 2012-11-21 | 2016-06-10 | Greentech | Procede de preparation d'un principe actif cosmetique ou dermatologique |
FR2999174B1 (fr) | 2012-12-10 | 2014-12-26 | Herakles | Composes solides generateurs de gaz azote, comprenant de l'azodicarbonamide et procede de generation de gaz azote par decomposition desdits composes |
-
2014
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- 2015-06-29 EP EP15736572.7A patent/EP3160922B1/de active Active
- 2015-06-29 CN CN201580035862.0A patent/CN107074673B/zh active Active
- 2015-06-29 WO PCT/FR2015/051753 patent/WO2016001549A1/fr active Application Filing
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US20170158576A1 (en) | 2017-06-08 |
CN107074673B (zh) | 2019-03-05 |
US9868678B2 (en) | 2018-01-16 |
CN107074673A (zh) | 2017-08-18 |
EP3160922A1 (de) | 2017-05-03 |
JP2017530920A (ja) | 2017-10-19 |
FR3022906A1 (fr) | 2016-01-01 |
FR3022906B1 (fr) | 2016-07-15 |
WO2016001549A1 (fr) | 2016-01-07 |
JP6657128B2 (ja) | 2020-03-04 |
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