CN102816038A - Rapid Gas Generating Pyrotechnical Composition and Method for Obtaining Same - Google Patents
Rapid Gas Generating Pyrotechnical Composition and Method for Obtaining Same Download PDFInfo
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- CN102816038A CN102816038A CN201210352802XA CN201210352802A CN102816038A CN 102816038 A CN102816038 A CN 102816038A CN 201210352802X A CN201210352802X A CN 201210352802XA CN 201210352802 A CN201210352802 A CN 201210352802A CN 102816038 A CN102816038 A CN 102816038A
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- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 14
- 229910002010 basic metal nitrate Inorganic materials 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims description 47
- 239000002245 particle Substances 0.000 claims description 23
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 19
- 238000005469 granulation Methods 0.000 claims description 17
- 230000003179 granulation Effects 0.000 claims description 17
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 150000002897 organic nitrogen compounds Chemical group 0.000 claims description 11
- 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 10
- MJFQUUWPZOGYQT-UHFFFAOYSA-O diaminomethylideneazanium;nitrate Chemical compound NC(N)=[NH2+].[O-][N+]([O-])=O MJFQUUWPZOGYQT-UHFFFAOYSA-O 0.000 claims description 8
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 8
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical group [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004049 embossing Methods 0.000 claims description 3
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 claims description 2
- ZEFNOZRLAWVAQF-UHFFFAOYSA-N Dinitolmide Chemical compound CC1=C(C(N)=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O ZEFNOZRLAWVAQF-UHFFFAOYSA-N 0.000 claims description 2
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- QGWDKKHSDXWPET-UHFFFAOYSA-E pentabismuth;oxygen(2-);nonahydroxide;tetranitrate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[O-2].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QGWDKKHSDXWPET-UHFFFAOYSA-E 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 229920002521 macromolecule Polymers 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 7
- 239000004615 ingredient Substances 0.000 abstract 2
- 230000001590 oxidative effect Effects 0.000 abstract 2
- 229910001485 alkali metal perchlorate Inorganic materials 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- -1 nitrogen-containing compound Chemical class 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000007906 compression Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000007907 direct compression Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008698 shear stress Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0033—Shaping the mixture
- C06B21/0041—Shaping the mixture by compression
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Air Bags (AREA)
Abstract
The invention concerns gas generating pyrotechnical compositions, of which at least 95 wt. % of the charges consist of the following constituting ingredients: a reducing charge in the form of at least one nitrogen-containing compound; an oxidizing charge in the form of at least one basic metal nitrate; and at least 30 wt. % of a second oxidizing charge in the form of at least one alkali metal perchlorate. Said compositions are obtained via a dry process roller compacting step of a powdery mixture consisting essentially of said ingredients in powder form. The invention also concerns the method for obtaining said compositions. The inventive compositions exhibit interesting combustion speeds.
Description
The application be that October 12, application number in 2006 are 200680043374.5 the applying date, name is called the dividing an application of application for a patent for invention of " a pyrotechnic compsn of rapid gas generating and preparation method thereof ".
Technical field
The present invention relates to the firework type gas-evolution agent, particularly give the gas-evolution agent of air cushion inflation used in car passenger protection system.Or rather, the present invention relates to be called as a pyrotechnic compsn cold smoke fire compsn, can produce clean nontoxic gas fast in the acceptable temperature of vehicle safety (being defined as the temperature that is lower than 2200K).The present invention also relates to prepare the method for such a pyrotechnic compsn.
Background technology
In the vehicle safety scope, a pyrotechnic compsn that adopts in the producer gas generator must (being generally 10 milliseconds～40 milliseconds) provide the gas of filling the necessary amount of inflatable packer in the extremely short time.And the gas of generation must be clean, promptly do not have solid particulate (possibly constitute the focus that can destroy the pad wall of said air cushion), and nontoxic, and promptly the content of carbon monoxide, oxynitride and chlorizate is lower.
Up to the present, various types of a pyrotechnic compsns have been proposed.
At present, those seem to comprise Guanidinium nitrate (GN) and basic copper nitrate (BCN) as staple at a pyrotechnic compsn of obtaining optimum balance aspect gas temperature, gas yield, the particulate ratio that is discharged and the toxicity.USP 5608183 has been described the such compsn that obtains through wet method.
Yet these compsns but have drawback: combustionvelocity is relatively slow, when 20MPa, is less than or equal to 20mm/s, and is difficult to light.Equally, be difficult to use it in the secondary producer of mixing (hybrid and side grenerator) of the running time (10 milliseconds～20 milliseconds) that to lack very much.
Prior art has proposed perchlorate is added in the such a pyrotechnic compsn based on Guanidinium nitrate (GN) and basic copper nitrate (BCN):
Described among-patented claim the EP 1526121 with lower ratio (less than 5 quality %) and added perchlorate (especially potassium perchlorate), thereby improved the ease of ignition of said compsn, and reduced the release of oxynitride;
-USP 6893517 has been described with higher relatively ratio (30 quality %～45 quality %) and has been added perchlorate (especially potassium perchlorate), thereby improves the combustionvelocity of said compsn.Such perchlorate ratio makes temperature of combustion up to about 2400K.With regard to regard to the air cushion of combustion gases inflations non-attacking, said a pyrotechnic compsn can not be considered to " cold " a pyrotechnic compsn again.
About the technical problem of increase based on the combustionvelocity of a pyrotechnic compsn of Guanidinium nitrate (GN) and basic copper nitrate (BCN), therefore, the interpolation of perchlorate itself is not a gratifying scheme.
The roll-in dry pelletizing method is the currently known methods that is used to handle powder (being generally powdered mixture) that can in different environment, implement.Send such powdered mixture of air dry powder mixer through for example metering screw, to be supplied to the cylinder shape compactor.Such compactor is formed by setting two rotating cylindrical bodys that rotate in the opposite direction with the speed that limits.Promote powdered mixture through the metering screw between said two right cylinders.Known reactive force is applied to said right cylinder.Therefore, be pressed into tabular through the material between right cylinder at a predetermined velocity.Such operation can be carried out high speed compression and shearing to said mixture, improves the tightness between composition.Thereby will smash and make it force to pass through masher from the product through compacting of compactor then and produce particle.Such particle is usually compared with beginning powder easy handling.Common single device can carry out compacting and granulation in succession.
Summary of the invention
In the scope of the present invention, just increase the technical problem of combustionvelocity, the contriver has confirmed that main key is in the process of a pyrotechnic compsn for preparing Guanidinium nitrate-basic copper nitrate type, to carry out the dry type roll-in.Surprisingly, observed real synergy: through carrying out the dry type roll-in, can be so that the positively effect (to combustionvelocity) that produces because of the intervention of limited amount perchlorate (temperature of combustion is not had detrimentally affect) be reinforced; When not having perchlorate, use dry type roll-in itself not have substantial effect.The following comparative data of combustionvelocity is supported this opinion in the time of can 20MPa being provided:
GN+BCN≤20mm/s
GN+BCN+ compacting 20-22mm/s
GN+BCN+KClO
4(embodiment 4 hereinafter) 32mm/s
GN+BCN+KClO
4+ compacting (embodiment 5 hereinafter) 38.2mm/s.
According to first purpose of the present invention, therefore the present invention relates to a pyrotechnic compsn of the generation gas that combines two characteristics.Said pyrotechnic gas compsn:
+ comprise following main composition (activity) composition:
-reductibility raw material, it is at least a organic nitrogen compound form;
-oxidisability raw material, it is at least a basic metal nitrate form; With
-less than the second oxidisability raw material of 30 quality %, it is at least a alkaline metal perchlorate form,
Said raw material accounts at least 95 quality % (being generally at least 98 quality %) of the raw material of existence; And
+ said compsn obtains via the dry type roll-in step of the pulverulent mixture that is basically become to be grouped into by said powder.
The a pyrotechnic compsn of the present invention that comprises specific reductibility raw material (at least a organic nitrogen compound form) and specific oxidisability raw material (at least a basic metal nitrate form) comprises the limited amount second specific oxidisability raw material (at least a alkaline metal perchlorate form), and obtains through accomplishing such method: said method comprises the dry type roll-in step of the pulverulent mixture that contains said specific reductibility raw material and oxidisability raw material.
As know that the dry type roll-in is carried out in cylindrical compactor, compaction pressure is generally 10
8Pa～6 * 10
8Pa.
In this article the method that is characterised in that the preparation a pyrotechnic compsn of the present invention that comprises dry type roll-in step has been carried out further detailed description.
Can (characterization step be " simply " roll-in and at least one additional step subsequently according to different modification; Characterization step for the roll-in of forming step coupling) implement said method, therefore a pyrotechnic compsn of the present invention exists with different forms.
In fact:
-after accomplishing with the dry type roll-in of moulding coupling (having the compacting right cylinder of teeth groove), obtain having the plate object of embossing pattern through using at least one outside surface, directly obtain the pyrotechnics formed body thereby can this plate object be smashed;
Roll-in of-dry type and granulation subsequently obtain particle after accomplishing;
Roll-in of-dry type and granulation subsequently, after compressing tablet (dry type compression) is accomplished then, obtain flap.
The roll-in of-dry type, granulation subsequently, the particle with gained mixes with extrudable tackiness agent then, and will contain the said tackiness agent of said particulate and extrude, and then obtains the monoblock thing of extruding (containing said particle).
Therefore a pyrotechnic compsn of the present invention possibly exist with following form:
-formed body directly is derived from (with the moulding coupling) roll-in;
-particle;
-flap; With
-monoblock the thing (containing particle) extruded.
Can point out with non-limiting way at this:
-particulate granularity of the present invention (median particle diameter) is generally 200 μ m～800 μ m, and (the apparent volume quality is 0.8cm
3/ g～1.2cm
3/ g);
The thickness of-flap of the present invention is generally 1mm～3mm; And
-in the monoblock thing of extruding, there is particle in the dry adhesives (gel).
Also can point out the special part that constitutes first purpose of the present invention of following content at this:
-flap, temperature of combustion are less than 2200K, and combustionvelocity is greater than 30mm/s during 20MPa, and oxygen balance is-2%～-4%;
-monoblock the thing extruded, temperature of combustion is less than 2200K, and combustionvelocity is greater than 24mm/s during 20MPa, and oxygen balance is-2%～-4%.
Some compositions about constituting a pyrotechnic compsn of the present invention and definite, the nonrestrictive details of their appearance ratios in said compsn will be provided now.
At least a organic nitrogen compound that constitutes the reductibility raw material can be selected from Guanidinium nitrate, nitroguanidine, guanylurea Zoamix and their mixture especially.Advantageously said reductibility raw material is made up of Guanidinium nitrate (GN).
At least a basic metal nitrate that constitutes (first) oxidisability raw material can be selected from basic copper nitrate, alkali formula zinc nitrate, Vikaline and their mixture especially.Advantageously, said oxidisability raw material is made up of basic copper nitrate (BCN).
Said at least a alkaline metal perchlorate can be selected from potassium perchlorate, sodium perchlorate and their mixture especially.Advantageously said alkaline metal perchlorate is by potassium perchlorate (KClO
4) form.
Therefore, according to a preferred variation, the main composition composition of compsn of the present invention is:
-Guanidinium nitrate (GN)
-basic copper nitrate (BCN) and
-potassium perchlorate (KClO
4).
About the amount separately of each said composition, advantageously combination independently usually in compsn:
-with said at least a organic nitrogen compound that 45 quality %～65 quality % ratios exist;
-with said at least a basic metal nitrate that 15 quality %～35 quality % ratios exist;
-said at least a alkaline metal perchlorate (as what pointed out, exists to be less than 30 quality %.Like this; The performance that it will obviously be strengthened because of debulking methods the beneficial effect of combustionvelocity; And the consequence that can not cause undesirable temperature of combustion to raise), there is ratio in it is 10 quality %～25 quality %, advantageously 10 quality %～20 quality %.
According to an advantageous variant, a pyrotechnic compsn of the present invention comprises:
The Guanidinium nitrate (GN) of-45 quality %～65 quality %,
The basic copper nitrate (BCN) of-15 quality %～35 quality %,
Potassium perchlorate (the KClO of-10 quality %～25 quality %
4).
Basic (at least 95 quality % of a pyrotechnic compsn of formed body of the present invention, particle and flap form; Be generally at least 98 quality %) in addition fully (100 quality %) form by the determined main composition compositions of preceding text (raw material): said at least a organic nitrogen compound, said at least a basic metal nitrate and said at least a alkaline metal perchlorate.In fact said composition self can constitute 100% said raw material (generally all being this situation) of said a pyrotechnic compsn, or even constitutes 100% said a pyrotechnic compsn.Yet; Other raw materials the existing (under any circumstance in compsn of the present invention that can not get rid of minimum; Determined raw material all accounts at least 95 quality % of the raw material of existence in the preceding text, is generally at least 98 quality %) and/or the existence of at least a additive (processing aid class).
The a pyrotechnic compsn of the monoblock thing form of extruding of the present invention comprises determined those main composition compositions (raw material) of preceding text (other raw materials that possibly also comprise minimum) in the xerogel.This gel (itself can extrude or with solvent after can extrude) get into to extrude with the mode of adverse current.Though the amount to gel has restriction so that it does not influence the performance of compsn of the present invention basically, gel exists with significant quantity (can extrude).
The monoblock thing of extruding of the present invention comprises the such xerogel that is no more than 10 quality % usually.Advantageously comprise 4 quality %～6 quality %.In this scope, synergy of the present invention is strengthened with identical intensity.
Do not get rid of the existence of at least a additive among this paper yet.Said main composition composition (raw material) and xerogel account at least 95 quality % of said compsn usually, and more general situation is at least 98 quality % (perhaps, even 100 quality %).
The character of said gel is not institute inherent own.Said gel is selected from cellulose gel, derives from the gel of acrylate elastomer, has higher acetate ratios vinyl-vinyl acetate copolymer, polyester polymers and their mixture of (comprising the acetic ester unit that surpasses 60 quality %) usually.Advantageously, said gel is made up of the Xylo-Mucine gel.
Second purpose of the present invention relates to the preparation method of aforesaid a pyrotechnic compsn; The method is characterized in that the dry type compacting that comprises powder.
In fact said method comprises:
-with powder (raw material) dry mixed; At least 95 quality % of this powder (raw material) are made up of powdery reductibility raw material, powdery oxidisability raw material and the second powdery oxidisability raw material; Said powdery reductibility raw material is at least a organic nitrogen compound form; Said powdery oxidisability raw material is at least a basic metal nitrate form, and the said second powdery oxidisability raw material is at least a alkaline metal perchlorate form, and the said second powdery oxidisability raw material is less than 30 quality %; With
-with the powdered mixture dry type roll-in of gained.
In this article, preceding text provide character and their the definite details that has ratio separately about the composition of being discussed.
The composition that constitutes desired a pyrotechnic compsn exists with pulverulence.Advantageously, said powder has thinner granularity, is less than or equal to 40 μ m.Said granularity (median particle diameter value) is generally 3 μ m～40 μ m.
The dry type roll-in step of the dry mixed of said powder and resulting mixture is undertaken by ordinary method.About the dry type roll-in, explained that it carries out through following process: powdered mixture is passed through between two right cylinders, and applied pressure is generally 10
8～6 * 10
8Pa.Carry out " simply " compacting (employing has two right cylinders of crude outside surface) or with the compacting of moulding coupling (at least one the outside surface in two used right cylinders is processed as the teeth groove shape).
Point out in passing that here the intention that the present invention requires to protect not is the intention based on the method for being discussed itself, but carries out the intention of said method with specific powdered mixture.
Can method of the present invention be defined as hereinafter mixing and these two consecutive steps of dry type roll-in: suppose to carry out the roll-in (the cylindrical outside surface of at least one said compacting is the teeth groove shape) with the moulding coupling, directly obtain the method for formed body.
Except described mixing and two steps of (" simply ") dry type roll-in, method of the present invention can comprise:
A) dry type granulation step (powdered mixture that forces compacting through rotor with mechanical means is through being generally the masher (grater) of the screen cloth of 500 μ m～3mm as mesh).Can in same device, carry out roll-in and granulation, also can in two independent device, carry out.The a pyrotechnic compsn of gained is particle form (referring to preceding text) so.
B) (dry type is compressed, and bears at particle described in this process and is generally 4 * 10 for dry type granulation step (referring to preceding text) and compressing tablet subsequently
8Pa～10
9The pressure of Pa.Point out along band that at this feed that carries out the compression mold die cavity with particle is easy to many than carry out feed with initial powder).Therefore a pyrotechnic compsn of gained is flap form (referring to preceding text).
C) dry type granulation step (referring to preceding text), the particle with gained mixes with extrudable tackiness agent subsequently, and said mixture is extruded.The a pyrotechnic compsn that finally obtains is to contain the monoblock thing that particulate is extruded.
Particularly preferably be and comprise step b) and c in the preceding text) the modification of method of the present invention.In the scope of said two modification, method of the present invention comprises (" simply ") the roll-in step and the dry type granulation step of the mixture of initial powder.
No matter the concrete modification that method of the present invention is implemented; Confirmed that when carrying out said granulation step recycling particularly suits as far as the combustionvelocity that increases a pyrotechnic compsn for preparing at least partially in the fine powder that compacting step and/or granulation step produced.Specifically, the fine powder recovery of implementation 10%～30%.
To carry out non-limitative illustration to the present invention through following embodiment now.Clearer and more definite, proposed to explain the embodiment (a pyrotechnic compsn of flap form (embodiment 5) and the monoblock thing form (embodiment 7) extruded) of two modification of the present invention, with the comparative example parallel.
Used powder (raw material) has thinner granularity: KClO
4Median particle diameter be about 20 μ m, the median particle diameter of BCN is about 4.5 μ m, the median particle diameter of GN is about 10 μ m.
Such powder does not flow, so itself can not be used for industrial compressing tablet (being difficult to fill it into the compression mold die cavity).
Following Table I represent to prepare embodiment and through without the compressing tablet of the powdered mixture of precompressed (5 * 10
8Pa carries out) thermomechanical property and the ballisticperformances of the flap (thickness is about 2mm) that obtains.
Table I (direct compression)
* Vc=combustionvelocity
* OB=oxygen balance
● before compressing tablet, (roll gap pressure is 4 * 10 through implementing roll-in method
8Pa) will provide the compositions-treated of the embodiment 4 of the optimum balance between combustionvelocity, gas yield and temperature of combustion to become the compsn of embodiment 5 with dry type granulation (force the material of compacting to pass through rotor and be equivalent to the masher of mesh) for the screen cloth of about 1mm.The particulate median particle of gained was about 500 μ m after roll-in and granulation step were accomplished.(pressure is 5 * 10 with the condition identical with the powder of embodiment 1～4
8Pa) with said particle compressing tablet (being easy to carry out) until no longer including flow problem.
Following Table II is represented the contribution of roll-in method to the ballisticperformances of said compsn
Table II
Combustionvelocity when the compsn that roll-in and dry pelletizing method are applied to embodiment 4 makes 20MPa has increased by 20% magnitude.The speed of this increase is owing to the improvement of passing the compactness of composition behind the compactor.The roll-in stage causes mixture is applied stress under compression and shear-stress, has improved the quality of mixture.The test of under the different pressures of compactor, carrying out has confirmed this point.Therefore, the ballisticperformances that can regulate preparation through the pressure that is applied in the packing stage on the roller to a certain extent.
And roll-in and granulation stage produce (granularity is lower) fine powder, can be with it once more in the drawing-in system.This is introduced once more and also makes combustionvelocity obtain bigger increase, has at the compsn of embodiment 5 under the situation of 20% recovery fine powder, and combustionvelocity can reach 40mm/s during 20MPa.
The Xylo-Mucine that uses 4 quality % has prepared a pyrotechnic compsn with prescription listed in the following Table III as tackiness agent through extruding.Implement identical continuous mixing and extrusion molding.
According to embodiment 6, with powder (with tackiness agent together) be introduced directly in the device.
According to embodiment 7, hereinbefore under the embodiment 5 described conditions with said powder precompressed and granulation, and with the particle of gained (with tackiness agent together) be incorporated in the device.
In following Table III, also listed the performance of two kinds of compsns processing the monoblock thing.
Table III
The intervention of tackiness agent is harmful really to the performance (aspect combustionvelocity) of (with embodiment 5 similar embodiment's 7) compsn.All of this paper of dry powder being carried out roll-in are extruded product (with regard to the flap product) all makes said combustionvelocity significantly improve.The increased value of gained is specially about 20% all at the same order of magnitude.
Claims (20)
1. a pyrotechnic compsn that produces gas, the raw material of at least 95 quality % of said compsn is made up of following constituent:
-reductibility raw material, said reductibility raw material are at least a organic nitrogen compound form;
-oxidisability raw material, said oxidisability raw material are at least a basic metal nitrate form; With
-the second oxidisability raw material, the said second oxidisability raw material is at least a alkaline metal perchlorate form, and the said second oxidisability raw material is to exist less than 30 quality %; And
Said compsn obtains through the method that may further comprise the steps:
Basically the dry type roll-in step that the pulverulent mixture that is made up of said powder composition is carried out; Thereby said dry type roll-in uses the roller with crude outside surface to carry out producing the tabular thing; Thereby perhaps use following roller to carry out producing the plate object with embossing pattern, the outside surface of at least one of said roller is processed as the teeth groove shape.
2. compsn as claimed in claim 1, said compsn are formed body, particle, flap or the monoblock thing form extruded.
3. according to claim 1 or claim 2 compsn is characterized in that said at least a organic nitrogen compound is selected from Guanidinium nitrate, nitroguanidine, guanylurea Zoamix and their mixture.
4. compsn as claimed in claim 3 is characterized in that, said at least a organic nitrogen compound is made up of Guanidinium nitrate.
5. according to claim 1 or claim 2 compsn is characterized in that said at least a basic metal nitrate is selected from basic copper nitrate, alkali formula zinc nitrate, Vikaline and their mixture.
6. compsn as claimed in claim 5 is characterized in that, said at least a basic metal nitrate is made up of basic copper nitrate.
7. according to claim 1 or claim 2 compsn is characterized in that said at least a alkaline metal perchlorate is selected from potassium perchlorate, sodium perchlorate and their mixture.
8. compsn as claimed in claim 7 is characterized in that, said at least a alkaline metal perchlorate is made up of potassium perchlorate.
9. according to claim 1 or claim 2 compsn is characterized in that the ratio that exists of said at least a organic nitrogen compound is 45 quality %～65 quality %.
10. according to claim 1 or claim 2 compsn is characterized in that the ratio that exists of said at least a basic metal nitrate is 15 quality %～35 quality %.
11. compsn according to claim 1 or claim 2 is characterized in that, the ratio that exists of said at least a alkaline metal perchlorate is 10 quality %～25 quality %.
12. compsn as claimed in claim 1 is characterized in that, said compsn is the monoblock thing form of extruding, and said monoblock thing comprises the xerogel of 10 quality % at the most.
13. compsn as claimed in claim 12 is characterized in that, vinyl-vinyl acetate copolymer, polyester macromolecule and their mixture that said gel is selected from cellulose gel, derives from the gel of acrylate elastomer, has high acetate ratios.
14., it is characterized in that said gel is the Xylo-Mucine gel like claim 12 or 13 described compsns.
15. obtain producing the method for a pyrotechnic compsn of gas, it is characterized in that said method comprises:
-with the powder dry mixed; At least 95 quality % of said powder are made up of powdery reductibility raw material, powdery oxidisability raw material and the second powdery oxidisability raw material; Said powdery reductibility raw material is at least a organic nitrogen compound form; Said powdery oxidisability raw material is at least a basic metal nitrate form, and the said second powdery oxidisability raw material is at least a alkaline metal perchlorate form, and the said second powdery oxidisability raw material is less than 30 quality %; With
-with the powdered mixture dry type roll-in of gained; Thereby said dry type roll-in uses the roller with crude outside surface to carry out producing the tabular thing, thereby perhaps uses following roller to carry out producing the plate object with embossing pattern, and the outside surface of at least one of said roller is processed as the teeth groove shape.
16. method as claimed in claim 15 is characterized in that, the granularity of said powder is less than or equal to 40 μ m.
17., it is characterized in that said method further comprises the dry type granulation of the powdered mixture that is used to produce the particulate compacting like claim 15 or 16 described methods.
18. method as claimed in claim 17 is characterized in that, said method further comprises said particulate compressing tablet.
19. method as claimed in claim 17 is characterized in that, said method further comprises mixes said particle with gel, and will comprise the said gel of said particulate and extrude.
20. method as claimed in claim 17 is characterized in that, said method is included in the dry type packing stage and/or the granulation stage reuses the fine powder that is produced.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0510437 | 2005-10-13 | ||
| FR0510437A FR2892117B1 (en) | 2005-10-13 | 2005-10-13 | FAST GAS GENERATING PYROTECHNIC COMPOSITION AND PROCESS FOR OBTAINING THE SAME |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200680043374.5A Division CN101312930B (en) | 2005-10-13 | 2006-10-12 | Rapid gas generating pyrotechnical composition and method for obtaining same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102816038A true CN102816038A (en) | 2012-12-12 |
Family
ID=36582022
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210352802XA Pending CN102816038A (en) | 2005-10-13 | 2006-10-12 | Rapid Gas Generating Pyrotechnical Composition and Method for Obtaining Same |
| CN200680043374.5A Expired - Fee Related CN101312930B (en) | 2005-10-13 | 2006-10-12 | Rapid gas generating pyrotechnical composition and method for obtaining same |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200680043374.5A Expired - Fee Related CN101312930B (en) | 2005-10-13 | 2006-10-12 | Rapid gas generating pyrotechnical composition and method for obtaining same |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20090308509A1 (en) |
| EP (1) | EP1934158A2 (en) |
| JP (1) | JP5273609B2 (en) |
| CN (2) | CN102816038A (en) |
| FR (1) | FR2892117B1 (en) |
| WO (1) | WO2007042735A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316724A (en) * | 2015-06-18 | 2017-01-11 | 浏阳市正能环保烟花研究中心 | Safe and environmentally-friendly firework propellant powder |
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| US7758709B2 (en) * | 2006-06-21 | 2010-07-20 | Autoliv Asp, Inc. | Monolithic gas generant grains |
| US9193639B2 (en) | 2007-03-27 | 2015-11-24 | Autoliv Asp, Inc. | Methods of manufacturing monolithic generant grains |
| US8057611B2 (en) * | 2007-08-13 | 2011-11-15 | Autoliv Asp, Inc. | Multi-composition pyrotechnic grain |
| US8815029B2 (en) | 2008-04-10 | 2014-08-26 | Autoliv Asp, Inc. | High performance gas generating compositions |
| JP5394040B2 (en) * | 2008-10-29 | 2014-01-22 | 株式会社ダイセル | Gas generant composition |
| US8808476B2 (en) | 2008-11-12 | 2014-08-19 | Autoliv Asp, Inc. | Gas generating compositions having glass fibers |
| FR2949778B1 (en) * | 2009-09-10 | 2013-05-10 | Snpe Materiaux Energetiques | PYROTECHNIC COMPOUNDS GENERATORS OF GAS |
| FR2964656B1 (en) | 2010-09-15 | 2012-10-12 | Snpe Materiaux Energetiques | PYROTECHNIC COMPOUNDS GENERATORS OF GAS |
| DE102010049765A1 (en) * | 2010-10-29 | 2012-05-03 | Trw Airbag Systems Gmbh | Process for the preparation of solid propellant tablets, gas generator and module with gas generator |
| FR2975097B1 (en) * | 2011-05-09 | 2015-11-20 | Sme | PYROTECHNIC COMPOUNDS GENERATORS OF GAS |
| DE102012005759A1 (en) | 2012-03-23 | 2013-09-26 | Trw Airbag Systems Gmbh | GAS-CREATING COMPOSITION |
| FR2992575B1 (en) | 2012-06-29 | 2015-07-17 | Herakles | DEVICE FOR SPRAYING A LIQUID |
| US9051223B2 (en) | 2013-03-15 | 2015-06-09 | Autoliv Asp, Inc. | Generant grain assembly formed of multiple symmetric pieces |
| FR3005724A1 (en) | 2013-05-17 | 2014-11-21 | Herakles | PYROTECHNIC GAS GENERATOR |
| FR3007659B1 (en) | 2013-06-28 | 2017-03-24 | Herakles | METHOD FOR DELIVERING A PRESSURIZED LIQUID FROM THE COMBUSTION GASES OF AT LEAST ONE PYROTECHNIC LOAD |
| FR3037812B1 (en) | 2015-06-29 | 2017-08-04 | Herakles | FIRE EXTINGUISHER |
| CN109219539B (en) * | 2016-05-23 | 2021-10-19 | 均胜安全系统收购有限责任公司 | Gas generating compositions and methods of making and using same |
| FR3077989B1 (en) | 2018-02-20 | 2021-11-19 | Arianegroup Sas | FIRE EXTINGUISHER |
| JP2024037522A (en) * | 2022-09-07 | 2024-03-19 | 株式会社ダイセル | Gas-generating agent composition |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20090308509A1 (en) | 2009-12-17 |
| JP5273609B2 (en) | 2013-08-28 |
| WO2007042735A3 (en) | 2007-06-21 |
| EP1934158A2 (en) | 2008-06-25 |
| JP2009511411A (en) | 2009-03-19 |
| FR2892117B1 (en) | 2008-05-02 |
| FR2892117A1 (en) | 2007-04-20 |
| CN101312930A (en) | 2008-11-26 |
| CN101312930B (en) | 2013-01-16 |
| WO2007042735A2 (en) | 2007-04-19 |
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