CA2648108A1 - Pyrotechnic grains of large dimensions, and their production and use - Google Patents
Pyrotechnic grains of large dimensions, and their production and use Download PDFInfo
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- CA2648108A1 CA2648108A1 CA002648108A CA2648108A CA2648108A1 CA 2648108 A1 CA2648108 A1 CA 2648108A1 CA 002648108 A CA002648108 A CA 002648108A CA 2648108 A CA2648108 A CA 2648108A CA 2648108 A1 CA2648108 A1 CA 2648108A1
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- Prior art keywords
- cndot
- pyrotechnic
- grains
- grain
- charge
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title description 7
- 239000000203 mixture Substances 0.000 claims abstract description 24
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 238000002485 combustion reaction Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 239000008187 granular material Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 14
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 5
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 230000000717 retained effect Effects 0.000 claims description 4
- 239000011872 intimate mixture Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000007873 sieving 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
- 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 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000004513 sizing Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical class [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000008188 pellet Substances 0.000 description 10
- 230000003466 anti-cipated effect Effects 0.000 description 4
- 239000007787 solid 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101000699762 Homo sapiens RNA 3'-terminal phosphate cyclase Proteins 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 102100029143 RNA 3'-terminal phosphate cyclase Human genes 0.000 description 1
- IWUCXVSUMQZMFG-AFCXAGJDSA-N Ribavirin Chemical compound N1=C(C(=O)N)N=CN1[C@H]1[C@H](O)[C@H](O)[C@@H](CO)O1 IWUCXVSUMQZMFG-AFCXAGJDSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007908 dry granulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- 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)
- Crystallography & Structural Chemistry (AREA)
- Air Bags (AREA)
- Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
Abstract
The present invention provides pyrotechnic grains of composition comprising at least one oxidizing charge and at least one reducing charge and no binder. In characteristic manner, said grains are in the form of substantially cylindrical blocks: with a thickness of more than 5 mm; with an equivalent diameter of 10 mm or more; and with porosity in the range 1% to 8%, limits included. Said grains, advantageously based on guanidine nitrate and basic copper nitrate, are suitable for the slow, low-pressure generation of gas over an extended period.
Description
PYROTECHNIC GRAINS OF LARGE DIMENSIONS, AND THEIR
PRODUCTION AND USE
The present invention relates to large pyrotechnic grains based on binder-free formulations, to their production, and to their use. More precisely, it relates to:
= pyrotechnic grains which are in the form of blocks (monolithic blocks) with large dimensions;
= a method of producing them; and = a method of generating gas comprising the combustion of said 1o grains.
Gas generation has a number of applications, both in the civilian and in military fields.
In the automotive safety sector, gas generators have been developed with a short operational duration, which use compositions with a high combustion rate. Those compositions are in the form of thin pellets (1 mm [millimeter] to 3 mm) with a small diameter (3 mm to 7 mm). This provides them with a large combustion surface, encouraging a high rate over a short period (necessary for airbag applications in automotive safety, of the driver's airbag type). The porosity of such pellets is generally less than 4%. Pelletization operations carried out to produce said pellets are well known, similar to those used in medicinal formulations. Compositions based on guanidine nitrate and basic copper nitrate have been used in that context (United States patent US-A-5 608 183). An attempt has even been made to improve the combustion rate (US-A-6 143 102) since said combustion rate of such compositions is rather low, compared with that of other compositions used in the same field.
In similar sectors (automotive safety, to inflate curtain types of airbag which need to remain inflated for a long period), or in completely 3o different sectors, gas generators have been proposed, especially for:
inflating or deforming a structure;
propelling a liquid or a gas;
actuating a jack or some other mechanical actuator;
causing a displacement.
PRODUCTION AND USE
The present invention relates to large pyrotechnic grains based on binder-free formulations, to their production, and to their use. More precisely, it relates to:
= pyrotechnic grains which are in the form of blocks (monolithic blocks) with large dimensions;
= a method of producing them; and = a method of generating gas comprising the combustion of said 1o grains.
Gas generation has a number of applications, both in the civilian and in military fields.
In the automotive safety sector, gas generators have been developed with a short operational duration, which use compositions with a high combustion rate. Those compositions are in the form of thin pellets (1 mm [millimeter] to 3 mm) with a small diameter (3 mm to 7 mm). This provides them with a large combustion surface, encouraging a high rate over a short period (necessary for airbag applications in automotive safety, of the driver's airbag type). The porosity of such pellets is generally less than 4%. Pelletization operations carried out to produce said pellets are well known, similar to those used in medicinal formulations. Compositions based on guanidine nitrate and basic copper nitrate have been used in that context (United States patent US-A-5 608 183). An attempt has even been made to improve the combustion rate (US-A-6 143 102) since said combustion rate of such compositions is rather low, compared with that of other compositions used in the same field.
In similar sectors (automotive safety, to inflate curtain types of airbag which need to remain inflated for a long period), or in completely 3o different sectors, gas generators have been proposed, especially for:
inflating or deforming a structure;
propelling a liquid or a gas;
actuating a jack or some other mechanical actuator;
causing a displacement.
2 Generating and supplying gas has also been exploited to operate fire extinguishing devices (FR-A-2 864 905 and FR-A-2 870 459).
That relates to the field of slow gas generation. For slowly generating and supplying gas under pressure, a gas stored under pressure is generally used. The use of chemical reactions or the combustion of pyrotechnic cartridges has also been mentioned. With the combustion of pyrotechnic cartridges, the flow rate of the gas that is generated is controlled by selecting the characteristics of the propellant, the geometry of the cartridges, and/or the conditions for ejecting said generated gas, io etc.
The present invention falls within the context of generators operation providing long duration, low flow rate, and low operating pressure.
In such a context, the present invention proposes pyrotechnic ls grains that are simple in shape and that satisfy the following specifications:
a) a long combustion period (50 ms [millisecond] to 1 min [minute]) due to a slow combustion rate (to ensure a long period of operation) and/or to a ratio of combustion area over burning thickness 20 that is low, and/or to a low operating pressure (for use in low pressure generators and to encourage a low combustion rate);
b) low dependency of the rate of combustion on the operating temperature of the grain, to ensure good ballistic behavior under extreme temperature conditions from -60 C to 110 C (hence an extension of the 25 application range (see below), especially in aeronautics);
c) suitable mechanical behavior (without the intervention of a binder, the presence of which would deleteriously affect ballistic performance), especially encouraging the use of said grains in an aggressive vibratory environment.
30 The pyrotechnic grains of the invention are also advantageously non-aggressive for the gas generator in which they are used and for the associated system (i.e., on combustion, they generate neither particles nor corrosive species). In the same manner, the generated species are advantageously of low toxicity.
That relates to the field of slow gas generation. For slowly generating and supplying gas under pressure, a gas stored under pressure is generally used. The use of chemical reactions or the combustion of pyrotechnic cartridges has also been mentioned. With the combustion of pyrotechnic cartridges, the flow rate of the gas that is generated is controlled by selecting the characteristics of the propellant, the geometry of the cartridges, and/or the conditions for ejecting said generated gas, io etc.
The present invention falls within the context of generators operation providing long duration, low flow rate, and low operating pressure.
In such a context, the present invention proposes pyrotechnic ls grains that are simple in shape and that satisfy the following specifications:
a) a long combustion period (50 ms [millisecond] to 1 min [minute]) due to a slow combustion rate (to ensure a long period of operation) and/or to a ratio of combustion area over burning thickness 20 that is low, and/or to a low operating pressure (for use in low pressure generators and to encourage a low combustion rate);
b) low dependency of the rate of combustion on the operating temperature of the grain, to ensure good ballistic behavior under extreme temperature conditions from -60 C to 110 C (hence an extension of the 25 application range (see below), especially in aeronautics);
c) suitable mechanical behavior (without the intervention of a binder, the presence of which would deleteriously affect ballistic performance), especially encouraging the use of said grains in an aggressive vibratory environment.
30 The pyrotechnic grains of the invention are also advantageously non-aggressive for the gas generator in which they are used and for the associated system (i.e., on combustion, they generate neither particles nor corrosive species). In the same manner, the generated species are advantageously of low toxicity.
3 Referring to point a) of the above specifications, the skilled person will understand that the pyrotechnic grain of the invention must be thick and have a small combustion area. Thus, it must be a large grain, larger than the pellets mentioned above.
Referring to point b) of the above specifications, the skilled person will know that said grain must have low porosity.
Said skilled person will also be aware of the difficulties in fabricating a large grain of that type (pyrotechnic grain) with low porosity, with appropriate mechanical behavior, and without using a binder. He knows io that pyrotechnic grains of large dimensions and without binder in their composition have generally porosity values which are not acceptable in reference to their ballistic properties, more particularly their combustion rate. This point is all the more crucial than their operating temperature is high.
ls Surprisingly, the Applicant has obtained pyrotechnic grains, from specific oxidizing and reducing charges, which are simple in shape and that satisfy the above specifications. Such pyrotechnic grains constitute the first aspect of the present invention.
Said pyrotechnic grains of the invention have a composition that 20 comprises at least one (specific) oxidizing charge and at least one (specific) reducing charge, but that includes no binder. In this respect, they are pyrotechnic grains of the pellet type mentioned above. The composition of the pyrotechnic grains of the invention generally essentially consists of at least one such (specific) oxidizing charge and at least one 25 such (specific) reducing charge. It generally essentially consists of a (specific) oxidizing charge (an oxidizer) and a(specific) reducing charge (a reducer).
Said at least one specific oxidizing charge is selected from ammonium, potassium, sodium, barium, strontium, and basic copper 3o nitrates, and ammonium, potassium, and sodium perchlorates, and mixtures thereof. Advantageously, it comprises basic copper nitrate and/or potassium perchlorate. Highly advantageously, it consists of basic copper nitrate or potassium perchlorate. Preferably, it consists of basic copper nitrate.
Referring to point b) of the above specifications, the skilled person will know that said grain must have low porosity.
Said skilled person will also be aware of the difficulties in fabricating a large grain of that type (pyrotechnic grain) with low porosity, with appropriate mechanical behavior, and without using a binder. He knows io that pyrotechnic grains of large dimensions and without binder in their composition have generally porosity values which are not acceptable in reference to their ballistic properties, more particularly their combustion rate. This point is all the more crucial than their operating temperature is high.
ls Surprisingly, the Applicant has obtained pyrotechnic grains, from specific oxidizing and reducing charges, which are simple in shape and that satisfy the above specifications. Such pyrotechnic grains constitute the first aspect of the present invention.
Said pyrotechnic grains of the invention have a composition that 20 comprises at least one (specific) oxidizing charge and at least one (specific) reducing charge, but that includes no binder. In this respect, they are pyrotechnic grains of the pellet type mentioned above. The composition of the pyrotechnic grains of the invention generally essentially consists of at least one such (specific) oxidizing charge and at least one 25 such (specific) reducing charge. It generally essentially consists of a (specific) oxidizing charge (an oxidizer) and a(specific) reducing charge (a reducer).
Said at least one specific oxidizing charge is selected from ammonium, potassium, sodium, barium, strontium, and basic copper 3o nitrates, and ammonium, potassium, and sodium perchlorates, and mixtures thereof. Advantageously, it comprises basic copper nitrate and/or potassium perchlorate. Highly advantageously, it consists of basic copper nitrate or potassium perchlorate. Preferably, it consists of basic copper nitrate.
4 Said at least one specific reducing charge is selected from nitroguanidine, guanidine nitrate, and mixtures thereof. Preferably, it consists of guanidine nitrate.
In characteristic manner, said pyrotechnic grains of the invention are in the form of substantially cylindrical blocks:
= with thickness of more than 5 mm;
= with an equivalent diameter of 10 mm or more; and with porosity in the range 1% to 8%, limits included.
Said (monolithic) blocks are large blocks, which are simple in shape io and of low porosity.
Said blocks have a substantially cylindrical shape. Generally, but not exclusively, they are circular cylinders or near (quasi) circular cylinders.
The shape of the grains of the invention is the signature of the last step of the method by which they are obtained: a compacting step (see below).
Said blocks may in particular consist of solid (quasi) cylinders or (quasi) cylindrical sleeves.
The grains in question are large objects (thickness more than
In characteristic manner, said pyrotechnic grains of the invention are in the form of substantially cylindrical blocks:
= with thickness of more than 5 mm;
= with an equivalent diameter of 10 mm or more; and with porosity in the range 1% to 8%, limits included.
Said (monolithic) blocks are large blocks, which are simple in shape io and of low porosity.
Said blocks have a substantially cylindrical shape. Generally, but not exclusively, they are circular cylinders or near (quasi) circular cylinders.
The shape of the grains of the invention is the signature of the last step of the method by which they are obtained: a compacting step (see below).
Said blocks may in particular consist of solid (quasi) cylinders or (quasi) cylindrical sleeves.
The grains in question are large objects (thickness more than
5 mm, equivalent diameter (or, clearly, diameter if it is a perfect circular cylinder) of 10 mm or more), and are relatively dense (porosity in the range 1% to 8%).
Non-limiting dimensions of said grains are detailed below.
Generally and independently :
= the thickness of the blocks is 75 mm or less; or = the equivalent diameter of said blocks is 75 mm or less.
In general, said thickness and said equivalent diameter are both 75 mm or less.
According to a first advantageous embodiment, independently . the thickness of the blocks is 7.5 mm or more ; or the equivalent diameter of said blocks is 20 mm or more.
In general, in the context of said first advantageous embodiment, said thickness and said equivalent diameter are both as precised above.
According to a second advantageous embodiment, independently:
= the thickness of the blocks is in the range 10 mm to 60 mm (values of 10 mm and 60 mm being included); or = the equivalent diameter of said blocks is in the range 10 mm to 60 mm (values of 10 mm and 60 mm being included).
5 In general, in the context of this second advantageous embodiment, said thickness and said equivalent diameter are both in the range 10 mm to 60 mm (values of 10 mm and 60 mm being included).
In particular, pyrotechnic blocks of the solid circular cylinder type and with the dimensions given below, have been produced in the context ia of the invention:
diameter of 25 mm and thickness of 10 mm;
= diameter of 50 mm and thickness of 50 mm.
Further, it has been stated that the porosity of the blocks is in the range 1% to 8% (it should be noted here that this parameter, expressed as a percentage, corresponds to the ratio between the actual density and the theoretical density; it is in fact the difference from the theoretical density).
Said porosity is advantageously 5% or less. It should be recalled that the lower said porosity, the lower the dependency of the rate of combustion on the operating temperature of the grain.
It should be indicated here that, in a non-limiting manner, blocks, which are of the circular cylinder type with the dimensions described above, have been respectively obtained with the porosities indicated below :
= porosity of about 5% (with diameter = 25 mm and thickness =
10 mm);
porosity of about 7% (with diameter = thickness = 50 mm).
As indicated above, the pyrotechnic grains of the invention, which are simple in shape, being substantially cylindrical, may in particular consist of solid cylinders or sleeves. The equivalent internal diameter of said sleeves is advantageously more than 10 mm; preferably, it is in the range 12 mm to 35 mm (that implies obviously a greater equivalent diameter of the sleeve).
Referring to the composition of the pyrotechnic grains of the invention, the following non-limiting details can furthermore be given.
Non-limiting dimensions of said grains are detailed below.
Generally and independently :
= the thickness of the blocks is 75 mm or less; or = the equivalent diameter of said blocks is 75 mm or less.
In general, said thickness and said equivalent diameter are both 75 mm or less.
According to a first advantageous embodiment, independently . the thickness of the blocks is 7.5 mm or more ; or the equivalent diameter of said blocks is 20 mm or more.
In general, in the context of said first advantageous embodiment, said thickness and said equivalent diameter are both as precised above.
According to a second advantageous embodiment, independently:
= the thickness of the blocks is in the range 10 mm to 60 mm (values of 10 mm and 60 mm being included); or = the equivalent diameter of said blocks is in the range 10 mm to 60 mm (values of 10 mm and 60 mm being included).
5 In general, in the context of this second advantageous embodiment, said thickness and said equivalent diameter are both in the range 10 mm to 60 mm (values of 10 mm and 60 mm being included).
In particular, pyrotechnic blocks of the solid circular cylinder type and with the dimensions given below, have been produced in the context ia of the invention:
diameter of 25 mm and thickness of 10 mm;
= diameter of 50 mm and thickness of 50 mm.
Further, it has been stated that the porosity of the blocks is in the range 1% to 8% (it should be noted here that this parameter, expressed as a percentage, corresponds to the ratio between the actual density and the theoretical density; it is in fact the difference from the theoretical density).
Said porosity is advantageously 5% or less. It should be recalled that the lower said porosity, the lower the dependency of the rate of combustion on the operating temperature of the grain.
It should be indicated here that, in a non-limiting manner, blocks, which are of the circular cylinder type with the dimensions described above, have been respectively obtained with the porosities indicated below :
= porosity of about 5% (with diameter = 25 mm and thickness =
10 mm);
porosity of about 7% (with diameter = thickness = 50 mm).
As indicated above, the pyrotechnic grains of the invention, which are simple in shape, being substantially cylindrical, may in particular consist of solid cylinders or sleeves. The equivalent internal diameter of said sleeves is advantageously more than 10 mm; preferably, it is in the range 12 mm to 35 mm (that implies obviously a greater equivalent diameter of the sleeve).
Referring to the composition of the pyrotechnic grains of the invention, the following non-limiting details can furthermore be given.
6 The said composition of the pyrotechnic grains of the invention advantageously includes basic copper nitrate as the oxidizing charge and guanidine nitrate as the reducing charge. Highly advantageously, it comprises basic copper nitrate as the only oxidizing charge and guanidine nitrate as the only reducing charge. In the automotive safety held (driver type airbags), said basic copper nitrate/guanidine nitrate combination is known to have a combustion rate that is rather low relative to that of other compositions used in this field. In the context of this highly advantageous embodiment, said composition generally comprises:
= 45% to 55% by weight of guanidine nitrate;
= 40% to 50% by weight of basic copper nitrate; and = 0 to 5% by weight of additives.
The additives in question, which are optionally present, are chemical compounds that are known per se as well as for their beneficial involvement in the general production of pyrotechnic grains. In particular, they may be:
= slagging agents supplied with the starting materials : oxidizing charge(s) and reducing charge(s) (for example: alumina);
= processing aids of the pressing aid or unmolding aid type (for 2o example: silica, calcium stearate, mica, etc).
In a second aspect, the present invention provides the production of large pyrotechnic grains, as described above.
The method in question comprises a series of steps that are known per se.
Surprisingly, it has been possible to find operating conditions for this series of steps (which are known per se) that enable, from the selected oxidizing and reducing charges, grains of the invention to be obtained without the involvement of a binder, and having simultaneously large dimensions, low porosity, and also acceptable mechanical properties (which can tolerate the vibrational environment of an automobile or aircraft).
The method of producing pyrotechnic grains of the invention comprises carrying out the following steps in succession:
= intimately dry or wet mixing said oxidizing and reducing charges used in the powder state;
= 45% to 55% by weight of guanidine nitrate;
= 40% to 50% by weight of basic copper nitrate; and = 0 to 5% by weight of additives.
The additives in question, which are optionally present, are chemical compounds that are known per se as well as for their beneficial involvement in the general production of pyrotechnic grains. In particular, they may be:
= slagging agents supplied with the starting materials : oxidizing charge(s) and reducing charge(s) (for example: alumina);
= processing aids of the pressing aid or unmolding aid type (for 2o example: silica, calcium stearate, mica, etc).
In a second aspect, the present invention provides the production of large pyrotechnic grains, as described above.
The method in question comprises a series of steps that are known per se.
Surprisingly, it has been possible to find operating conditions for this series of steps (which are known per se) that enable, from the selected oxidizing and reducing charges, grains of the invention to be obtained without the involvement of a binder, and having simultaneously large dimensions, low porosity, and also acceptable mechanical properties (which can tolerate the vibrational environment of an automobile or aircraft).
The method of producing pyrotechnic grains of the invention comprises carrying out the following steps in succession:
= intimately dry or wet mixing said oxidizing and reducing charges used in the powder state;
7 = dry or wet granulating the powdered mixture obtained;
sizing the granules obtained; and shaping the retained sized granules by compacting under conditions that produce the anticipated result, i.e. the production of pyrotechnic grains having the dimensional and porosity characteristics defined above.
The conditions in question are principally = the characteristics of the starting powders ;
= the characteristics of the retained sized granules; and = the compacting parameters.
The Applicant has discovered that suitable conditions may be combined to obtain the desired result.
Before detailing said conditions (parameters) of the method of the invention, it should in general be indicated :
= that the powders are advantageously intimately dry mixed ;
= that granulation is also advantageously a dry granulation (independently of the manner of said intimate mixing) ;
= that the granules are advantageously sized by sieving; and = that at least one shaping additive (a pressing aid, such as calcium stearate or mica) may advantageously be added to said sized granules before shaping them by compacting.
In characteristic manner, to obtain the anticipated result, more particularly to obtain a slow rate of combustion, at least one of the charges used in the powder state has a median diameter that is substantially larger than that which is used in the prior art to prepare pellets (of small dimensions). Thus, it is recommended in the context of carrying out the method of the present invention to use at least part of the reducing charge(s) with a median diameter that is substantially higher (x 4, x 6) than that known to be used in the preparation of prior art pellets. It is recommended that a reducing charge with a median diameter of 200 pm [micrometer] or more be used. In particular, it is recommended that guanidine nitrate with a median diameter of 200 pm to 300 pm be used. Said guanidine nitrate is conventionally used for the fabrication of pellets, with a median diameter of 50 pm.
sizing the granules obtained; and shaping the retained sized granules by compacting under conditions that produce the anticipated result, i.e. the production of pyrotechnic grains having the dimensional and porosity characteristics defined above.
The conditions in question are principally = the characteristics of the starting powders ;
= the characteristics of the retained sized granules; and = the compacting parameters.
The Applicant has discovered that suitable conditions may be combined to obtain the desired result.
Before detailing said conditions (parameters) of the method of the invention, it should in general be indicated :
= that the powders are advantageously intimately dry mixed ;
= that granulation is also advantageously a dry granulation (independently of the manner of said intimate mixing) ;
= that the granules are advantageously sized by sieving; and = that at least one shaping additive (a pressing aid, such as calcium stearate or mica) may advantageously be added to said sized granules before shaping them by compacting.
In characteristic manner, to obtain the anticipated result, more particularly to obtain a slow rate of combustion, at least one of the charges used in the powder state has a median diameter that is substantially larger than that which is used in the prior art to prepare pellets (of small dimensions). Thus, it is recommended in the context of carrying out the method of the present invention to use at least part of the reducing charge(s) with a median diameter that is substantially higher (x 4, x 6) than that known to be used in the preparation of prior art pellets. It is recommended that a reducing charge with a median diameter of 200 pm [micrometer] or more be used. In particular, it is recommended that guanidine nitrate with a median diameter of 200 pm to 300 pm be used. Said guanidine nitrate is conventionally used for the fabrication of pellets, with a median diameter of 50 pm.
8 In characteristic manner, to obtain the anticipated result, more particularly to obtain low porosity, the granules selected are those that have a median diameter of more than 200 pm, preferably in the range 500 pm to 1000 pm. It is thus recommended, in the context of the present invention, that basic copper nitrate/guanidine nitrate granules with a median diameter in the range 500 pm to 700 pm or potassium perchlorate/guanidine nitrate granules with a median diameter in the range 500 pm to 1000 pm be selected.
The skilled person is capable of optimizing this parameter (granule io size) as well as the others (powder mean diameter and compacting parameters) as a function of the exact nature of the products in question.
Regarding the compacting parameters, in general, to obtain the anticipated result, more particular to obtain low porosity, a pressure in the range 15 x 106 Pa [pascal] to 35 x 106 Pa is applied for 0.1 s [second] to 30s.
Compacting is clearly carried out in a mold the shape of which corresponds to that envisaged for the prepared pyrotechnic grain (substantially cylindrical shape).
The method of the invention is very advantageously carried out with all the above advantageous embodiments, i.e. :
- a median diameter of the at least one reducing charge of 200 pm or more ;
- a median diameter of the granules of more than 200 pm ; and - a compacting step carried out at 15-35 x 106 Pa during 0.1 to 30s.
The method of the invention is advantageously carried out with a combination of basic copper nitrate or potassium perchlorate/guanidine nitrate; highly advantageously, it is carried out with a basic copper nitrate/guanidine nitrate combination. In the context of the present invention, the combustion rate of compositions based on these two elements (BCN/NG) is reduced. The teaching of the present invention thus goes against that of US-A-6143 102.
In a third aspect, the present invention provides a method of generating gas, the method comprising, in conventional manner, the combustion of at least one pyrotechnic grain. In characteristic manner,
The skilled person is capable of optimizing this parameter (granule io size) as well as the others (powder mean diameter and compacting parameters) as a function of the exact nature of the products in question.
Regarding the compacting parameters, in general, to obtain the anticipated result, more particular to obtain low porosity, a pressure in the range 15 x 106 Pa [pascal] to 35 x 106 Pa is applied for 0.1 s [second] to 30s.
Compacting is clearly carried out in a mold the shape of which corresponds to that envisaged for the prepared pyrotechnic grain (substantially cylindrical shape).
The method of the invention is very advantageously carried out with all the above advantageous embodiments, i.e. :
- a median diameter of the at least one reducing charge of 200 pm or more ;
- a median diameter of the granules of more than 200 pm ; and - a compacting step carried out at 15-35 x 106 Pa during 0.1 to 30s.
The method of the invention is advantageously carried out with a combination of basic copper nitrate or potassium perchlorate/guanidine nitrate; highly advantageously, it is carried out with a basic copper nitrate/guanidine nitrate combination. In the context of the present invention, the combustion rate of compositions based on these two elements (BCN/NG) is reduced. The teaching of the present invention thus goes against that of US-A-6143 102.
In a third aspect, the present invention provides a method of generating gas, the method comprising, in conventional manner, the combustion of at least one pyrotechnic grain. In characteristic manner,
9 PCT/EP2007/053241 said method of the invention comprises the combustion of at least one pyrotechnic grain as described above (large pyrotechnic grain) and/or produced using the method described above.
Said gas generation method is carried out in a suitable device which, in particular, has a combustion chamber adapted to the dimensions of the original pyrotechnic charge, based on large pyrotechnic grains. In common with currently known devices, said device comprises:
= elements for retaining, positioning, and adjusting the pyrotechnic charge based on large pyrotechnic grains (which constitutes the first 1o aspect of the present invention);
= ignition elements;
= at least one safety cap ensuring depressurization of the generator in the event of accidental overpressure;
= at least one nozzle; and = a filter to retain the majority of the solid combustion residues.
Interesting applications for the pyrotechnic grains of the invention are specified below, i.e. fields in which gas generation must be maintained for a relatively long period.
The following applications are particularly contemplated = the generation of gas intended to propel a fluid, either directly or via a separating membrane, for example, to extinguish fire in civilian or military aircraft engines, to inert bays in civilian or military aircraft, to extinguish fire in a building, in all types of civilian vehicles (automobiles, etc) or military vehicles (tanks, etc), to inject grease or active principle, etc;
= the generation of gas in a pyrotechnic actuator intended to actuate a jack, for example (to open an aircraft door, for example);
= the generation of gas to inflate or deform inflatable structures that are deformable, such as aircraft escape chutes, automotive safety 3o anti-submarining structures, or releasers.
Finally, examples of the present invention are described below.
Example 1 Pyrotechnic grains of the invention were prepared from the following starting materials:
= basic copper nitrate (BCN): powder with a median diameter of 5 8iam;
= guanidine nitrate (GN): powder with a median diameter of 218 pm;
= alumina (slagging agent): powder with a median diameter of 1pm.
Said gas generation method is carried out in a suitable device which, in particular, has a combustion chamber adapted to the dimensions of the original pyrotechnic charge, based on large pyrotechnic grains. In common with currently known devices, said device comprises:
= elements for retaining, positioning, and adjusting the pyrotechnic charge based on large pyrotechnic grains (which constitutes the first 1o aspect of the present invention);
= ignition elements;
= at least one safety cap ensuring depressurization of the generator in the event of accidental overpressure;
= at least one nozzle; and = a filter to retain the majority of the solid combustion residues.
Interesting applications for the pyrotechnic grains of the invention are specified below, i.e. fields in which gas generation must be maintained for a relatively long period.
The following applications are particularly contemplated = the generation of gas intended to propel a fluid, either directly or via a separating membrane, for example, to extinguish fire in civilian or military aircraft engines, to inert bays in civilian or military aircraft, to extinguish fire in a building, in all types of civilian vehicles (automobiles, etc) or military vehicles (tanks, etc), to inject grease or active principle, etc;
= the generation of gas in a pyrotechnic actuator intended to actuate a jack, for example (to open an aircraft door, for example);
= the generation of gas to inflate or deform inflatable structures that are deformable, such as aircraft escape chutes, automotive safety 3o anti-submarining structures, or releasers.
Finally, examples of the present invention are described below.
Example 1 Pyrotechnic grains of the invention were prepared from the following starting materials:
= basic copper nitrate (BCN): powder with a median diameter of 5 8iam;
= guanidine nitrate (GN): powder with a median diameter of 218 pm;
= alumina (slagging agent): powder with a median diameter of 1pm.
10 Said powders were dry mixed in a Sofraden type powder mixer (a Guedu type mixer would also have been suitable) in the following proportions:
BCN 44.87%
GN 52.44%
Alumina 2.69% (weight %).
The intimate mixture of powders obtained was dry granulated in a Sahut Conreur type granulator (an Alexanderwerk type granulator would also have been suitable). Said intimate mixture of powders was forced through a screen. The granulometric distribution of the granules obtained was from 10 pm to 1000 pm.
The granules obtained were then sieved, and those with a mean diameter of more than 200 pm were selected.
Said selected granules were then compacted on a 35 (metric) tonne single action press. The compacting pressure applied was 230 bars (23 x 106 Pa). It was applied for 10 s.
Pyrotechnic grains in accordance with the invention were obtained, which grains were cylindrical monoliths (shape of mold) with a thickness of 10 mm, a diameter of 24.6 mm, and porosity of 3%.
3o Example 2 In similar manner, cylindrical grains were prepared as follows:
with a thickness of 50 mm;
with a diameter of 50 mm;
with porosity of 7%.
Example 3 (prior art) In similar manner, prior art pellets, which were cylindrical grains, were prepared as follows:
= with a thickness of 1.8 mm;
= with a diameter of 6.3 mm;
= with porosity of 2%.
The grains of said Examples 1 to 3 were tested in generators with the same architecture. The graphs of the operating pressures of said io generators as a function of time are given in the accompanying Figures 1 to 3.
With the prior art pellet, as expected, an operating peak was obtained (Figure 3). With the blocks of the invention, the desired spread over time was observed (Figures 1 and 2).
Further, the mechanical behavior of the grains of the invention as regards aeronautical vibrations was tested, with satisfactory results (standard RTCA DO-160D: "Environmental Conditions and Test Procedures for Airborne Equipment").
BCN 44.87%
GN 52.44%
Alumina 2.69% (weight %).
The intimate mixture of powders obtained was dry granulated in a Sahut Conreur type granulator (an Alexanderwerk type granulator would also have been suitable). Said intimate mixture of powders was forced through a screen. The granulometric distribution of the granules obtained was from 10 pm to 1000 pm.
The granules obtained were then sieved, and those with a mean diameter of more than 200 pm were selected.
Said selected granules were then compacted on a 35 (metric) tonne single action press. The compacting pressure applied was 230 bars (23 x 106 Pa). It was applied for 10 s.
Pyrotechnic grains in accordance with the invention were obtained, which grains were cylindrical monoliths (shape of mold) with a thickness of 10 mm, a diameter of 24.6 mm, and porosity of 3%.
3o Example 2 In similar manner, cylindrical grains were prepared as follows:
with a thickness of 50 mm;
with a diameter of 50 mm;
with porosity of 7%.
Example 3 (prior art) In similar manner, prior art pellets, which were cylindrical grains, were prepared as follows:
= with a thickness of 1.8 mm;
= with a diameter of 6.3 mm;
= with porosity of 2%.
The grains of said Examples 1 to 3 were tested in generators with the same architecture. The graphs of the operating pressures of said io generators as a function of time are given in the accompanying Figures 1 to 3.
With the prior art pellet, as expected, an operating peak was obtained (Figure 3). With the blocks of the invention, the desired spread over time was observed (Figures 1 and 2).
Further, the mechanical behavior of the grains of the invention as regards aeronautical vibrations was tested, with satisfactory results (standard RTCA DO-160D: "Environmental Conditions and Test Procedures for Airborne Equipment").
Claims (14)
1. A pyrotechnic grain, the composition of which comprises at least one oxidizing charge selected from ammonium, potassium, sodium, barium, strontium, and basic copper nitrates, and ammonium, potassium, and sodium perchlorates, and mixtures thereof ;
at least one reducing charge selected from nitroguanidine, guanidine nitrate, and mixtures thereof ; and no binder, characterized in that it is in the form of a substantially cylindrical block:
.cndot. with a thickness of more than 5 mm;
.cndot. with an equivalent diameter of 10 mm or more; and .cndot. with porosity in the range 1% to 8%, limits included.
at least one reducing charge selected from nitroguanidine, guanidine nitrate, and mixtures thereof ; and no binder, characterized in that it is in the form of a substantially cylindrical block:
.cndot. with a thickness of more than 5 mm;
.cndot. with an equivalent diameter of 10 mm or more; and .cndot. with porosity in the range 1% to 8%, limits included.
2. The pyrotechnic grain according to claim 1, characterized in that the thickness of said block is 7.5 mm or more and/or the equivalent diameter of said block is 20 mm or more.
3. The pyrotechnic grain according to claim 1, characterized in that the thickness and/or equivalent diameter of said block is in the range mm to 60 mm, limits included.
4. The pyrotechnic grain according to any one of claims 1 to 3, characterized in that the porosity of said block is 5% or less.
5. The pyrotechnic grain according to any one of claims 1 to 4, characterized in that it is in the form of a sleeve of internal equivalent diameter that is advantageously more than 10 mm.
6. The pyrotechnic grain according to any one of claims 1 to 5, characterized in that said at least one oxidizing charge consists of basic copper nitrate.
7. The pyrotechnic grain according to any one of claims 1 to 6, characterized in that said at least one reducing charge consists of guanidine nitrate.
8. The pyrotechnic grain according to any one of claims 1 to 7, characterized in that its composition comprises:
.cndot. 45% to 55% by weight of guanidine nitrate;
.cndot. 40% to 50% by weight of basic copper nitrate; and .cndot. 0 to 5% by weight of additives.
.cndot. 45% to 55% by weight of guanidine nitrate;
.cndot. 40% to 50% by weight of basic copper nitrate; and .cndot. 0 to 5% by weight of additives.
9. A method of producing a pyrotechnic grain according to any one of the preceding claims, characterized in that it comprises:
.cndot. intimately dry or wet mixing said oxidizing and reducing charges used in the powder state;
.cndot. dry or wet granulating the powdered mixture obtained;
.cndot. sizing the granules obtained; and .cndot. shaping the retained sized granules by compacting;
the characteristics of the starting powders, the retained sized granules and the compacting parameters being selected to produce said pyrotechnic grains having said dimensional and porosity characteristics.
.cndot. intimately dry or wet mixing said oxidizing and reducing charges used in the powder state;
.cndot. dry or wet granulating the powdered mixture obtained;
.cndot. sizing the granules obtained; and .cndot. shaping the retained sized granules by compacting;
the characteristics of the starting powders, the retained sized granules and the compacting parameters being selected to produce said pyrotechnic grains having said dimensional and porosity characteristics.
10. The method according to claim 9, characterized in that the intimate mixture or (and) granulation is (are) carried out by a dry method.
11. The method according to claim 9 or claim 10, characterized in that the granules are sized by sieving.
12. The method according to any one of claims 9 to 11, characterized in that it comprises:
.cndot. using at least one reducing charge with a median diameter of 200 µm or more; and/or, advantageously and .cndot. sieving the granules to retain those with a median diameter of more than 200 µm; and/or, advantageously and .cndot. shaping by compacting at a pressure in the range 15 × 10 6 Pa to 35 × 10 6 Pa for 0.1 s to 30 s.
.cndot. using at least one reducing charge with a median diameter of 200 µm or more; and/or, advantageously and .cndot. sieving the granules to retain those with a median diameter of more than 200 µm; and/or, advantageously and .cndot. shaping by compacting at a pressure in the range 15 × 10 6 Pa to 35 × 10 6 Pa for 0.1 s to 30 s.
13. The method according to any one of claims 9 to 12, characterized in that it is carried out with guanidine nitrate as the reducing charge and basic copper nitrate or potassium perchlorate as the oxidizing charge.
14. A method of generating gas, comprising the combustion of at least one pyrotechnic grain, characterized in that said at least one pyrotechnic grain is a grain according to any one of claims 1 to 8 and/or a grain produced according to any one of claims 9 to 13.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0651183A FR2899227B1 (en) | 2006-04-04 | 2006-04-04 | LARGE-SIZE MONOLITH PYROTECHNIC OBJECTS, OBTAINING AND USING |
| FR0651183 | 2006-04-04 | ||
| PCT/EP2007/053241 WO2007113299A1 (en) | 2006-04-04 | 2007-04-03 | Pyrotechnic grains of large dimensions, and their production and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2648108A1 true CA2648108A1 (en) | 2007-10-11 |
| CA2648108C CA2648108C (en) | 2014-04-22 |
Family
ID=37806959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2648108A Expired - Fee Related CA2648108C (en) | 2006-04-04 | 2007-04-03 | Pyrotechnic grains of large dimensions, and their production and use |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20100051149A1 (en) |
| EP (1) | EP2001822B1 (en) |
| CN (1) | CN101415659A (en) |
| CA (1) | CA2648108C (en) |
| FR (1) | FR2899227B1 (en) |
| NO (1) | NO20084308L (en) |
| RU (1) | RU2437867C2 (en) |
| WO (1) | WO2007113299A1 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9193639B2 (en) | 2007-03-27 | 2015-11-24 | Autoliv Asp, Inc. | Methods of manufacturing monolithic generant grains |
| FR2926545B1 (en) | 2008-01-21 | 2010-09-17 | Snpe Materiaux Energetiques | NITROGEN GENERATING COMPOSITION COMPRISING AZODICARBONAMIDE AND PROCESS FOR GENERATING NITROGEN GAS BY DECOMPOSITION OF SAID COMPOSITION |
| DE102008020087B4 (en) * | 2008-04-22 | 2019-10-10 | GM Global Technology Operations LLC (n. d. Ges. d. Staates Delaware) | Pyrotechnic actuator with filter |
| FR2964656B1 (en) * | 2010-09-15 | 2012-10-12 | Snpe Materiaux Energetiques | PYROTECHNIC COMPOUNDS GENERATORS OF GAS |
| US9051223B2 (en) | 2013-03-15 | 2015-06-09 | Autoliv Asp, Inc. | Generant grain assembly formed of multiple symmetric pieces |
| CN103214322A (en) * | 2013-05-15 | 2013-07-24 | 浏阳市合力高科发展有限公司 | Sulfur-smoke-free powder composition and preparation method thereof |
| 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 |
| CN103739416B (en) * | 2013-12-17 | 2016-08-24 | 江西省李渡烟花集团有限公司 | A kind of Novel firework silver willow powder |
| FR3022906B1 (en) | 2014-06-30 | 2016-07-15 | Herakles | MONOLITHIC PYROTECHNIC BLOCKS GENERATORS OF GAS |
| FR3037812B1 (en) | 2015-06-29 | 2017-08-04 | Herakles | FIRE EXTINGUISHER |
| CN105237315A (en) * | 2015-08-18 | 2016-01-13 | 帅银飞 | Automatic pelletizer for brightening beads of fireworks |
| 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 |
| CN107698415A (en) * | 2017-10-24 | 2018-02-16 | 湖北航鹏化学动力科技有限责任公司 | A kind of gas generant composition, preparation method, application and gas generator |
| FR3077989B1 (en) | 2018-02-20 | 2021-11-19 | Arianegroup Sas | FIRE EXTINGUISHER |
| CN109160868A (en) * | 2018-10-31 | 2019-01-08 | 湖北航天化学技术研究所 | A kind of gas generant for air cell |
| RU2722031C1 (en) * | 2019-08-29 | 2020-05-26 | Акционерное общество "Федеральный научно-производственный центр "Научно-исследовательский институт прикладной химии" | Red fire pyrotechnic composition |
| CN111675589B (en) * | 2020-05-15 | 2021-08-06 | 湖北航鹏化学动力科技有限责任公司 | Gas generating agent composition, preparation method and application thereof |
| CN111548242B (en) * | 2020-05-15 | 2021-09-03 | 湖北航鹏化学动力科技有限责任公司 | Gas generator |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3814694A (en) * | 1971-08-09 | 1974-06-04 | Aerojet General Co | Non-toxic gas generation |
| US4998751A (en) * | 1990-03-26 | 1991-03-12 | Morton International, Inc. | Two-stage automotive gas bag inflator using igniter material to delay second stage ignition |
| CA2094888A1 (en) * | 1992-08-24 | 1994-02-25 | Bradley W. Smith | Gas generant body having pressed-on burn inhibitor layer |
| US5423384A (en) * | 1993-06-24 | 1995-06-13 | Olin Corporation | Apparatus for suppressing a fire |
| US5682014A (en) * | 1993-08-02 | 1997-10-28 | Thiokol Corporation | Bitetrazoleamine gas generant compositions |
| US5641938A (en) * | 1995-03-03 | 1997-06-24 | Primex Technologies, Inc. | Thermally stable gas generating composition |
| US5608183A (en) * | 1996-03-15 | 1997-03-04 | Morton International, Inc. | Gas generant compositions containing amine nitrates plus basic copper (II) nitrate and/or cobalt(III) triammine trinitrate |
| US6143102A (en) * | 1999-05-06 | 2000-11-07 | Autoliv Asp, Inc. | Burn rate-enhanced basic copper nitrate-containing gas generant compositions and methods |
| WO2001000276A1 (en) * | 1999-06-25 | 2001-01-04 | Paul Scherrer Institut | Device for carrying out proton therapy |
| WO2001025169A1 (en) * | 1999-10-06 | 2001-04-12 | Nof Corporation | Gas generator composition |
| JP2005538834A (en) * | 2002-09-12 | 2005-12-22 | テクストロン システムズ コーポレーション | Multistage gas generator and gas generator |
| US20040173922A1 (en) * | 2003-03-04 | 2004-09-09 | Barnes Michael W. | Method for preparing pyrotechnics oxidized by basic metal nitrate |
| FR2864905B1 (en) * | 2004-01-09 | 2006-07-14 | Airbus France | FIRE EXTINGUISHING DEVICE |
| FR2870459B1 (en) * | 2004-05-19 | 2006-08-25 | Airbus France Sas | DEVICE FOR EXTINGUISHING FIRE BY INJECTION OF A GAS GENERATED BY THE COMBUSTION OF A PYROTECHNIC BLOCK |
| US20060219340A1 (en) * | 2005-03-31 | 2006-10-05 | Dunham Steven M | Gas generating system |
| FR2887247B1 (en) * | 2005-06-15 | 2007-10-12 | Snpe Materiaux Energetiques | PROCESS FOR MANUFACTURING GAS GENERATOR PELLETS COMPRISING A DRY GRANULATION STEP |
-
2006
- 2006-04-04 FR FR0651183A patent/FR2899227B1/en not_active Expired - Fee Related
-
2007
- 2007-04-03 CA CA2648108A patent/CA2648108C/en not_active Expired - Fee Related
- 2007-04-03 EP EP07727712.7A patent/EP2001822B1/en active Active
- 2007-04-03 RU RU2008142975/05A patent/RU2437867C2/en active
- 2007-04-03 US US12/225,812 patent/US20100051149A1/en not_active Abandoned
- 2007-04-03 CN CNA2007800117600A patent/CN101415659A/en active Pending
- 2007-04-03 WO PCT/EP2007/053241 patent/WO2007113299A1/en active Application Filing
-
2008
- 2008-10-15 NO NO20084308A patent/NO20084308L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| NO20084308L (en) | 2008-10-23 |
| FR2899227B1 (en) | 2008-10-24 |
| EP2001822B1 (en) | 2017-08-16 |
| CN101415659A (en) | 2009-04-22 |
| RU2437867C2 (en) | 2011-12-27 |
| RU2008142975A (en) | 2010-05-10 |
| FR2899227A1 (en) | 2007-10-05 |
| WO2007113299A1 (en) | 2007-10-11 |
| CA2648108C (en) | 2014-04-22 |
| US20100051149A1 (en) | 2010-03-04 |
| EP2001822A1 (en) | 2008-12-17 |
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