CA2172822A1 - Gas developing agent - Google Patents
Gas developing agentInfo
- Publication number
- CA2172822A1 CA2172822A1 CA002172822A CA2172822A CA2172822A1 CA 2172822 A1 CA2172822 A1 CA 2172822A1 CA 002172822 A CA002172822 A CA 002172822A CA 2172822 A CA2172822 A CA 2172822A CA 2172822 A1 CA2172822 A1 CA 2172822A1
- Authority
- CA
- Canada
- Prior art keywords
- gas generator
- weight
- component
- generator propellant
- propellant according
- 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.)
- Abandoned
Links
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/06—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires containing gas-producing, chemically-reactive components
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
-
- 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
Abstract
The present invention provides a gas generator propellant, in particular for airbags, which contains (A) at least one carbonate, hydrogen carbonate or nitrate of guanidine, aminoguanidine, diaminoguanidine or triaminoguanidine, (B) at least one alkali-metal or alkaline-earth-metal nitrate or ammonium nitrate as oxidizing agent, and (C) at least one carrier substance selected from silicon dioxide, alkali-metal silicates, alkaline-earth-metal silicates or aluminosilicates and/or at least one oxygen-supplying carrier substance selected from iron(III) oxide, cobalt oxides, manganese dioxide and copper(II) oxide to moderate burn-up and improve slag formation. This gas generator propellant has improved burn-up behaviour and slag formation.
Description
-,' E, ~t~ I ;. J ;~ 217 2 ~ 2 2 l:E~ TR~ I$N
Gas generator propellant The invention relates to solid gas generator propellants based on guanidine compounds on suitable carriers.
JP H5-254977 discloses gas generator propellants for airbags based on triaminoguanidine nitrate (TAGN), which may additionally contain oxidizing agents such as alkali-metal and alkaline-earth-metal nitrates, nitrites, chlorates or perchlorates. Molybdenum sulphide may be present as a further component. The advantage of using TAGN instead of the known sodium azides is the nontoxic nature and also the good stability of TAGN, which, in addition, does not form any salts which are sensitive to friction and impact in combination with heavy metals. The burn-up rate of the gas generator propellants should be possible via a variation in the compression pressure during the production of pellets or tablets from the component mixture.
Disadvantages of such gas generator propellants are a still inadequate controllability of the burn-up, the development of toxic gases such as CO and an imperfect formation of slag during burn-up, which results in an increased development of dusts, some of which enter the lungs.
Compared with JP H5-254977, the object of the present invention is to provide improved gas generator propellants whose burn-up behaviour can be systematically adjusted and which form readily retainable slags during burn-up and minimize the production of toxic gases. The gas generator propellants are intended to be thermally stable, readily ignitable, fast-burning, even at low temperature, and satisfactorily storable and to ensure a high gas yield. In addition, said gas generator propellants are intended to make it possible to reduce the size of the generator casing and consequently reduce its weight compared with known generators operated with sodium azide.
According to the invention, these objects are achieved by a gas generator propellant, comprising (A) at least one carbonate, hydrogen carbonate or nitrate of guanidine, aminoguanidine, diaminoguanidine or triamino-guanldlne, (B) at least one alkali-metal or alkaline-earth-metal nitrate or ammonium nitrate as oxidizing agent, and (C) at least one carrier substance selected from silicon dioxide, alkali-metal silicates, alkaline-earth-metal silicates or aluminosilicates and/or at least one oxygen-supplying carrier substance selected from iron(III) oxide, cobalt oxides, manganese dioxide and copper(II) oxide, to moderate burn-up and improve slag formation.
Carbonates, hydrogen carbonates or nitrates of guanidine, aminoguanidine, diaminoguanidine or triaminoguanidine (TAGN) or its mixtures can be used as component (A). TAGN is preferably used. TAGN is virtually nontoxic (LD50 ' 3500 mg/kg rat), nonhygroscopic, sparingly soluble in water, thermally stable, combustible at low temperature and has low sensitivity to impact and friction. The gas yield in the burn-up of TAGN is very high, in which process a large proportion of nitrogen gas is produced.
Optionally, the TAGN may be replaced by 1 to 50% by weight of nitroguanidine. The cost of the component (A) can thereby be reduced and a beneficial burn-up behaviour achieved, since nitroguanidine has a lower burn-up rate than TAGN.
Alkali-metal or alkaline-earth-metal nitrates, ammonium nitrate and mixtures thereof can be used as oxidizing agents, component (B). Potassium nitrate is preferably used. Potassium nitrate is nonhygroscopic, nontoxic and makes possible a high gas yield during burn-up and a low burn-up temperature.
In the mixture of (A) and (B), component (A) is present in a quantity of about 20 to 55, preferably about 50 to 55% by weight, and component (B) in a quantity of about 80 to 45, preferably about 50 to 45% by weight. Preferably, component (A) is present 2172~22 in a quantity of about 50 to 55~ by weight and component (B) in a quantity of about 50 to 45~ by weight.
Silicon dioxide, alkali-metal silicates, alkaline-earth-metal silicates or aluminosilicates or mixtures thereof can be used as carrier substance, component (C). Examples of these are Aerosil 200 and Aerosil 300, highly disperse silicic acid and kieselgur (diatomaceous earth). Preferred carrier substance is silicic acid having a pH of about 7.
Iron(III) oxide, cobalt oxides, manganese dioxide and copper(II) oxide or mixtures thereof can also be used as component (C). The preferred oxygen-supplying carrier substance is iron(III) oxide.
Relative to the total quantity of the components (A) and (B), component (C) is present in a quantity of about 5 to 45, preferably about 8 to 20% by weight. If iron(III) oxide is used as oxygen-supplying carrier substance (C), it is present in a quantity of about 20 to 40, preferably about 25 to 35~ by weight, relative to the total quantity of the components (A) and (B).
Component (C) serves to moderate burn-up, i.e. to adjust the burn-up rate. Simultaneously, the slag or melt formation is improved. The slag formation is absolutely necessary, for example, in the case of an airbag.
An airbag essentially comprises a gas generator casing filled with the gas generator propellant, generally in tablet form, and an initial detonator (squib) for detonating the gas generator propellant, and also a gas bag. Suitable detonators are disclosed, for example, in US-PS 49 31 111. The gas bag, which is initially folded into a small pack, is filled, after the initial detonation, with the gases produced in the burn-up of the gas generator propellant and reaches its full volume in a time period of about 10 - 50 ms. The escape of hot sparks, molten material or solids from the gas generator into the gas bag has to be largely prevented, since it could result in a destruction ~172822 of the gas bag or in injury to the vehicle occupants. Thls is achieved by the slag formation.
The formation of slags simultaneously reduces the production of dust-type components which enter the lungs and which could escape from the gas generator of an airbag. Dust-type particles which enter the lungs have a diameter of about 6 ~m or less. The oxygen-supplying carrier substances additionally suppress the formation of toxic gases, such as carbon monoxide, during burn-up .
Optionally, the gas generator propellant may furthermore contain,as component (D), a binder which is soluble in water at room temperature. Preferred binders are cellulose compounds or polymers of one or more polymerizable olefinic unsaturated monomers. Examples of cellulose compounds are cellulose ethers, such as carboxymethylcellulose, methylcellulose ether, in particular methylhydroxyethylcellulose. A methylhydroxyethyl-cellulose which can be used satisfactorily is CULMINAL(R) MHEC
30000 PR supplied by the company Aqualon. Suitable polymers having binding action are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and polycarbonates.
Relative to the total quantity of components (A) and (B), component (D) is present in a quantity of about 0.1 to 5, preferably about 1.5 to 2.5~ by weight.
The binder (D) serves as desensitizing agent and as processing aid in the production of granular material or tablets from the gas generator propellant. It furthermore serves to reduce the hydrophilic nature of the gas generator propellant and to stabilize it.
The tablets or pellets of the gas generator propellant used in the gas generator can be produced by known methods, for instance by hot press working, extrusion, in rotary compression presses or in tableting machines. The size of the pellets or tablets 2172~22 depends on the desired burn time in the particular application case.
Working Examples The calculated quantities of triaminoguanidine nitrate (TAGN), optionally also nitroguanidine, and also potassium nitrate and optionally cellulose ether are dissolved in as little water as possible at 90C and iron oxide and/or silicon dioxide having a mean particle size of approximately 1 ~m is stirred into the solution. After predrying at 60C and 16 hPa with mechanical agitation, the mixture is comminuted in the still moist state and then, after drying at 60C, is compressed into tablets having a diameter of 6 mm and a height of 2 mm using a tableting machine.
The tested mixtures are listed in Table I. Mixture 1 does not contain any silicon dioxide and Mixture 5 does not contain any iron(III) oxide. As a comparison mixture, Mixture 6 does not contain either silicon dioxide or iron(III) oxide.
Table I: Composition of the mixtures in percentaqe by weiqht TAGN 39.1 39.1 39.1 29.1 47.3 53.0 Nitroguanidine - - - 10.0 -KNO3 30.9 30.9 30.9 30.9 40.7 47.0 Fe2O3 30.0 20.0 14.0 14.0 -SiO2 - 10.0 14.0 14.0 12.0 -Cellulose ether - - 2.0 2.0 -Table II shows an overview of the reaction parameters determined by calculation. A high reaction temperature occurs in Mixture 5 and particularly in Mixture 6.
~1 7~822 Table II: Calculated values 2 balance % +2.13 +1.13 -1.84 -1.57 +0.25 +0.84 Volume ccm 1000 1000 1000 1000 10001000 Charging density (g/ccm)0.1 0.1 0.1 0.10.1 0.1 Pressure bar 427 444 470 457 654810 Temperature K 1973 2116 2116 2116 24682666 Number of moles of the gases used mol/kg21.1 22.6 23.9 23.427.5 28.8 Heat of explosion J/g 3369 3092 29982913 3852 4566 Table III shows an overview of the reaction products produced during burn-up and their quantities.
Table III: Reaction products at 298 K, freeze-out temperature 1,500 K
Compound 1 2 3 4 5 6 (% by wt) C2 3.604 10.086 11.538 13.228 12.408 3.768 H2O 18.952 18.817 18.828 17.711 22.935 26.692 N2 27.219 27.219 27.217 26.735 33.383 37.596 CO 0.000 0.134 1.283 1.223 0.0000.000 H2 - 0.017 0.139 0.109 0.0000.000 NO 0.001 0.000 0.000 0.000 0.0090.018 2 0.001 0.000 0.000 0.000 0.2480.826 HCN 0.000 0.000 0.000 0.000 0.0000.000 NH3 0.000 0.000 0.003 0.002 0.0000.000 KOH 0.086 0.000 0.003 0.003 0.0530.101 K2CO3 21.014 0.000 0.000 0.000 0.150 31.997 FeO - - 12.597 12.597 - -Fe2O3 3.726 0.000 0.000 0.000 - 0.000 Fe3O4 25.396 19.331 0.000 0.000 - 0.000 K2SiO3 - 23.572 23.572 23.572 30.813 SiO2 - 0.820 4.820 4.820 '~172822 , Table IV shows the test results on the susceptibility to decomposition, stability, slag formation and burn-up behaviour of the various mixtures. Mixtures 1 to 5 exhibited good to very good burn-up behaviour, in particular in relation to a constant, high burn rate. Only inadequate slag formation and inadequate burn-up behaviour was observed for the comparison Mixture 6, which did not contain either silicon dioxide or iron(III) oxide as component (C).
Table IV: Test results Mixture 1 2 3 4 5 6 Decomposition temperature C *) - 207 178 203 Measurement conditions:
Heating rate 2C/min from 15C below decomposition temperature Stability : Holland test Sample weight : 2.5 g Test temperature: 105C
Test time : 72 h Weight loss (~ by weight) - - 0.28 0.40 0.13 -Slag formation ++ ++ ++ ++ ++
Burn-up behaviour + ++ ++ ++ +
Note: ++ very good; + good; - inadequate *) For Mixture 1, other stability tests were performed:
Stability tests on Mixture 1 1. Differential thermal analysis Apparatus: HERAEUS - FUS-O-MAT
Heating rate 10C/min, initial sample mass 10 mg 'L 8 Result: KNO3 conversion: 129/130C
Start of exothermic reaction: 168C
2. Differential thermogravimetry Apparatus: LINSEIS - Simultan DTA/TG
Heating rate 5C/min, initial sample mass 20 mg Result: KNO3 conversion: 127C
Start of exothermic reaction: 135C
Deflagration: 158C
Test burn-uP of Mixture 1 A test burn-up of Mixture 1 was carried out in a normal aluminium gas generator casing for a 60 litre airbag, provided with a bore for pressure measurement, in a 60 litre can. The test temperature for Test 1 was -35C and the propellant charge weight was 51.0 g. The propellant charge was composed of tablets having a diameter of 6 mm and a height of 2 mm.
Figure 1 shows the pressure in the burn-up chamber in units of 105 pascals as a function of the time after detonation in milliseconds for Test 1.
The pressure build-up takes place within approximately 1.5 ms and the pressure drop to half the maximum pressure takes place after approximately 27 ms. The maximum pressure is 1.88*107 Pa and is reached after 12.3 ms.
Analysis of the toxic qas components formed in ppm CO 300 NH3 > 70 NOx 60 Test burn-up of Mixture 2 The test burn-up of Mixture 2 was carried out in an aluminium Euro gas generator casing for a 35 litre airbag, provided with a bore for pressure measurement, in a 60 litre can. The test g temperature was -35C in Test 2 and +20C in Test 3. The propellant charge weight was 41.0 g in Test 2 and 30.0 g in Test 3. The propellant charge was composed of tablets having a diameter of 6 mm and a height of 2 mm.
Figure 2 shows the pressure in the burn-up chamber in units of 105 pascals as a function of the time after the detonation in milliseconds for Test 2.
The pressure build-up takes place within approximately 1.5 ms and the pressure drop to half the maximum pressure takes place after approximately 27 ms. The maximum pressure was 1.45*107 Pa and was reached after 15.7 ms.
Figure 3 shows the pressure in the burn-up chamber in units of 105 pascals as a function of the time after the detonation in milliseconds for Test 3.
The pressure build-up takes place within approximately 1.5 ms and the pressure drop to half the maximum pressure takes place after approximately 27 ms. The maximum pressure was 1.33*107 Pa and was reached after 7.5 ms.
The gas generator propellant according to the invention is composed of nontoxic, easily producible and inexpensive components whose processing does not present problems. Their thermal stability results in good storage capability. Despite low burn-up temperature, the ignitability of the mixtures is good. They burn rapidly and provide high gas yield with very low CO and NO components. The mixtures according to the invention are therefore particularly suitable for use as gas generating agents in the various airbag systems, as extinguishing agents or propellants. In addition, the gas generator propellants are readily recyclable.
Gas generator propellant The invention relates to solid gas generator propellants based on guanidine compounds on suitable carriers.
JP H5-254977 discloses gas generator propellants for airbags based on triaminoguanidine nitrate (TAGN), which may additionally contain oxidizing agents such as alkali-metal and alkaline-earth-metal nitrates, nitrites, chlorates or perchlorates. Molybdenum sulphide may be present as a further component. The advantage of using TAGN instead of the known sodium azides is the nontoxic nature and also the good stability of TAGN, which, in addition, does not form any salts which are sensitive to friction and impact in combination with heavy metals. The burn-up rate of the gas generator propellants should be possible via a variation in the compression pressure during the production of pellets or tablets from the component mixture.
Disadvantages of such gas generator propellants are a still inadequate controllability of the burn-up, the development of toxic gases such as CO and an imperfect formation of slag during burn-up, which results in an increased development of dusts, some of which enter the lungs.
Compared with JP H5-254977, the object of the present invention is to provide improved gas generator propellants whose burn-up behaviour can be systematically adjusted and which form readily retainable slags during burn-up and minimize the production of toxic gases. The gas generator propellants are intended to be thermally stable, readily ignitable, fast-burning, even at low temperature, and satisfactorily storable and to ensure a high gas yield. In addition, said gas generator propellants are intended to make it possible to reduce the size of the generator casing and consequently reduce its weight compared with known generators operated with sodium azide.
According to the invention, these objects are achieved by a gas generator propellant, comprising (A) at least one carbonate, hydrogen carbonate or nitrate of guanidine, aminoguanidine, diaminoguanidine or triamino-guanldlne, (B) at least one alkali-metal or alkaline-earth-metal nitrate or ammonium nitrate as oxidizing agent, and (C) at least one carrier substance selected from silicon dioxide, alkali-metal silicates, alkaline-earth-metal silicates or aluminosilicates and/or at least one oxygen-supplying carrier substance selected from iron(III) oxide, cobalt oxides, manganese dioxide and copper(II) oxide, to moderate burn-up and improve slag formation.
Carbonates, hydrogen carbonates or nitrates of guanidine, aminoguanidine, diaminoguanidine or triaminoguanidine (TAGN) or its mixtures can be used as component (A). TAGN is preferably used. TAGN is virtually nontoxic (LD50 ' 3500 mg/kg rat), nonhygroscopic, sparingly soluble in water, thermally stable, combustible at low temperature and has low sensitivity to impact and friction. The gas yield in the burn-up of TAGN is very high, in which process a large proportion of nitrogen gas is produced.
Optionally, the TAGN may be replaced by 1 to 50% by weight of nitroguanidine. The cost of the component (A) can thereby be reduced and a beneficial burn-up behaviour achieved, since nitroguanidine has a lower burn-up rate than TAGN.
Alkali-metal or alkaline-earth-metal nitrates, ammonium nitrate and mixtures thereof can be used as oxidizing agents, component (B). Potassium nitrate is preferably used. Potassium nitrate is nonhygroscopic, nontoxic and makes possible a high gas yield during burn-up and a low burn-up temperature.
In the mixture of (A) and (B), component (A) is present in a quantity of about 20 to 55, preferably about 50 to 55% by weight, and component (B) in a quantity of about 80 to 45, preferably about 50 to 45% by weight. Preferably, component (A) is present 2172~22 in a quantity of about 50 to 55~ by weight and component (B) in a quantity of about 50 to 45~ by weight.
Silicon dioxide, alkali-metal silicates, alkaline-earth-metal silicates or aluminosilicates or mixtures thereof can be used as carrier substance, component (C). Examples of these are Aerosil 200 and Aerosil 300, highly disperse silicic acid and kieselgur (diatomaceous earth). Preferred carrier substance is silicic acid having a pH of about 7.
Iron(III) oxide, cobalt oxides, manganese dioxide and copper(II) oxide or mixtures thereof can also be used as component (C). The preferred oxygen-supplying carrier substance is iron(III) oxide.
Relative to the total quantity of the components (A) and (B), component (C) is present in a quantity of about 5 to 45, preferably about 8 to 20% by weight. If iron(III) oxide is used as oxygen-supplying carrier substance (C), it is present in a quantity of about 20 to 40, preferably about 25 to 35~ by weight, relative to the total quantity of the components (A) and (B).
Component (C) serves to moderate burn-up, i.e. to adjust the burn-up rate. Simultaneously, the slag or melt formation is improved. The slag formation is absolutely necessary, for example, in the case of an airbag.
An airbag essentially comprises a gas generator casing filled with the gas generator propellant, generally in tablet form, and an initial detonator (squib) for detonating the gas generator propellant, and also a gas bag. Suitable detonators are disclosed, for example, in US-PS 49 31 111. The gas bag, which is initially folded into a small pack, is filled, after the initial detonation, with the gases produced in the burn-up of the gas generator propellant and reaches its full volume in a time period of about 10 - 50 ms. The escape of hot sparks, molten material or solids from the gas generator into the gas bag has to be largely prevented, since it could result in a destruction ~172822 of the gas bag or in injury to the vehicle occupants. Thls is achieved by the slag formation.
The formation of slags simultaneously reduces the production of dust-type components which enter the lungs and which could escape from the gas generator of an airbag. Dust-type particles which enter the lungs have a diameter of about 6 ~m or less. The oxygen-supplying carrier substances additionally suppress the formation of toxic gases, such as carbon monoxide, during burn-up .
Optionally, the gas generator propellant may furthermore contain,as component (D), a binder which is soluble in water at room temperature. Preferred binders are cellulose compounds or polymers of one or more polymerizable olefinic unsaturated monomers. Examples of cellulose compounds are cellulose ethers, such as carboxymethylcellulose, methylcellulose ether, in particular methylhydroxyethylcellulose. A methylhydroxyethyl-cellulose which can be used satisfactorily is CULMINAL(R) MHEC
30000 PR supplied by the company Aqualon. Suitable polymers having binding action are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and polycarbonates.
Relative to the total quantity of components (A) and (B), component (D) is present in a quantity of about 0.1 to 5, preferably about 1.5 to 2.5~ by weight.
The binder (D) serves as desensitizing agent and as processing aid in the production of granular material or tablets from the gas generator propellant. It furthermore serves to reduce the hydrophilic nature of the gas generator propellant and to stabilize it.
The tablets or pellets of the gas generator propellant used in the gas generator can be produced by known methods, for instance by hot press working, extrusion, in rotary compression presses or in tableting machines. The size of the pellets or tablets 2172~22 depends on the desired burn time in the particular application case.
Working Examples The calculated quantities of triaminoguanidine nitrate (TAGN), optionally also nitroguanidine, and also potassium nitrate and optionally cellulose ether are dissolved in as little water as possible at 90C and iron oxide and/or silicon dioxide having a mean particle size of approximately 1 ~m is stirred into the solution. After predrying at 60C and 16 hPa with mechanical agitation, the mixture is comminuted in the still moist state and then, after drying at 60C, is compressed into tablets having a diameter of 6 mm and a height of 2 mm using a tableting machine.
The tested mixtures are listed in Table I. Mixture 1 does not contain any silicon dioxide and Mixture 5 does not contain any iron(III) oxide. As a comparison mixture, Mixture 6 does not contain either silicon dioxide or iron(III) oxide.
Table I: Composition of the mixtures in percentaqe by weiqht TAGN 39.1 39.1 39.1 29.1 47.3 53.0 Nitroguanidine - - - 10.0 -KNO3 30.9 30.9 30.9 30.9 40.7 47.0 Fe2O3 30.0 20.0 14.0 14.0 -SiO2 - 10.0 14.0 14.0 12.0 -Cellulose ether - - 2.0 2.0 -Table II shows an overview of the reaction parameters determined by calculation. A high reaction temperature occurs in Mixture 5 and particularly in Mixture 6.
~1 7~822 Table II: Calculated values 2 balance % +2.13 +1.13 -1.84 -1.57 +0.25 +0.84 Volume ccm 1000 1000 1000 1000 10001000 Charging density (g/ccm)0.1 0.1 0.1 0.10.1 0.1 Pressure bar 427 444 470 457 654810 Temperature K 1973 2116 2116 2116 24682666 Number of moles of the gases used mol/kg21.1 22.6 23.9 23.427.5 28.8 Heat of explosion J/g 3369 3092 29982913 3852 4566 Table III shows an overview of the reaction products produced during burn-up and their quantities.
Table III: Reaction products at 298 K, freeze-out temperature 1,500 K
Compound 1 2 3 4 5 6 (% by wt) C2 3.604 10.086 11.538 13.228 12.408 3.768 H2O 18.952 18.817 18.828 17.711 22.935 26.692 N2 27.219 27.219 27.217 26.735 33.383 37.596 CO 0.000 0.134 1.283 1.223 0.0000.000 H2 - 0.017 0.139 0.109 0.0000.000 NO 0.001 0.000 0.000 0.000 0.0090.018 2 0.001 0.000 0.000 0.000 0.2480.826 HCN 0.000 0.000 0.000 0.000 0.0000.000 NH3 0.000 0.000 0.003 0.002 0.0000.000 KOH 0.086 0.000 0.003 0.003 0.0530.101 K2CO3 21.014 0.000 0.000 0.000 0.150 31.997 FeO - - 12.597 12.597 - -Fe2O3 3.726 0.000 0.000 0.000 - 0.000 Fe3O4 25.396 19.331 0.000 0.000 - 0.000 K2SiO3 - 23.572 23.572 23.572 30.813 SiO2 - 0.820 4.820 4.820 '~172822 , Table IV shows the test results on the susceptibility to decomposition, stability, slag formation and burn-up behaviour of the various mixtures. Mixtures 1 to 5 exhibited good to very good burn-up behaviour, in particular in relation to a constant, high burn rate. Only inadequate slag formation and inadequate burn-up behaviour was observed for the comparison Mixture 6, which did not contain either silicon dioxide or iron(III) oxide as component (C).
Table IV: Test results Mixture 1 2 3 4 5 6 Decomposition temperature C *) - 207 178 203 Measurement conditions:
Heating rate 2C/min from 15C below decomposition temperature Stability : Holland test Sample weight : 2.5 g Test temperature: 105C
Test time : 72 h Weight loss (~ by weight) - - 0.28 0.40 0.13 -Slag formation ++ ++ ++ ++ ++
Burn-up behaviour + ++ ++ ++ +
Note: ++ very good; + good; - inadequate *) For Mixture 1, other stability tests were performed:
Stability tests on Mixture 1 1. Differential thermal analysis Apparatus: HERAEUS - FUS-O-MAT
Heating rate 10C/min, initial sample mass 10 mg 'L 8 Result: KNO3 conversion: 129/130C
Start of exothermic reaction: 168C
2. Differential thermogravimetry Apparatus: LINSEIS - Simultan DTA/TG
Heating rate 5C/min, initial sample mass 20 mg Result: KNO3 conversion: 127C
Start of exothermic reaction: 135C
Deflagration: 158C
Test burn-uP of Mixture 1 A test burn-up of Mixture 1 was carried out in a normal aluminium gas generator casing for a 60 litre airbag, provided with a bore for pressure measurement, in a 60 litre can. The test temperature for Test 1 was -35C and the propellant charge weight was 51.0 g. The propellant charge was composed of tablets having a diameter of 6 mm and a height of 2 mm.
Figure 1 shows the pressure in the burn-up chamber in units of 105 pascals as a function of the time after detonation in milliseconds for Test 1.
The pressure build-up takes place within approximately 1.5 ms and the pressure drop to half the maximum pressure takes place after approximately 27 ms. The maximum pressure is 1.88*107 Pa and is reached after 12.3 ms.
Analysis of the toxic qas components formed in ppm CO 300 NH3 > 70 NOx 60 Test burn-up of Mixture 2 The test burn-up of Mixture 2 was carried out in an aluminium Euro gas generator casing for a 35 litre airbag, provided with a bore for pressure measurement, in a 60 litre can. The test g temperature was -35C in Test 2 and +20C in Test 3. The propellant charge weight was 41.0 g in Test 2 and 30.0 g in Test 3. The propellant charge was composed of tablets having a diameter of 6 mm and a height of 2 mm.
Figure 2 shows the pressure in the burn-up chamber in units of 105 pascals as a function of the time after the detonation in milliseconds for Test 2.
The pressure build-up takes place within approximately 1.5 ms and the pressure drop to half the maximum pressure takes place after approximately 27 ms. The maximum pressure was 1.45*107 Pa and was reached after 15.7 ms.
Figure 3 shows the pressure in the burn-up chamber in units of 105 pascals as a function of the time after the detonation in milliseconds for Test 3.
The pressure build-up takes place within approximately 1.5 ms and the pressure drop to half the maximum pressure takes place after approximately 27 ms. The maximum pressure was 1.33*107 Pa and was reached after 7.5 ms.
The gas generator propellant according to the invention is composed of nontoxic, easily producible and inexpensive components whose processing does not present problems. Their thermal stability results in good storage capability. Despite low burn-up temperature, the ignitability of the mixtures is good. They burn rapidly and provide high gas yield with very low CO and NO components. The mixtures according to the invention are therefore particularly suitable for use as gas generating agents in the various airbag systems, as extinguishing agents or propellants. In addition, the gas generator propellants are readily recyclable.
Claims (12)
1. A gas generator propellant, comprising (A) at least one carbonate, hydrogen carbonate or nitrate of guanidine, aminoguanidine, diaminoguanidine or triaminoguanidine in a quantity of 20 to 55% by weight, (B) at least one alkali-metal or alkaline-earth-metal nitrate or ammonium nitrate as oxidizing agent in a quantity of 80 to 45% by weight, and to moderate burn-up and improve slag formation in a quantity of 5 to 45% by weight, relative to the total quantity of components (A) and (B), (C1) at least one carrier substance selected from silicon dioxide, alkali-metal silicates, alkaline-earth-metal silicates or aluminosilicates and/or (C2) at least one oxygen-supplying carrier substance selected from iron(III) oxide, cobalt oxides, manganese dioxide and copper(II) oxide.
2. A gas generator propellant according to Claim 1, wherein component (A) is present in a quantity of 50 to 55% by weight, component (B) in a quantity of 50 to 45% by weight and components (C1) and/or (C2), relative to the total quantity of components (A) and (B), in a quantity of 8 to 20% by weight.
3. A gas generator propellant according to Claim 1 or 2, wherein component (A) is triaminoguanidine nitrate.
4. A gas generator propellant according to any one of Claims 1 to 3, wherein component (B) is potassium nitrate.
5. A gas generator propellant according to any one of Claims 1 to 4, wherein component (C1) is silicon dioxide with a pH
of about 7.
of about 7.
6. A gas generator propellant according to any one of Claims 1 to 5, wherein component (A) is composed of 99 to 50% by weight of triaminoguanidine nitrate and 1 to 50% by weight of nitroguanidine, relative to the total quantity of component (A).
7. A gas generator propellant according to any one of Claims 1 to 6, wherein component (C2) is iron(III) oxide.
8. A gas generator propellant according to Claim 7, wherein the iron(III) oxide is present in a quantity of 20 to 40, preferably 25 to 35% by weight, relative to the total quantity of the components (A) and (B).
9. A gas generator propellant according to any one of Claims 1 to 8, additionally comprising (D) a binder which is soluble in water at room temperature.
10. A gas generator propellant according to Claim 9, wherein the binder is a cellulose ether, such as carboxymethyl-cellulose, methylcellulose ether and in particular methyl-hydroxyethylcellulose or a polymer of one or more polymerizable olefinic unsaturated monomers.
11. A gas generator propellant according to Claim 9 or 10, wherein the binder is present in a quantity of 0.1 to 5, preferably 1.5 to 2.5% by weight, relative to the total quantity of the components (A) and (B).
12. Use of the gas generator propellant according to any one of Claims 1 to 11 as gas generating agent in airbags, as extinguishing agent or as propellant.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4334099.7 | 1993-10-06 | ||
| DE4334099 | 1993-10-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2172822A1 true CA2172822A1 (en) | 1995-04-13 |
Family
ID=6499558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002172822A Abandoned CA2172822A1 (en) | 1993-10-06 | 1994-10-06 | Gas developing agent |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0722429B1 (en) |
| JP (1) | JPH09503195A (en) |
| CN (1) | CN1132501A (en) |
| AT (1) | ATE178304T1 (en) |
| AU (1) | AU687895B2 (en) |
| BR (1) | BR9407761A (en) |
| CA (1) | CA2172822A1 (en) |
| CZ (1) | CZ88796A3 (en) |
| DE (2) | DE9416112U1 (en) |
| ES (1) | ES2130448T3 (en) |
| HU (1) | HUT76867A (en) |
| PL (1) | PL175606B1 (en) |
| RU (1) | RU2117649C1 (en) |
| SK (1) | SK45596A3 (en) |
| WO (1) | WO1995009825A1 (en) |
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| US6555083B1 (en) | 1997-05-08 | 2003-04-29 | Technostar Co., Ltd | Method of preparation of sealed gas chambers |
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| 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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| DE884170C (en) * | 1946-11-08 | 1953-07-23 | Ici Ltd | Gas Generating Charge |
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-
1994
- 1994-10-06 CZ CZ96887A patent/CZ88796A3/en unknown
- 1994-10-06 BR BR9407761A patent/BR9407761A/en not_active Application Discontinuation
- 1994-10-06 SK SK455-96A patent/SK45596A3/en unknown
- 1994-10-06 JP JP7510558A patent/JPH09503195A/en active Pending
- 1994-10-06 AT AT94928758T patent/ATE178304T1/en not_active IP Right Cessation
- 1994-10-06 PL PL94313943A patent/PL175606B1/en unknown
- 1994-10-06 HU HU9600744A patent/HUT76867A/en unknown
- 1994-10-06 ES ES94928758T patent/ES2130448T3/en not_active Expired - Lifetime
- 1994-10-06 WO PCT/DE1994/001184 patent/WO1995009825A1/en active IP Right Grant
- 1994-10-06 CA CA002172822A patent/CA2172822A1/en not_active Abandoned
- 1994-10-06 CN CN94193677A patent/CN1132501A/en active Pending
- 1994-10-06 RU RU96109379A patent/RU2117649C1/en active
- 1994-10-06 AU AU78066/94A patent/AU687895B2/en not_active Ceased
- 1994-10-06 DE DE9416112U patent/DE9416112U1/en not_active Expired - Lifetime
- 1994-10-06 DE DE59408048T patent/DE59408048D1/en not_active Expired - Fee Related
- 1994-10-06 EP EP94928758A patent/EP0722429B1/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002511828A (en) * | 1996-07-29 | 2002-04-16 | オートモーティブ システムズ ラボラトリー インコーポレーテッド | Thermostable non-azide propellant for automotive airbags |
| US6555083B1 (en) | 1997-05-08 | 2003-04-29 | Technostar Co., Ltd | Method of preparation of sealed gas chambers |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0722429B1 (en) | 1999-03-31 |
| WO1995009825A1 (en) | 1995-04-13 |
| ATE178304T1 (en) | 1999-04-15 |
| CZ88796A3 (en) | 1996-08-14 |
| SK45596A3 (en) | 1997-01-08 |
| AU687895B2 (en) | 1998-03-05 |
| AU7806694A (en) | 1995-05-01 |
| EP0722429A1 (en) | 1996-07-24 |
| DE59408048D1 (en) | 1999-05-06 |
| DE9416112U1 (en) | 1994-12-15 |
| PL313943A1 (en) | 1996-08-05 |
| ES2130448T3 (en) | 1999-07-01 |
| HUT76867A (en) | 1997-12-29 |
| RU2117649C1 (en) | 1998-08-20 |
| HU9600744D0 (en) | 1996-05-28 |
| PL175606B1 (en) | 1999-01-29 |
| BR9407761A (en) | 1997-03-04 |
| CN1132501A (en) | 1996-10-02 |
| JPH09503195A (en) | 1997-03-31 |
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Legal Events
| Date | Code | Title | Description |
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| FZDE | Discontinued | ||
| FZDE | Discontinued |
Effective date: 20011009 |