Pyrotechnic agent

Abstract

The invention relates to a pyrotechnic agent containing at least one azotetrazolate as a component thereof.

Claims

1. A pyrotechnic consisting of 20 to 50 wt. % of at least one azotetrazolate component selected from the group consisting of aminoguanidine-5,5′-azotetrazolate (AGATZ) and guanidine-5,5′-azotetrazolate (GATZ), and 50 to 80 wt. % of at least one additive selected from the group consisting of ammonium picrate, aminoguanidinium picrate, guanidinium picrate, aminoguanidinium styphnate, guanidinium styphnate, nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of tetrazole and/or its salts, nitraminotetrazole and/or its salts, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, guanidine nitrate, dicyandiamidine nitrate, diaminoguanidine azotetrazolate, nitrates of alkali and/or alkaline-earth metals and/or of ammonium, perchlorates of alkali and/or alkaline-earth metals and/or of ammonium, peroxides of alkali and/or alkaline-earth metals and/or of zinc, aluminium, titanium, titanium hydride, boron, boron hydride, zirconium, zirconium hydride, silicon, graphite, activated charcoal, carbon black, cellulose and/or its derivatives, polyvinylbutyrals, polynitropolyphenylene, polynitrophenyl ether, plexigum, polyvinyl acetate and copolymers, hexogen, octogen, nitrocellulose, ferrocene and/or its derivatives, acetonylacetates, salicylates, carbonates, melamine, silicates, silica gels, and boron nitride, wherein a deflagration temperature of the pyrotechnic agent in a range from 165° C. to 195° C.

2. The pyrotechnic agent according to claim 1, comprising 30 to 60 wt. % of at least one oxidising agent selected from the group consisting of nitrates of alkali and/or alkaline-earth metals and/or of ammonium, perchlorates of alkali and/or alkaline-earth metals and/or of ammonium, and peroxides of alkali and/or alkaline-earth metals and/or of zinc.

3. The pyrotechnic agent according to claim 1, comprising 15 to 40 wt. % of at least one nitrogen-containing compound selected from the group consisting of ammonium picrate, aminoguanidinium picrate, guanidinium picrate, aminoguanidinium styphnate, guanidinium styphnate, nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of tetrazole and/or its salts, nitraminotetrazole and/or its salts, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, guanidine nitrate, dicyandiamidine nitrate, and diaminoguanidine azotetrazolate.

4. The pyrotechnic agent according to claim 1, comprising 1 to 40 wt. % of at least one high-energy additive selected from the group consisting of hexogen, octogen and nitrocellulose.

5. The pyrotechnic agent according to claim 1, comprising 1 to 15 wt. % of at least one reducing agent selected from the group consisting of aluminium, titanium, titanium hydride, boron, boron hydride, zirconium, zirconium hydride, silicon, graphite, activated charcoal, and carbon black.

6. A pyrotechnic agent according to claim 1, comprising 1 to 20 wt. % of a binder selected from the group consisting of cellulose and its derivatives, polyvinylbutyrals, polynitropolyphenylene, polynitrophenyl ether, plexigum, polyvinyl acetate and copolymers.

7. The pyrotechnic agent according to claim 1, comprising 1 to 10 wt. % of at least one combustion moderator and processing aid selected from the group consisting of ferrocene and its derivatives, acetonylacetates, salicylates, silicates, silica gels and boron nitride.

8. A thermal early-ignition agent comprising the pyrotechnic agent according to claim 1.

9. A thermal safety fuse comprising the pyrotechnic agent according to claim 1.

10. A vehicle safety system comprising the pyrotechnic agent according to claim 1.

11. A gas generator comprising the pyrotechnic agent according to claim 1.

12. A separator for battery terminals comprising the pyrotechnic agent according to claim 1.

13. The pyrotechnic agent according to claim 1, wherein the at least one azotetrazolate component and the at least one additive are not coated.

14. The pyrotechnic agent according to claim 1, wherein the at least one azotetrazolate component and the at least one additive are not coated with silicone.

15. A pyrotechnic agent consisting essentially of 20 to 50 wt. % of aminoguanidine-5,5′-azotetrazolate (AGATZ), and 50 to 80 wt. % of at least one additive selected from the group consisting of ammonium picrate, aminoguanidinium picrate, guanidinium picrate, aminoguanidinium styphnate, guanidinium styphnate, nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of tetrazole and/or its salts, nitraminotetrazole and/or its salts, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, guanidine nitrate, dicyandiamidine nitrate, diaminoguanidine azotetrazolate, nitrates of alkali and/or alkaline-earth metals and/or of ammonium, perchlorates of alkali and/or alkaline-earth metals and/or of ammonium, peroxides of alkali and/or alkaline-earth metals and/or of zinc, aluminium, titanium, titanium hydride, boron, boron hydride, zirconium, zirconium hydride, silicon, graphite, activated charcoal, carbon black, cellulose and/or its derivatives, polyvinylbutyrals, polynitropolyphenylene, polynitrophenyl ether, plexigum, polyvinyl acetate and copolymers, hexogen, octogen, nitrocellulose, ferrocene and/or its derivatives, acetonylacetates, salicylates, carbonates, melamine, silicates, silica gels, and boron nitride.

Description

(1) The invention is described in more detail by means of the following examples, without however being restricted thereto:

(2) The compositions of 27 different mixtures of the pyrotechnic agent are listed in Table 1. The components were weighed out in the specified amounts (amounts refer to weight percent) into plastics containers and homogenised for 30 minutes in a tumble mixer.

(3) TABLE-US-00001 TABLE 1 Mixtures Amino- AGATZ guanidinium Sodium Potassium Mixture (GATZ) Hexogen Octogen picrate Others nitrate nitrate 1 30 20 50 2 30 20 50 3 30 30 40 4 30 10 20 40 5 30 10 20 40 6 30 10 AGSt: 20 40 7 30 10 20 40 8 30 10 AGSt: 20 40 9 30 GPik: 10 40 AGSt: 20 10 30 GPik: 30 40 11 30 20 AGSt: 10 40 12 30 30 40 13 30 30 40 14 30 30 40 15 30 AGSt: 30 40 16 30 10 GPik: 20 40 17 30 10 Nigu: 20 40 18 30 AGSt: 30 40 19 30 10  GSt: 20 40 20 GATZ: 30 AGSt: 30 40 21 GATZ: 30 30 40 22 GATZ: 30 10 AGSt: 20 40 23 30 AGSt: 10 40 APik: 20 24 30 20 APik: 10 40 25 30 APik: 30 40 26 30 10 GPik: 20 40 27 30 10 GPik: 20 40 AGSt: Aminoguanidinium styphnate GPik: Guanidinium picrate Nigu: Nitroguanidine APik: Ammonium picrate

(4) The deflagration temperatures and friction and impact sensitivities of the mixtures are given in Table 2. The friction and impact sensitivities were measured according to the methods of the Bundesanstalt für Materialforschung (BAM) (Federal Institute for Materials Testing), while the deflagration temperatures were measured by thermo-gravimetric analysis (Mettler Company) at a heating rate of 10° C. per minute.

(5) TABLE-US-00002 TABLE 2 Summary of the deflagration temperatures and friction and impact sensitivities Deflagration Friction Impact temperature sensitivity sensitivity Mixture [° C.] [N] [J] 1 180 240 3 2 190 240 3 3 182 >360 4 4 165 240 3 5 172 360 2 6 190 >360 2 7 172 >360 2 8 172 >360 4 9 181 >360 5 10 192 >360 8 11 178 >360 6 12 182 >360 4 13 221 360 2 14 217 240 3 15 172 >360 6 16 192 >360 5 17 191 >360 6 18 174 >360 6 19 182 >360 10 20 181 >360 8 21 195 >360 10 22 180 >360 4 23 180 >360 5 24 180 >360 4 25 175 >360 3 26 175 >360 2 27 180 >360 3

(6) The weight losses and deflagration temperatures after thermal loading (24 hours, 125° C. and 400 hours, 110° C.) of some of the mixtures chosen from the examples are summarised in Table 3. The measurement of the weight loss was carried out in a similar way to the Holland Test. The deflagration temperatures were measured by thermo-gravimetric analysis (Mettler Company) at a heating rate of 10° C. per minute.

(7) After 400 hours only slight weight losses of 0.1 to 0.7 wt. % are detected, and there are no significant changes in the deflagration temperature after thermal loading.

(8) TABLE-US-00003 TABLE 3 Summary of the weight losses and deflagration temperatures Deflagration Deflagration Weight loss Weight loss temp, after temp, after Mix- 24 h, 125° C. 400 h, 110° C. 24 h, 125° C. 400 h, 110° C. ture [wt. %] [wt. %] [° C.] [° C.] 5 0.34 0.7 172 178 12 0.03 0.1 182 191 26 2.11 0.7 175 175 27 0.36 0.2 180 186

(9) These results show that the specific pyrotechnic agents according to the invention have deflagration temperatures in the range from 172° to 191° C. and should be regarded as stable according to the requirements of the automobile industry.

(10) In addition the following mixtures have proved to be particularly advantageous, in particular also for use in separators for battery terminals: 30 wt. % aminoguanidine-5,5′-azotetrazolate, 27.5 wt. % guanidinium picrate, 40 wt. % sodium nitrate, 2 wt. % titanium and 0.5 wt. % graphite; 29 wt. % aminoguanidine-5,5′-azotetrazolate, 29 wt. % guanidinium picrate, 40 wt. % sodium nitrate, 1.5 wt. % barium carbonate and 0.5 wt. % Aerosil; 24 wt. % aminoguanidine-5,5′-azotetrazolate, 24 wt. % guanidinium picrate, 50 wt. % sodium nitrate, 1.5 wt. % barium carbonate and 0.5 wt. % Aerosil; 29 wt. % aminoguanidine-5,5′-azotetrazolate, 29 wt. % guanidinium picrate, 40 wt. % sodium nitrate, 1.5 wt. % strontium carbonate and 0.5 wt. % Aerosil.