Metal hydrazine complexes used as gas generants

• US 5,970,703 A
• Filed: 09/22/1997
• Issued: 10/26/1999
• Est. Priority Date: 01/19/1994
• Status: Expired due to Term

• Current Assignee: Northrop Grumman Innovation Systems, Inc. (Northrop Grumman Corporation)
• Original Assignee: Cordant Technologies, Inc. (Howmet Aerospace, Inc.)
• Inventors: Doll, Daniel W., Lund, Gary K., Blau, Reed J., Hinshaw, Jerald C.
• Primary Examiner(s): Miller, Edward A.
• Application Number:
  US08/934,900
• Time in Patent Office: 764 Days
• Field of Search: 149/36, 149/45, 280/741, 60/219
• US Class Current: 60/219
• CPC Class Codes: C06B 29/00 Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
• CPC Class Codes: C06B 31/00 Compositions containing an inorganic nitrogen-oxygen salt
• CPC Class Codes: C06B 41/00 Compositions containing a nitrated metallo-organic compound
• CPC Class Codes: C06B 43/00 Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
• CPC Class Codes: C06D 5/06 by reaction of two or more solids

Abstract

Gas generating compositions and methods for their use are provided. Metal complexes are used as gas generating compositions. These complexes are comprised of a metal cation template, a neutral ligand containing hydrogen and nitrogen, and sufficient oxidizing anion to balance the charge of the complex. The complexes are formulated such that when the complex combusts, nitrogen gas and water vapor is produced. Specific examples of such complexes include metal nitrite ammine, metal nitrate ammine, and metal perchlorate ammine complexes, as well as hydrazine complexes. A binder and co-oxidizer can be combined with the metal complexes to improve crush strength of the gas generating compositions and to permit efficient combustion of the binder. Such gas generating compositions are adaptable for use in gas generating devices such as automobile air bags.

Claims

1. A method of inflating an inflatable air bag or balloon comprising

generating substantially non-toxic gas by combusting an at least essentially azide-free gas generating formulation containing at least one metal complex having a transition metal cation or alkaline earth metal cation and at least one neutral ligand comprised of hydrazine, and sufficient oxidizing anion to balance the charge of the metal cation, wherein when the gas generating formulation combusts, a substantially non-toxic mixture of gases containing nitrogen gas and water vapor is produced;

and

inflating said air bag or balloon using said gases.

2. A method according to claim 1, wherein the metal cation is of a metal selected from the group consisting of manganese, magnesium, cobalt and zinc.

3. A method according to claim 1, wherein said formulation includes an effective amount of additional oxidizing agent for combusting during said generating step, and said oxidizing agent is other than said metal hydrazine complex and is at least one member selected from the group consisting of nitrates, nitrites, chlorates, perchlorates, peroxides, and metal oxides.

4. A method according to claim 1, wherein said formulation includes an effective amount of additional fuel for combusting during said generating step.

5. A method according to claim 1, wherein said formulation is in the form of pellets or granules.

6. A method according to claim 1, wherein said transition metal cation is a cobalt cation.

7. A method according to claim 1, wherein said formulation contains a binder in an amount of 0.5 to 12% by weight of the formulation.

8. A method according to claim 7, wherein said binder is present in an amount of 2 to 8% by weight of the formulation.

9. A method claim 1, wherein said formulation contains a binder which is comprised of at least one naturally occurring gum.

10. A method according to claim 9, wherein said binder comprises guar gum or acacia gum.

11. A method according to claim 1, wherein said formulation contains a binder in an amount of 0.5 to 12% by weight of the formulation, and said binder comprises a naturally occurring gum.

12. A method according to claim 1, wherein said formulation contains carbon powder in an amount of 0.1% to 6% by weight of said formulation.

13. A method according to claim 10, wherein said formulation also contains 0.5 to 12% by weight of the formulation of a binder.

14. A method according to claim 9, wherein said formulation contains carbon powder in an amount of 0.3% to 3% by weight of said formulation.

15. A method according to claim 9, wherein said binder is present in an amount of 0.5 to 12% by weight of the formulation, and said formulation contains carbon powder in an amount of 0.1% to 3% by weight of said formulation.

16. A method according to claim 1, wherein said formulation contains at least one additive selected from the group consisting of burn rate modifiers, slag formers, release agents, coolants and NO_x reducing agents.

17. A method according to claim 1, wherein said formulation contains at least about 60% by weight of said complex.

18. A method according to claim 1, wherein said formulation contains at least about 65% by weight of said complex.

19. A method according to claim 1, wherein said formulation contains at least about 50% by weight but less than 100% by weight of said complex.

20. A method according to claim 1, wherein said formulation contains at least about 50% to about 80% by weight of said complex.

21. A method according to claim 1, wherein said formulation contains carbon powder in an amount effective to improve the crush strength of said composition.

22. A method of inflating an air bag as defined in claim 1, wherein the combustion of the metal complex is initiated by heat.

23. A method of inflating an air bag as defined in claim 1, wherein the complex is a metal nitrite hydrazine.

24. A method of inflating an air bag as defined in claim 1, wherein the complex is a metal nitrate hydrazine.

25. A method of inflating an air bag as defined in claim 1, wherein the complex is a metal perchlorate hydrazine.

26. A method of inflating an air bag as defined in claim 1, wherein the transition metal cation or alkaline earth metal cation is selected from the group consisting of magnesium, manganese, nickel, titanium, copper, chromium, and zinc.

27. A method of inflating an air bag as defined in claim 1, wherein the transition metal cation is selected from the group consisting of rhodium, iridium, ruthenium, palladium, and platinum.

28. A method of inflating an air bag as defined in claim 1, wherein the oxidizing anion is coordinated with the metal cation.

29. A method of inflating an air bag as defined in claim 1, wherein the oxidizing anion is selected from the group consisting of nitrate, nitrite, chlorate, perchlorate, peroxide, superoxide, and mixtures thereof.

30. A method of inflating an air bag as defined in claim 1, wherein the inorganic oxidizing anion and the inorganic neutral ligand are free of carbon.

31. A method of inflating an air bag as defined in claim 1, wherein the complex includes at least one other common ligand, in addition to the neutral ligand.

32. A method of inflating an air bag as defined in claim 1, wherein the common ligand is selected from the group consisting of aquo (H₂ O), hydroxo (OH), perhydroxo (O₂ H), peroxo (O₂), carbonate (CO₃), carbonyl (CO), oxalato (C₂ O₄), nitrosyl (NO), cyano (CN), isocyanato (NC), isothiocyanato (NCS), thiocyanato (SCN), amido (NH₂), imdo (NH), sulfato (SO₄) , chloro (Cl), fluoro (F), phosphato (PO₄), and ethylenediaminetetraacetic acid (EDTA) ligands.

33. A method of inflating an air bag as defined in claim 1, wherein the complex includes a common counter ion in addition to the oxidizing anion.

34. A method of inflating an air bag as defined in claim 33, wherein the common counter ion is selected from the group consisting of hydroxide (OH^-), chloride (Cl^-), fluoride (F^-), cyanide (CN^-), thiocyanate (SCN^-), carbonate (CO₃^-2), sulfate (SO₄^-2), phosphate (PO₄^-3), oxalate (C₂ O₄^-2), borate (BO₄^-5), and ammonium (NH₄⁺) counter ions.

35. A method of inflating an air bag as defined in claim 1, wherein the complex and oxidizing anion combined have a concentration in the gas generating composition from 50% to 80% by weight, wherein the gas generating composition further comprises a binder and a co-oxidizer such that the binder has a concentration in the gas generating composition from 0.5% to 10% by weight and the co-oxidizer has a concentration in the gas generating composition from 5% to 50% by weight.

36. A method of inflating an air bag as defined in claim 1, wherein the gas generating composition which is combusted further comprising a co-oxidizer.

37. A method of inflating an air bag as defined in claim 36, wherein the co-oxidizer is selected from alkali, alkaline earth, or ammonium perchlorates, chlorates, peroxides, and nitrates.

38. A method of inflating an air bag as defined in claim 36, wherein the co-oxidizer is selected from metal oxides, metal hydroxides, metal peroxides, metal oxide hydrates, metal oxide hydroxides, metal hydrous oxides, basic metal carbonates, basic metal nitrates, and mixtures thereof.

39. A method of inflating an air bag as defined in claim 36, wherein the co-oxidizer is selected from oxides of copper, cobalt, manganese, tungsten, bismuth, molybdenum, and iron.

40. A method of inflating an air bag as defined in claim 36, wherein the co-oxidizer is a metal oxide selected from CuO, Co₂ O₃, Co₃ O₄, CoFe₂ O₄, Fe₂ O₃, MoO₃, Bi₂ MoO₆, and Bi₂ O₃.

41. A method of inflating an air bag as defined in claim 36, wherein the co-oxidizer is a metal hydroxide selected from Fe(OH)₃, Co(OH)₃, Co(OH)₂, Ni(OH)₂, CU(OH)₂, and Zn(OH)₂.

42. A method of inflating an air bag as defined in claim 36, wherein the co-oxidizer is a metal oxide hydrate or metal hydrous oxide selected from Fe₂ O₃.xH₂ O, SnO₂.xH₂ O, and MoO₃.H₂ O.

43. A method of inflating an air bag as defined in claim 36, wherein the co-oxidizer is a metal oxide hydroxide selected from CoO(OH)₂, FeO(OH)₂, MnO(OH)₂, and MnO(OH)₃.

44. A method of inflating an air bag as defined in claim 36, wherein the co-oxidizer is a basic metal carbonate selected from CuCO₃.Cu(OH)₂ (malachite), 2Co(CO₃).3Co(OH)₂.H₂ O, Co₀.69 Fe₀.34 (CO₃)₀.2 (OH)₂, Na₃ [Co(CO₃)₃ ].3H₂ O, Zn₂ (CO₃) (OH)₂, Bi₂ Mg(CO₃)₂ (OH)₄, Fe(CO₃)₀.12 (OH)₂.76, Cu₁.54 Zn₀.46 (CO₃) (OH)₂, Co₀.49 Cu₀.51 (CO₃)₀.43 (OH)₁.1, Ti₃ Bi₄ (CO₃)₂ (OH)₂ O₉ (H₂ O)₂, and (BiO)₂ CO₃.

45. A method of inflating an air bag as defined in claim 36, wherein the co-oxidizer is a basic metal nitrate selected from Cu₂ (OH)₃ NO₃, Co₂ (OH)₃ NO₃, CuCo(OH)₃ NO₃, Zn₂ (OH)₃ NO₃, Mn(OH)₂ NO₃, Fe₄ (OH)₁₁ NO₃.2H₂ O, Mo (NO₃)₂ O₂, BiONO₃.H₂ O, and Ce(OH) (NO₃)₃.3H₂ O.

46. A method of inflating an air bag as defined in claim 1, wherein the gas generating composition which is combusted further comprising a binder.

47. A method of inflating an air bag as defined in claim 46, wherein the binder is water soluble.

48. A method of inflating an air bag as defined in claim 47, wherein the binder is selected from naturally occurring gums, polyacrylic acids, and polyacrylamides.

49. A method of inflating an air bag as defined in claim 46, wherein the binder is not water soluble.

50. A method of inflating an air bag as defined in claim 49, wherein the binder is selected from nitrocellulose, VAAR, and nylon.

51. A method of inflating an air bag as defined in claim 1, wherein the complex is hexaamminecobalt(III) nitrate, ([(NH₃)₆ Co] (NO₃)₃) and the co-oxidizer is copper(II) trihydroxy nitrate (Cu₂ (OH)₃ NO₃).