Metal complexes for use as gas generants

• US 5,725,699 A
• Filed: 07/26/1995
• Issued: 03/10/1998
• Est. Priority Date: 01/19/1994
• Status: Expired due to Term

• Current Assignee: Northrop Grumman Innovation Systems, Inc. (Northrop Grumman Corporation)
• Original Assignee: Thiokol Corporation (Howmet Aerospace, Inc.)
• Inventors: Doll, Daniel W., Lund, Gary K., Blau, Reed J., Hinshaw, Jerald C.
• Primary Examiner(s): Miller, Edward A.
• Application Number:
  US08/507,552
• Time in Patent Office: 958 Days
• Field of Search: 149/45, 149/75, 149/19.1, 280/741
• US Class Current: 149/19.1
• 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 gas generating composition formulated from ingredients comprising:

at least one complex of,

a metal cation,

ammonia ligand, and

sufficient oxidizing anion to balance the charge of the metal complex,

wherein said composition contains about 48.5% to less than about 100% by weight of said complex; and

at least 0.1% by weight of at least one additional ingredient selected for inclusion said gas generating composition.

2. A gas generating composition as defined in claim 1, wherein the complex is selected from the group consisting of metal nitrite ammines, metal nitrate ammines, metal perchlorate ammines, and mixtures thereof.

3. A gas generating composition as defined in claim 1, wherein the metal cation is a transition metal, alkaline earth metal, metalloid, or lanthanide metal cation.

4. A gas generating composition as defined in claim 1, wherein the metal cation is a transition metal cation.

5. A gas generating composition as defined in claim 4, wherein the transition metal cation is a cobalt cation.

6. A gas generating composition as defined in claim 4, wherein the transition metal cation is a cation of a metal selected from the group consisting of cobalt, magnesium, manganese, nickel, titanium, copper, chromium, zinc, tin, rhodium, iridium, ruthenium, palladium and platinum.

7. A gas generating composition as defined in claim 1, wherein the oxidizing anion is coordinated with the metal cation.

8. A gas generating composition as defined in claim 1, wherein the oxidizing anion is selected from the group consisting of nitrate, nitrite, chlorate, perchlorate, peroxide, and superoxide.

9. A gas generating composition as defined in claim 1, wherein the oxidizing anion is free of carbon.

10. A gas generating composition as defined in claim 1, wherein the complex includes at least one common ligand, in addition to the ammonia ligand.

11. A gas generating composition as defined in claim 10, wherein the common ligand is selected from the group consisting of aquo (H₂ O), hydroxo (OH), perhydroxo (O₂ H), peroxo (O₂), carbonato (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.

12. A gas generating composition as defined in claim 1, wherein the complex includes a common counter ion in addition to the oxidizing anion.

13. A gas generating composition as defined in claim 12, 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.

15. A gas generating composition as defined in claim 1, further comprising a co-oxidizer.

16. A gas generating composition as defined in claim 15, wherein the co-oxidizer is selected from the group consisting of alkali, alkaline earth, lanthanide or ammonium perchlorates, chlorates, peroxides, nitrites and nitrates.

17. A gas generating composition as defined in claim 15, wherein the co-oxidizer is selected from the group consisting of metal oxides, metal hydroxides, metal peroxides, metal oxide hydrates, metal oxide hydroxides, metal hydrous oxides, basic metal carbonates, basic metal nitrates, and mixtures thereof.

18. A gas generating composition as defined in claim 15, wherein the co-oxidizer is selected from the group consisting of oxides of copper, cobalt, manganese, tungsten, bismuth, molybdenum, and iron.

19. A gas generating composition as defined in claim 15, wherein the co-oxidizer is a metal oxide selected from the group consisting of CuO, Co₂ O₂₃, Co₃ O₄, CoFe₂ O₄, Fe₂ O₃, MoO₃, Bi₂ MoO₆, and Bi₂ O₃.

20. A gas generating composition as defined in claim 15, wherein the co-oxidizer is a metal hydroxide selected from the group consisting of Fe(OH)₃, Co(OH)₃, Co(OH)₂, Ni(OH)₂, Cu(OH)₂, and Zn(OH)₂.

21. A gas generating composition as defined in claim 15, wherein the co-oxidizer is a metal oxide hydrate or metal hydrous oxide selected from the group consisting of Fe₂ O₃.xH₂ O, SnO₂.xH₂ O, and MoO₃.H₂ O.

22. A gas generating composition as defined in claim 15, wherein the co-oxidizer is a metal oxide hydroxide selected from the group consisting of CoO(OH)₂, FeO(OH)₂, MnO(OH)₂, and MnO(OH)₃.

23. A gas generating composition as defined in claim 15, wherein the co-oxidizer is a basic metal carbonate selected from the group consisting of 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.

24. A gas generating composition as defined in claim 15, wherein the co-oxidizer is a basic metal nitrate selected from the group consisting of Cu₂ (OH)₃ NO₃, Co₂ (OH)₃ NO₃, CuCo(OH)₃ NO₃, Zn₂ (OH)₃ NO₃, Zn₂ (OH)₂ 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.

25. A gas generating composition as defined in claim 1, further comprising a binder.

26. A gas generating composition as defined in claim 25, wherein the binder is water soluble.

27. A gas generating composition as defined in claim 26, wherein the binder is selected from naturally occurring gums, polyacrylic acids, and polyacrylamides.

28. A gas generating composition as defined in claim 25, wherein the binder is not water soluble.

29. A gas generating composition as defined in claim 28, wherein the binder is selected from nitrocellulose, VAAR (vinyl acetate vinyl alcohol resin), and nylon.

30. A gas generating composition 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).

31. A gas generating composition as defined in claim 1, further comprising carbon powder present from 0.1% to 6% by weight of the gas generating composition.

36. A gas generating composition as defined in claim 1, wherein the complex is hexaamminecobalt(III) nitrate ( (NH₃)₆ Co!(NO₃)₃).

39. A composition according to claim 1, 37 or 38 which is in the form of pellets or granules.

46. A composition according to claim 1, 37 or 38, wherein said composition contains carbon powder in an amount of 0.3% to 3% by weight of said composition.

50. A composition according to claim 1, wherein said composition contains at least about 60% by weight of said complex.

51. A composition according to claim 1, wherein said composition contains at least about 65% by weight of said complex.

53. A composition according to claim 1, wherein said composition contains about 50% to about 80% by weight of said complex.

14. A gas generating composition formulated from ingredients comprising:

at least one complex of

a metal cation

ammonia ligand, and

sufficient oxidizing anion to balance the charge of the metal complex,

wherein said composition contains about 50% to about 80% by weight of said complex and said anion;

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

a co-oxidizer in an amount of from 5% to 50% by weight of said gas generant composition.

32. A gas generating device containing a gas generating composition, wherein said

gas generating composition comprises a complex of a transition metal cation or alkaline earth metal cation and ammonia ligand, and sufficient oxidizing anion to balance the charge of the complex, such that when said complex combusts, a mixture of gases containing nitrogen gas and water vapor is produced;

and

wherein said gas generating device has an igniter to ignite the composition.

33. A gas generating device as defined in claim 32, wherein the igniter includes an igniter composition comprising a mixture of Mg/Sr(NO₃)₂ /nylon and B/KNO₃.

54. A gas generating device according to claim 32, wherein said gas generating composition contains about 48.5% to less than about 100% by weight of said complex.

55. A gas generating device according to claim 32, wherein said composition comprises at least one said complex;

at least one member selected from the group consisting of binder and carbon powder in an amount of 0.1% to 6% of said composition; and

inorganic co-oxidizing agent in an amount less than 50% by weight of said composition.

56. A gas generating device according to claim 54 or 55, wherein said gas generant composition contains a binder and said binder is a water-soluble binder.

57. A gas generating device according to claim 54, wherein said binder is present in an amount of 0.5 to 12% by weight of the composition.

58. A gas generating device according to claim 54 or 55, wherein the igniter includes an igniter composition.

59. A gas generating device according to claim 54 or 55, wherein the igniter composition is comprised of a mixture of Mg/Sr(NO₃)₂ /nylon and B/KNO₃.

68. A gas generating device according to claim 32, wherein said composition comprises hexaammine cobalt (III) nitrate, up to 12% by weight water soluble binder, up 6% by weight of carbon powder, and, optionally, CU₂ (OH)₃ NO₃.

69. A gas generating device according to claim 68, wherein said water soluble binder comprises guar gum.

70. A gas generating device according to claim 32, wherein said composition comprises hexaammine cobalt(III) nitrate and, optionally, Cu₂ (OH)₃ NO₃.

76. A gas generating device as defined in claim 32, wherein the igniter includes at least one igniter composition.

34. An air bag system for a vehicle comprising:

a collapsed, inflatable air bag;

a gas-generating device connected to the air bag for inflating the air bag, wherein the gas-generating device contains a gas-generating composition formulated from ingredients comprising;

a complex of a transition metal cation and ammonia ligand, and sufficient oxidizing anion to balance the charge of the metal cation; and

an igniter to ignite the gas-generating composition.

60. An air bag system for a vehicle according to claim 34, wherein said gas generating composition contains from 48.5% to less than about 100% by weight of said complex.

61. An air bag system for a vehicle according to claim 34, wherein said gas generating composition comprises at least one said complex;

at least one member selected from the group consisting of water-soluble binder and carbon powder in an amount of 0.1% to 6% of said composition; and

less than 50% by weight of an inorganic co-oxidizer.

71. An air bag system according to claim 34, wherein said composition comprises hexaammine cobalt(III) nitrate and, optionally, Cu₂ (OH)₃ NO₃.

35. A vehicle equipped with a supplemental restraint system, said supplemental restraint system including an air bag system which comprises:

a collapsed, inflatable air bag;

a gas-generating device connected to the air bag for inflating the air bag, wherein the gas-generating device contains a gas-generating composition comprising;

a complex of a transition metal cation and ammonia, and sufficient oxidizing anion to balance the charge of the metal cation; and

an igniter to ignite the gas-generating composition.

62. A vehicle according to claim 35, wherein said gas generating composition further comprises a binder, and, optionally carbon powder in a small but effective amount whereby the crush strength of the composition is increased compared to the composition without the carbon powder.

63. A vehicle according to claim 35, wherein said gas-generating composition contains about 48.5% by weight to less than 100% by weight of said complex.

64. A vehicle according to claim 35, wherein said gas-generating composition further comprises a binder, and optionally carbon powder in an amount of 0.1% to 6% of said composition.

65. A vehicle according to claim 35, wherein said gas generating composition comprises

at least one said complex;

at least one member selected from the group consisting of a binder and carbon powder in an amount of 0.1 to 6% by weight,

optionally, an additive which is at least one selected from the group consisting of burn rate modifiers, slag formers, release agents, coolants and NO_x reducing agents,

optionally a secondary fuel, and

optionally less than 50% by weight of inorganic co-oxidizer.

72. A vehicle according to claim 35, wherein said composition comprises hexaammine cobalt (III) nitrate, up to 12% by weight water soluble binder, up to 6% by weight of carbon powder, and, optionally, Cu₂ (OH)₃ NO₃.

73. A vehicle according to claim 72, wherein said water soluble binder comprises guar gum.

74. A vehicle according to claim 35, wherein said composition comprises hexaammine cobalt (III) nitrate and, optionally, CU₂ (OH)₃ NO₃.

37. A gas generant composition which is formulated from ingredients which comprises

at least one complex of a metal cation and at least one neutral ligand which comprises ammonia, wherein said metal cation is a transition metal cation or an alkaline earth metal cation, and sufficient oxidizing anion to balance the charge of the metal cation;

at least one of

binder;

or

a small but effective amount of carbon powder whereby the crush strength of the composition is increased compared to the composition without the carbon powder; and

optionally inorganic co-oxidizer in an amount less than 50% by weight of said composition.

38. A composition according to claim 37, wherein said composition consists essentially of hexaammine cobalt(III) nitrate;

water-soluble binder;

carbon powder in an amount of 0.1 to 6% by weight of said composition; and

optionally, inorganic co-oxidizer in an amount less than 50% by weight of said composition.

40. A composition according to claim 37, wherein said transition metal cation is a cobalt cation.

41. A composition according to claim 37 or 38, wherein said binder is present in an amount of 0.5 to 12% by weight of the composition.

42. A composition according to claim 37 or 38, wherein said binder is present in an amount of 2 to 8% by weight of the composition.

43. A composition according to claim 37 or 38, wherein said binder comprises at least one naturally occurring gum.

44. A composition according to claim 37 or 38, wherein said binder comprises guar gum or acacia gum.

45. A composition according to claim 37, wherein said composition contains carbon powder in an amount of 0.1% to 6% by weight of said composition, and binder in an amount of 0.5 to 12% by weight of said composition.

47. A composition according to claim 37 or 38, wherein said binder is present in an amount of 0.5 to 12% by weight of the composition, and said binder comprises a naturally occurring gum.

48. A composition according to claim 37 or 38, wherein said binder is present in an amount of 0.5 to 12% by weight of the composition, said binder comprises a naturally occurring gum, and said composition contains carbon powder in an amount of 0.1% to 3% by weight of said composition.

49. A gas generant composition according to claim 37 or 38, wherein said composition optionally contains at least one additive selected from the group consisting of burn rate modifiers, slag formers, release agents, coolants and NO_x reducing agents.

52. A composition according to claim 37, wherein said composition contains about 48.5% by weight but less than 100% by weight of said complex.

66. A gas generant composition according to claim 37, wherein said composition comprises hexaammine cobalt(III) nitrate, up to 12% by weight of a water soluble binder, up to 6% by weight of carbon powder, and, optionally, Cu₂ (OH)₃ NO₃.

67. A gas generant composition according to claim 66, wherein said water soluble binder comprises guar gum.

75. A vehicle equipped with a supplemental restraint system, said supplemental restraint system including an air bag system which comprises:

(i) a collapsed, inflatable air bag;

(ii) a gas-generating device connected to the air bag for inflating the air bag, wherein the gas-generating device contains a gas-generating composition which is formulated from ingredients which comprise

at least one complex of a metal cation and at least one neutral ligand which comprises ammonia, wherein said metal cation is a transition metal cation or an alkaline earth metal cation, and sufficient oxidizing anion to balance the charge of the metal cation;

at least one of

binder;

or

a small but effective amount of carbon powder whereby the crush strength of the composition is increased compared to the composition without the carbon powder; and

optionally inorganic co-oxidizer in an amount less than 50% by weight of said composition; and

(iii) an igniter to ignite the gas-generating composition.