Metal complexes for use as gas generants

• US 6,039,820 A
• Filed: 07/24/1997
• Issued: 03/21/2000
• Est. Priority Date: 07/24/1997
• 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): Nelson, Peter A.
• Application Number:
  US08/899,599
• Time in Patent Office: 971 Days
• Field of Search: 149/45, 102/289
• US Class Current: 149/45
• 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, sufficient oxidizing anion to balance the charge of the complex, and at least one cool burning organic nitrogen-containing compound. 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 comprising:

a complex of a metal cation, at least one neutral ligand containing hydrogen and nitrogen, and sufficient oxidizing anion to balance the charge of the metal cation such that when the complex combusts, a mixture of gases containing nitrogen gas and water vapor is produced; and

at least one cool burning organic nitrogen-containing compound.

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, metal nitrite hydrazines, metal nitrate hydrazines, metal perchlorate hydrazines, and mixtures thereof.

3. A gas generating composition as defined in claim 1, wherein the complex is a metal nitrite ammine.

4. A gas generating composition as defined in claim 1, wherein the complex is a metal nitrate ammine.

5. A gas generating composition as defined in claim 1, wherein the complex is a metal perchlorate ammine.

6. A gas generating composition as defined in claim 1, wherein the complex is a metal nitrite hydrazine.

7. A gas generating composition as defined in claim 1, wherein the complex is a metal nitrate hydrazine.

8. A gas generating composition as defined in claim 1, wherein the complex is a metal perchlorate hydrazine.

9. 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.

10. A gas generating composition as defined in claim 9, wherein the metal cation is selected from the group consisting of magnesium, manganese, nickel, titanium, copper, chromium, zinc, and tin.

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

12. A gas generating composition as defined in claim 11, wherein the transition metal cation is cobalt.

13. A gas generating composition as defined in claim 11, wherein the transition metal cation is selected from the group consisting of rhodium, iridium, ruthenium, palladium, and platinum.

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

15. 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.

16. A gas generating composition as defined in claim 1, wherein the inorganic oxidizing anion and the inorganic neutral ligand are free of carbon.

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

18. A gas generating composition as defined in claim 17, 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.

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

20. A gas generating composition as defined in claim 19, 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.

21. A gas generating composition as defined in claim 1, wherein the complex has a concentration in the gas generating composition from 30% to 90% 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 12% by weight, and wherein the sum of the amount of co-oxidizer and cool burning compound in the gas generating composition is from 10% to 60% by weight.

22. A gas generating composition as defined in claim 1, further comprising a co-oxidizer other than said cool burning compound.

23. A gas generating composition as defined in claim 22, wherein the co-oxidizer is selected from alkali, alkaline earth, lanthanide, or ammonium perchlorates, chlorates, peroxides, nitrites, and nitrates.

24. A gas generating composition as defined in claim 22, 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.

25. A gas generating composition as defined in claim 22, wherein the co-oxidizer is selected from oxides of copper, cobalt, manganese, tungsten, bismuth, molybdenum, and iron.

26. A gas generating composition as defined in claim 22, 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.

27. A gas generating composition as defined in claim 22, 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.

28. A gas generating composition as defined in claim 22, 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.

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

30. A gas generating composition as defined in claim 22, 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.

31. A gas generating composition as defined in claim 22, 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.

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

33. A gas generating composition as defined in claim 32, wherein the binder is water soluble.

34. A gas generating composition as defined in claim 33, wherein the binder is selected from naturally occurring gums, polyacrylic acids, and polyacrylamides.

35. A gas generating composition as defined in claim 32, wherein the binder is not water soluble.

36. A gas generating composition as defined in claim 35, wherein the binder is selected from nitrocellulose, VAAR, and nylon.

37. 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).

38. 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, wherein the composition exhibits improved crush strength compared to the composition without carbon powder.

39. A gas generating composition as defined in claim 1, further comprising carbon powder present from 0.3% to 3% by weight of the gas generating composition.

45. A gas generating composition as defined in claim 1, wherein said cool burning compound has a heat of formation of less than about -400 cal/g.

46. A gas generating composition as defined in claim 1, wherein said cool burning compound has a heat of formation of less than about -600 cal/g.

47. A gas generating composition as defined in claim 1, wherein said cool burning compound is a guanidine salt or a guanidine derivative.

48. A gas generating composition as defined in claim 1, wherein said cool burning compound is guanidine nitrate.

49. A gas generating composition as defined in claim 1, wherein the amount of said cool burning compound is greater than about 0 wt. % and up to about 40 wt. %.

40. A gas generating device comprising:

a gas generating composition comprising;

a complex of a transition metal cation or alkaline earth metal cation and a neutral ligand containing hydrogen and nitrogen, such that when the complex combusts, a mixture of gases containing nitrogen gas and water vapor is produced;

sufficient oxidizing anion to balance the charge of the metal cation; and

at least one cool burning organic nitrogen-containing compound; and

an ignitor for initiating the combustion of the composition.

41. A gas generating device as defined in claim 40, wherein the ignitor for initiating the combustion includes an igniter composition comprising a mixture of different igniter compositions.

42. A gas generating device as defined in claim 40, wherein the ignitor for initiating the combustion includes an igniter composition comprising a mixture of Mg/Sr(NO₃)₂ /nylon and B/KNO₃.

43. An automobile air bag system comprising:

a collapsed, inflatable air bag;

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

a complex of a transition metal cation or alkaline earth metal cation and a neutral ligand containing hydrogen and nitrogen, such that when the complex combusts, a mixture of gases containing nitrogen gas and water vapor is produced;

sufficient oxidizing anion to balance the charge of the metal cation; and

and at least one cool burning organic nitrogen-containing compound; and

an ignitor to ignite the gas-generating composition.

44. A vehicle containing a supplemental restraint system having an air bag system comprising:

a collapsed, inflatable air bag;

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

a complex of a transition metal cation or alkaline earth metal cation and a neutral ligand containing hydrogen and nitrogen, such that when the complex combusts, a mixture of gases containing nitrogen gas and water vapor is produced;

sufficient oxidizing anion to balance the charge of the metal cation; and

at least one cool burning organic nitrogen-containing compound; and

an ignitor for igniting the gas-generating composition.