Methods of making multilayered, hydrogen-containing thermite structures

• US 7,829,157 B2
• Filed: 04/07/2006
• Issued: 11/09/2010
• Est. Priority Date: 04/07/2006
• Status: Expired due to Fees

• Current Assignee: Lockheed Martin Corporation (Martin Marietta Corporation)
• Original Assignee: Lockheed Martin Corporation (Martin Marietta Corporation)
• Inventors: Schild, Ilissa Brooke, Johnson, James Neil
• Primary Examiner(s): Padgett; Marianne L
• Application Number:
  US11/399,263
• Publication Number:
  US 20100119728A1
• Time in Patent Office: 1,677 Days
• Field of Search: None
• US Class Current: 427/535
• CPC Class Codes: B23K 23/00 Alumino-thermic welding
• CPC Class Codes: C01B 6/00 Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds use of some thereof for reversible sorption of hydrogen C01B3/0005, C01B3/508; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof higher hydrides of boron, substituted hydrides of boron C01B35/00
• CPC Class Codes: C01B 6/02 Hydrides of transition elements; Addition complexes thereof
• CPC Class Codes: C06B 33/00 Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
• CPC Class Codes: C22C 1/11 Making amorphous alloys
• CPC Class Codes: C23C 28/322 only coatings of metal elements only
• CPC Class Codes: C23C 28/345 with at least one oxide layer
• CPC Class Codes: C23C 28/3455 with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
• CPC Class Codes: C23C 28/42 characterized by the composition of the alternating layers
• CPC Class Codes: F42B 1/00 Explosive charges characterised by form or shape but not dependent on shape of container
• CPC Class Codes: F42B 33/00 Manufacture of ammunition; Dismantling of ammunition; Apparatus therefor F42B5/188 takes precedence; manufacturing processes for hollow charges F42B1/036; manufacture of blasting cartridge initiators F42B3/195

Abstract

Methods of making multi-layered, hydrogen-containing thermite structures including at least one metal layer and at least one metal oxide layer adjacent to the metal layer are disclosed. At least one of the metal layers contains hydrogen, which can be introduced by plasma hydrogenation. The thermite structures can have high hydrogen contents and small dimensions, such as micrometer-sized and nanometer-sized dimensions.

Claims

1. A method of making a multilayered, hydrogen-containing thermite structure, the method comprising:

depositing a metal layer;

depositing a metal oxide layer, the metal layer and the metal oxide layer contacting each other and having respective compositions effective to undergo a thermite reaction when activated, thereby forming an initial structure; and

introducing hydrogen into the metal layer by plasma hydrogenation after the metal layer has been deposited;

whereby the multilayered, hydrogen-containing thermite structure is thus formed.

2. The method of claim 1, wherein the metal layer and the metal oxide layer are of a combination of materials selected from the group consisting of Ti/CuO, Ti/Pb₃O₄, Zr/CuO, Ti/Fe₂O₃, Ti/Fe₃O₄, Ti/MnO₂, Zr/Fe₂O₃ and Zr/MnO₂.

3. The method of claim 2, wherein the metal layer and the metal oxide layer are of a combination of materials selected from the group consisting of Ti/CuO, Ti/Pb₃O₄ and Zr/CuO.

4. The method of claim 1, wherein the metal layer is subjected to plasma hydrogenation before the metal oxide layer is deposited.

5. The method of claim 1, wherein the metal layer has an average hydrogen concentration of at least about 50 at % after the plasma hydrogenation.

6. The method of claim 5, wherein the metal layer has an average hydrogen concentration of at least about 60 at % after the plasma hydrogenation.

7. The method of claim 1, wherein one of the metal layer and the metal oxide layer is deposited on a substrate of a material selected from the group consisting of metals, ceramics, glasses, semiconductors, polymers and combinations thereof.

8. The method of claim 7, wherein:

the substrate is of a metal; and

the method further comprises introducing hydrogen into the substrate by plasma hydrogenation.

9. The method of claim 1, wherein each of the metal layer and the metal oxide layer has a thickness of less than about 100 nm.

10. The method of claim 9, wherein each of the metal layer and the metal oxide layer has a thickness of less than about 10 nm.

11. The method of claim 1, wherein the hydrogen introduced by plasma hydrogenation sits interstitially in the metal layer.

12. The method of claim 1, wherein the plasma hydrogenation comprises:

placing the metal layer or the initial structure in a reaction chamber;

supplying hydrogen gas into the chamber at a rate of about 50 sccm to about 500 sccm; and

energizing the hydrogen gas in the chamber.

13. The method of claim 12, wherein the hydrogen gas is energized by a RF power source having an input power of about 200 W to about 600 W, and a frequency of about 100 KHz to about 2.45 GHz.

14. The method of claim 13, wherein the metal layer or the initial structure is heated to about 50°

C. to about 125°

C.

15. The method of claim 14, wherein the chamber is maintained at a pressure of about 10 to about 1,000 mTorr during hydrogenation.

16. A method of making a multilayered, hydrogen-containing thermite structure, the method comprising:

depositing a first metal layer;

depositing a first metal oxide layer, the first metal layer and the first metal oxide layer contacting each other and having respective compositions effective to undergo a first thermite reaction when activated;

depositing a second metal layer;

depositing a second metal oxide layer, the second metal layer and the second metal oxide layer contacting each other and having respective compositions effective to undergo a second thermite reaction when activated; and

introducing hydrogen into at least one of the first and second metal layers by plasma hydrogenation after the first and/or second metal layer has been deposited;

wherein each of the first and second metal layers and each of the first and second metal oxide layers has a thickness of less than about 100 nm;

whereby the multilayered, hydrogen-containing thermite structure is thus formed.

17. The method of claim 16, wherein (i) the first metal layer and the first metal oxide layer and (ii) the second metal layer and the second metal oxide layer are of a combination of materials selected from the group consisting of Ti/CuO, Ti/Pb₃O₄, Zr/CuO, Ti/Fe₂O₃, Ti/Fe₃O₄, Ti/MnO₂, Zr/Fe₂O₃ and Zr/MnO₂.

18. The method of claim 17, wherein (i) the first metal layer and the first metal oxide layer and (ii) the second metal layer and the second metal oxide layer are of a combination of materials selected from the group consisting of Ti/CuO, Ti/Pb₃O₄ and Zr/CuO.

19. The method of claim 16, wherein the first metal layer subjected to plasma hydrogenation before the second metal layer is deposited.

20. The method of claim 16, wherein each of the first and second metal layers and each of the first and second metal oxide layers has a thickness of less than about 10 nm.

21. The method of claim 16, wherein:

the first and second metal layers are of the same metal; and

the first and second metal oxide layers are of the same metal oxide.

22. The method of claim 16, wherein:

the first metal layer is of a first metal;

the second metal layer is of a second metal different from the first metal;

the first and second metal oxide layers are of the same metal oxide; and

the first and second thermite reactions are different from each other.

23. The method of claim 16, wherein:

the first and second metal layers are of the same metal;

the first metal oxide layer is of a first metal oxide;

the second metal oxide layer is of a second metal oxide different from the first metal oxide; and

the first and second thermite reactions are different from each other.

24. The method of claim 16, wherein at least one of the first and second metal layers has an average hydrogen concentration of at least about 50 at % after the plasma hydrogenation.

25. The method of claim 16, wherein one of the first and second metal layers and first and second metal oxide layers is deposited on a substrate of a material selected from the group consisting of metals, ceramics, glasses, semiconductors, polymers and combinations thereof.

26. The method of claim 25, wherein:

the substrate is of a metal; and

the method further comprises introducing hydrogen into the substrate by plasma hydrogenation.

27. The method of claim 16, wherein the hydrogen introduced by plasma hydrogenation sits interstitially in at least one of the first and second metal layers.

28. A method of making a multilayered, hydrogen-containing thermite structure, the method comprising:

depositing a plurality of metal layers and metal oxide layers to form a multilayered thermite structure, at least one metal layer and at least one adjacent metal oxide layer contacting each other and having respective compositions effective to undergo a thermite reaction when activated; and

introducing hydrogen into the at least one metal layer by plasma hydrogenation after the at least one metal layer has been deposited;

wherein each of the metal layers and each of the metal oxide layers has a thickness of less than about 100 nm;

whereby the multilayered, hydrogen-containing thermite structure is thus formed.

29. The method of claim 28, wherein the thermite structure comprises adjacent metal layers and metal oxide layers of a combination of materials selected from the group consisting of Ti/CuO, Ti/Pb₃O₄, Zr/CuO, Ti/Fe₂O₃, Ti/Fe₃O₄, Ti/MnO₂, Zr/Fe₂O₃ and Zr/MnO₂.

30. The method of claim 28, wherein the thermite structure is subjected to plasma hydrogenation after each metal layer is deposited.

31. The method of claim 28, wherein at least one of the metal layers has an average hydrogen concentration of at least about 50 at % after the plasma hydrogenation.

32. The method of claim 28, wherein one of the metal layers or one of the metal oxide layers is deposited on a substrate of a material selected from the group consisting of metals, ceramics, glasses, semiconductors, polymers and combinations thereof.

33. The method of claim 32, wherein:

the substrate is of a metal; and

the method further comprises introducing hydrogen into the substrate by plasma hydrogenation.

34. The method of claim 28, wherein each of the metal layers has a thickness of less than about 10 nm.

35. The method of claim 28, wherein the thermite structure comprises a total of at least 10 metal layers and metal oxide layers.

36. The method of claim 28, wherein the thermite structure comprises a total of at least 100 metal layers and metal oxide layers.

37. The method of claim 28, wherein the thermite structure comprises a total of at least 1000 metal layers and metal oxide layers.