Processes for fabricating structural ceramic bodies and structural ceramic-bearing composite bodies

• US 5,447,291 A
• Filed: 10/08/1993
• Issued: 09/05/1995
• Est. Priority Date: 10/08/1993
• Status: Expired due to Fees

• Current Assignee: Ohio State University
• Original Assignee: Ohio State University
• Inventors: Sandhage, Kenneth H.
• Primary Examiner(s): Simmons, David A.
• Assistant Examiner(s): MAYES, MELVIN C
• Application Number:
  US08/134,321
• Time in Patent Office: 697 Days
• Field of Search: 501/117, 501/118, 501/121, 501/122, 501/125, 148/277, 148/284, 148/285, 148/286, 427/383.5, 427/372.2, 427/376.3, 264/60, 264/65, 264/66
• US Class Current: 148/516
• CPC Class Codes: C04B 35/65 Reaction sintering of free metal- or free silicon-containing compositions C04B35/573, C04B35/591 take precedence
• CPC Class Codes: C23C 8/10 Oxidising

Abstract

Shaped refractory ceramic and refractory ceramic composite objects are made from corresponding shaped, oxidation-resistant-metal-bearing objects through exposure to an oxidizing environment without substantial changes in dimensions by providing in the shaped metal-bearing objects a combination of a) metals which when oxidized form a ceramic compound with a larger molar volume than the molar volume of the metals consumed to make the ceramic compound with b) metals which when oxidized form a ceramic compound with a smaller molar volume than the molar volume of the metals consumed to make the ceramic compound. Metal-bearing objects, containing metals such as silicon or aluminum, which when oxidized form ceramic or ceramic-composite objects containing refractory ceramic compounds of desired properties, such as compounds containing silicon oxide or aluminum oxide, for which the ceramic compounds have a molar volume that is greater than the molar volumes of the metals consumed to make the ceramic compounds, expand upon oxidation, thereby having an adverse effect on the properties of the resulting ceramic and preventing the maintenance of the dimensions of the metal-bearing objects. The present invention is the discovery that when alkali or alkaline earth metals, which when oxidized have molar volumes that are less than such metals, are alloyed with or otherwise combined with oxidation-resistant metals that are formed into the metal-bearing objects and converted into desired refractory ceramics, swelling, resulting loss of mechanical properties, and dimensional changes are reduced or eliminated. Further, such combination of a) metals that after oxidation form ceramic compounds having a molar volume greater than the molar volumes of the metals consumed to make the ceramic compound with b) alkali or alkaline earth metals that after oxidation form ceramic compounds having a molar volume less than the molar volume of the alkali or alkaline earth metals consumed to make the ceramic compounds provides an unexpectedly advantageous brazing alloy for joining ceramic-bearing bodies.

Claims

1. A method of making a refractory ceramic body or refractory ceramic composite body of preselected shape comprising:

a) combining metallic elements, or metallic elements and oxidized metallic elements, of said ceramic to produce a metal-bearing precursor consisting at least in part of an alloy of at least one oxidation-resistant metal disposed to form a ceramic upon oxidation having a molar volume that is greater than the sum of the molar volumes of the metals consumed to make the ceramic and at least one second metal disposed to form a ceramic upon oxidation that has a molar volume that is less than the sum of the molar volumes of the metals consumed to make the ceramic;

b) forming the metal-bearing precursor into a solid metal-bearing precursor of said preselected shape; and

c) exposing said solid metal-bearing precursor to an oxidizing environment at a temperature lower than the melting point of said solid metal-bearing precursor to convert said solid metal-bearing precursor into said refractory ceramic body or composite.

2. The method of claim 1 wherein said at least one second metal is at least one metal selected from the group of alkaline earth elements and alkali elements.

3. The method of claim 1 wherein said at least one second metal is at least one metal selected from the group Mg, Ca, Sr, Ba, Ra, H, Li, Na, K, Rb, Cs, and Fr.

4. The method of claim 1 wherein said at least one oxidation-resistant metal is a metal selected from the group of Aluminum, Silicon, and Chromium and metallic alloys that include at least one of the metals from the group of Aluminum, Silicon, and Chromium.

5. The method of claim 4 wherein said alloy contains at least 1 atomic percent of Aluminum, Silicon, or Chromium.

6. The method of claim 1 wherein said at least one second metal is present in said precursor in the amount of at least 5 atomic percent.

7. The method of claim 1 wherein said at least one second metal is present in said precursor within the range of at least 10 to 50 atomic percent.

8. The method of claim 1 wherein said combining consists of mechanical alloying.

9. The method of claim 1 wherein said combining consists of alloying said metals while in a molten or partially molten state to form a molten alloy.

10. The method of claim 9 wherein forming consists of solidification within a mold or preform of a preselected shape.

11. The method of claim 9 wherein step b) is conducted rapidly by melt spinning, planar flow casting, or gas atomization.

12. The method of claim 11 wherein said precursor is a porous ceramic body.

13. The method of claim 1 wherein said combining consists of alloying said elements while vaporized or partially vaporized and forming said precursor by condensation or deposition of the vapor onto a substrate.

14. The method of claim 1 wherein said forming consists of drawing, extrusion, pressing, swaging, or rolling.

15. The method of claim 1 wherein said forming is conducted by solidification of a molten or partially molten precursor.

16. The method of claim 1 wherein said formed precursor is a coating on a substrate.

17. The method of claim 16 wherein said coating is prepared by one or more of co-extrusion, co-rolling, co-drawing, co-swaging, or co-pressing with the substrate.

18. The method of claim 16 wherein said coating is prepared by dipping the substrate into said metal-bearing precursor that is molten or partially molten, and then solidification of the metal-bearing precursor on the substrate.

19. The method of claim 16 wherein said coating is prepared by one or more of laser ablation, sputtering, evaporation, plasma spraying, chemical vapor deposition, molecular beam epitaxy, ion beam mixing, or ion implantation.

20. The method of claim 16 wherein said substrate is a porous body of desired shape which is at least partially internally coated by the said formed precursor.

21. The method of claim 1 wherein said oxidizing environment is at least one oxidizing means selected from the group of a gas containing a vapor-phase oxidant, a solid containing a solid-phase oxidant and a liquid containing a liquid-phase oxidant.

22. The method of claim 21 wherein said oxidants contain at least one of the elements oxygen, nitrogen, sulfur, phosphorus, carbon, hydrogen, chlorine, fluorine, bromine, or iodine.

23. The method of claim 1 wherein said oxidizing environment contains a gradient in electric potential.

24. The method of claim 1 wherein said oxidizing step c) is performed at a substantially isothermal temperature.

25. The method of claim 1 wherein at least one surface of said metal precursor from step a) or step b) is brought into contact with a ceramic surface of a ceramic-bearing component and heated in an inert or vacuum environment prior to step c) to effect complete oxidation of the metal alloy in the oxidizing atmosphere of step c) and bonding between said precursor and ceramic component.

26. The method of claim 25 wherein said at least one second metal is a metal selected from the group of alkaline earth elements and alkali elements.

27. The method of claim 25 wherein said second metal is selected from the group of Mg, Ca, Sr, Ba, Ra, H, Li, Na, K, Rb, Cs, and Fr.

28. The method of claim 25 wherein said ceramic-bearing component contains at least one cation that can be reduced by at least one element in the precursor.

29. The method of claim 25 wherein said ceramic-bearing component is composed of mullite and said at least one second metal is Barium.

30. The method of claim 28 wherein said precursor is a malleable alloy.

31. The method of claim 25 wherein said precursor upon oxidation has a melting point of at least 700°

C.