Oxidation resistant carbon and method for making same

• US 5,286,565 A
• Filed: 12/03/1987
• Issued: 02/15/1994
• Est. Priority Date: 09/24/1984
• Status: Expired due to Fees

• Current Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Holzl, Robert A., Withers, Howard P. Jr., Dyer, Paul N., Magnotta, Vincent L.
• Primary Examiner(s): Walsh, Donald P.
• Assistant Examiner(s): CARROLL, CHRISMAN DION
• Application Number:
  US07/131,479
• Time in Patent Office: 2,266 Days
• Field of Search: 427/249, 427/279, 428/408, 428/698, 428/699, 428/702, 501/42, 501/49, 501/90, 501/91, 501/92, 501/96, 501/97, 501/99
• US Class Current: 428/408
• CPC Class Codes: C04B 41/5057 Carbides
• CPC Class Codes: C04B 41/52 Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
• CPC Class Codes: C04B 41/5346 Dry etching
• CPC Class Codes: C04B 41/87 Ceramics
• CPC Class Codes: C04B 41/89 for obtaining at least two superposed coatings having different compositions
• CPC Class Codes: C04B 41/91 involving the removal of part of the materials of the treated articles, e.g. etching
• CPC Class Codes: C09K 13/10 containing a boron compound
• CPC Class Codes: C23C 16/0272 Deposition of sub-layers, e.g. to promote the adhesion of the main coating
• CPC Class Codes: C23C 16/24 Deposition of silicon only
• CPC Class Codes: C23C 16/28 Deposition of only one other non-metal element
• CPC Class Codes: C23C 16/32 Carbides
• CPC Class Codes: C23C 16/34 Nitrides C23C16/303 takes precedence
• CPC Class Codes: C23C 16/38 Borides
• CPC Class Codes: C23C 16/40 Oxides
• CPC Class Codes: C23C 8/28 more than one element being applied in one step
• CPC Class Codes: C23C 8/80 After-treatment
• CPC Class Codes: Y10T 428/30 Self-sustaining carbon mass or layer with impregnant or other layer

Abstract

A coated carbon body having improved resistance to high temperature oxidation and a method for producing the coated carbon body are described. The coated carbon body comprises a carbon body, an intermediate glass forming coating and an outer refractory coating on the intermediate coating. The body has a converted porous layer formed by etching and reacting the body with boron oxide and the resulting converted layer contains interconnecting interstices and boron carbide formed by the reaction of the boron oxide and the carbon body. The method comprises contacting a carbon body with boron oxide at an elevated temperature sufficient to cause the reaction between the carbon body and boron oxide to form a converted porous layer which contains interconnecting interstices in the body and boron carbide and then applying the glass forming coating over the converted layer. Preferably an outer refractory coating is applied over the glass forming coating. The glass forming coating comprises compounds selected from the group consisting of silicon nitride, silicon oxynitride and mixtures thereof. Additionally, both the refractory outer coating and the glass forming coating can contain compounds selected from the group consisting of silicon nitride, silicon oxynitride, and mixtures thereof.

Claims

1. A coated carbon body having improved resistance to high temperature oxidation comprising:

a carbon body,

said body having a converted porous layer formed by etching and reacting said carbon body with boron oxide, said converted layer containing interconnecting interstices and boron carbide formed by the reaction of boron oxide and said carbon body and

a glass forming coating at least a portion of which is within said converted layer, said coating comprising compounds selected from the group consisting of silicon nitride, silicon oxynitride and mixtures thereof.

2. A coated body in accordance with claim 1 wherein a refractory coating is on the glass forming coating.

3. A coated body in accordance with claim 2 wherein the refractory coating comprises carbides, borides or nitrides of silicon, zirconium, tantalum, hafnium, niobium and titanium, silicon oxynitride, and aluminum boride or nitride or mixtures thereof.

4. A coated body in accordance with claim 3 wherein the converted layer has a depth of between about 3 and about 250 microns.

5. A coated body in accordance with claim 4 wherein the converted layer has a void volume of up to about 50 percent of the volume originally occupied by the carbon layer.

6. A coated body in accordance with claim 1 wherein the glass forming coating partially fills the interstices of said converted layer.

7. A coated carbon body having improved resistance to high temperature oxidation comprising:

a carbon body,

said body having converted porous layer formed by etching and reacting said carbon body with boron oxide, said converted layer containing interconnecting interstices and boron carbide formed by the reaction of boron and said carbon body,

a boron-containing intermediate glass forming coating within said converted layer, said intermediate coating comprising compounds selected from the group consisting of silicon nitride, silicon oxynitride and mixtures thereof, and

an outer refractory coating on said intermediate coating.

8. A coated body in accordance with claim 7 wherein the refractory coating is silicon nitride.

9. A coated body in accordance with claim 7 wherein the refractory coating is silicon oxynitride.

10. A coated carbon body having improved resistance to high temperature oxidation comprising:

a carbon body,

said body having converted porous layer formed by etching and reacting said carbon body with gaseous boron oxide, said converted layer containing interconnecting interstices and boron carbide formed by the reaction of boron and said carbon body,

a boron and silicon-containing intermediate glass forming coating within said converted layer, said intermediate coating comprising compounds selected from the group consisting of silicon nitride, silicon oxynitride and mixtures thereof, and

an outer refractory coating on said intermediate coating

11. A coated body in accordance with claim 10 wherein the refractory coating is silicon nitride.

12. A coated body in accordance with claim 10 wherein the refractory coating is silicon oxynitride.

13. A method for the manufacture of a coated carbon body having improved resistance to high temperature oxidation comprising:

providing a carbon body,

contacting said carbon body with boron oxide at an elevated temperature sufficient to cause reaction between the carbon body and the boron oxide thereby forming a converted porous layer containing interconnecting interstices in said body, which layer contains boron carbide,

applying a glass forming coating over said converted layer, said glass forming coating comprising compounds selected from the group consisting of silicon nitride, silicon oxynitride and mixtures thereof.

14. A method in accordance with claim 13 wherein an outer refractory coating is applied over said glass forming coating.

15. A method in accordance with claim 13 wherein the elevated temperature is at least about 1500°

C. to cause said converted layer to reach a depth of between about 2 and 250 microns.

16. A method in accordance with claim 13 wherein said converted layer has a void volume of up to about 50 percent of the volume originally occupied by the carbon layer.

17. A method in accordance with claim 13 wherein the glass forming coating comprises a primary glass forming species selected from boron, boron carbide, boron oxide, silicon, silicon alloys, silicon dioxide, germania, and mixtures thereof.

18. A method in accordance with claim 13 wherein said glass forming coating also contains borides and oxides of zirconium, aluminum, magnesium, hafnium, titanium, carbides of zirconium, hafnium, titanium, nitrides of zirconium, hafnium, titanium, silicon and mixtures thereof.

19. A method in accordance with claim 13 wherein the glass forming coating is applied by chemical vapor deposition.

20. A method in accordance with claim 14 wherein the outer refractory coating is applied by chemical vapor deposition.

21. A method in accordance with claim 14 wherein the outer refractory coating comprises carbides, borides or nitrides of silicon, zirconium, tantalum, hafnium, niobium, titanium, aluminum boride or nitride or mixtures thereof.

22. A method in accordance with claim 14 wherein the refractory coating is silicon nitride.

23. A method in accordance with claim 14 wherein the refractory coating is silicon oxynitride.

24. A method in accordance with claim 13 wherein the glass forming coating is applied by sol-gel technology.

25. A method for the manufacture of a coated carbon body having improved resistance to high temperature oxidation comprising:

providing a carbon body,

contacting said carbon body with gaseous boron oxide at an elevated temperature sufficient to cause reaction between the carbon body and the boron oxide thereby forming a converted porous layer containing interconnecting interstices in said body, which layer contains boron carbide,

applying an intermediate glass forming coating over said converted layer, said intermediate coating comprising silicon or a silicon-containing compound,

subjecting said body with a nitriding atmosphere to convert said silicon or silicon-containing compound to silicon nitride, and

applying an outer refractory coating over said intermediate coating.

26. A method in accordance with claim 25 wherein the nitriding atmosphere is selected from the group consisting of N₂, NH₃, N₂ H₄, and mixtures thereof.

27. A method in accordance with claim 26 wherein said carbon body is subjected to the nitriding atmosphere at temperatures in the range of about 1350°

to about 1500°

C.

28. A method in accordance with claim 27 wherein the nitriding atmosphere contains small amounts of hydrogen.

29. A method in accordance with claim 25 wherein the nitriding atmosphere contains oxygen or an oxygen-containing compound to convert the silicon or silicon-containing compound to an oxynitride of silicon.

30. A method in accordance with claim 29 wherein the oxygen-containing compound is H2O or CO/CO₂.