Method for waterproofing ceramic materials

• US 5,814,397 A
• Filed: 09/13/1995
• Issued: 09/29/1998
• Est. Priority Date: 09/13/1995
• Status: Expired due to Fees

• Current Assignee: Administrator of The National Aeronautics and Space Administration, The United States of America As Represented By The Secretary of Agriculture
• Original Assignee: United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration
• Inventors: Hsu, Ming-Ta S., Cagliostro, Domenick E.
• Primary Examiner(s): Kiliman, Leszek
• Assistant Examiner(s): TARAZANO, DONALD LAWRENCE
• Application Number:
  US08/537,585
• Time in Patent Office: 1,112 Days
• Field of Search: 428/446, 428/447, 428/704, 428/698, 428/216, 428/336, 428/307.3, 428/307.7, 428/312.6, 428/920, 427/412, 427/407.1, 427/344, 427/515, 427/244, 427/245, 427/255.3, 427/226, 244/158 A, 244/163, 244/121, 244/133, 442/79, 442/81, 442/86, 442/87
• US Class Current: 428/216
• CPC Class Codes: B64G 1/226 Special coatings for spacecraft
• CPC Class Codes: B64G 1/58 Thermal protection, e.g. heat shields
• CPC Class Codes: C04B 2111/00982 as construction elements for space vehicles or aeroplanes
• CPC Class Codes: C04B 2111/27 Water resistance, i.e. waterproof or water-repellent materials
• CPC Class Codes: C04B 30/02 containing fibrous materials
• CPC Class Codes: C04B 41/009 characterised by the material treated
• CPC Class Codes: C04B 41/4554 the coating or impregnating material being an organic or organo-metallic precursor of an inorganic material
• CPC Class Codes: C04B 41/4961 Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
• CPC Class Codes: C04B 41/5035 Silica
• 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: Y10S 428/92 Fire or heat protection feature
• CPC Class Codes: Y10T 428/24975 No layer or component greater than 5 mils thick
• CPC Class Codes: Y10T 428/249956 Void-containing component is inorganic
• CPC Class Codes: Y10T 428/249957 Inorganic impregnant
• CPC Class Codes: Y10T 428/249969 Of silicon-containing material [e.g., glass, etc.]
• CPC Class Codes: Y10T 428/265 1 mil or less
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane
• CPC Class Codes: Y10T 442/2164 Coating or impregnation specified as water repellent
• CPC Class Codes: Y10T 442/218 Organosilicon containing
• CPC Class Codes: Y10T 442/2221 Coating or impregnation is specified as water proof
• CPC Class Codes: Y10T 442/223 : Organosilicon containing

Abstract

Hygroscopic ceramic materials which are difficult to waterproof with a silane, substituted silane or silazane waterproofing agent, such as an alumina containing, fibrous, flexible and porous, fibrous ceramic insulation used on a reentry space vehicle, are rendered easy to waterproof if the interior, porous surface of the ceramic is first coated with a thin coating of silica. The silica coating is achieved by coating the interior surface of the ceramic with a silica precursor, converting the precursor to silica either in-situ or by oxidative pyrolysis and then applying the waterproofing agent to the silica coated ceramic. The silica precursor comprises almost any suitable silicon containing material such as a silane, silicone, siloxane, silazane and the like applied by solution, vapor deposition and the like. If the waterproofing is removed by, e.g., burning, the silica remains and the ceramic is easily rewaterproofed. An alumina containing TABI insulation which absorbs more that five timed its weight of water, absorbs less than 10 wt. % water after being waterproofed according to the method of the invention.

Claims

1. A method for waterproofing porous ceramic thermal insulation having an exterior and an interior surface which comprises coating said exterior and interior surfaces with a silica precursor, converting said precursor to silica to form a silica coating less than one micron thick, and then coating said silica coated ceramic with a coating of a silicon containing waterproofing agent less than one micron thick.

2. A method according to claim 1 wherein said precursor is converted to silica by heating in an oxidizing atmosphere at a temperature and for a time sufficient to effect said conversion.

3. A method according to claim 1 wherein said silica precursor decomposes on said exterior and interior surface to form said silica coating during said deposition process.

4. A method according to claim 3 wherein said waterproofing agent is selected from the group consisting of a substituted silane, a silazane and mixture thereof.

5. A method according to claim 4 wherein said thermal insulation has a void volume of more than 90%.

6. A method according to claim 5 wherein said ceramic includes alumina.

7. A method according to claim 2 wherein said waterproofing agent is selected from the group consisting of a substituted silane, a silazane and mixture thereof.

8. A method according to claim 7 wherein said ceramic includes alumina.

10. A method according to claim 1 wherein said waterproofed insulation is exposed to a high temperature environment which removes said waterproofing agent, but not said silica coating, and wherein a coating of said waterproofing agent is reapplied to said silica coated surfaces.

11. A method according to claim 1 wherein said waterproofed thermal insulation absorbs less than 25 wt. % water after being immersed in distilled water for fifteen minutes.

12. A method according to claim 5 wherein said waterproofed thermal insulation absorbs less than 15 wt. % water after being immersed in distilled water for fifteen minutes.

13. A method according to claim 5 wherein said waterproofed thermal insulation absorbs less than 5 wt. % water after being immersed in distilled water for fifteen minutes.

9. A flexible waterproofed ceramic composite comprising a porous ceramic blanket insulation fabricated from ceramic fibers, wherein said composite has an exterior surface which is coated with a thin coating of silica less than one micron thick and wherein a thin coating of a silicon containing waterproofing agent less than one micron thick is disposed over said silica coating.

14. A method for waterproofing porous thermal insulation having an exterior and an interior surface which comprises at least one ceramic material and which is useful for the thermal protection system on a space vehicle, said method comprising coating said exterior and interior surface with a silica precursor, converting said precursor to silica to form a silica coating less than one micron thick, and then coating said silica coated exterior and interior surfaces with a coating less than one micron thick of a silicon containing waterproofing agent.

15. A method according to claim 14 wherein said waterproofed insulation absorbs less than 15 wt. % water after being immersed in distilled water for fifteen minutes.

16. A method according to claim 14 wherein said insulation includes alumina.

17. A method according to claim 16 wherein said alumina is in the form of a batting made of alumina fibers.

18. A method according to claim 14 wherein said silica precursor converts to silica during said coating process.

19. A method according to claim 18 wherein said waterproofed insulation absorbs less than 15 wt. %, water after being immersed in distilled water for fifteen minutes.

20. A method according to claim 19 wherein said insulation includes alumina.

21. A method according to claim 16 wherein said alumina is in the form of a batting made of alumina fibers.

22. A method according to claim 21 wherein said waterproofed insulation absorbs less than 15 wt. % water after being immersed in distilled water for fifteen minutes.

23. A method according to claim 19 wherein said waterproofed insulation absorbs less than 10 wt. % water after being immersed in distilled water for fifteen minutes.

24. A method according to claim 14 wherein said insulation has a void volume of at least 90%.

25. A method according to claim 14 wherein said waterproofed insulation is exposed to a high temperature environment which removes said waterproofing agent, but not said silica coating, and wherein a coating of said waterproofing agent is reapplied to said silica coated surfaces.

26. A method for waterproofing a porous and flexible thermal insulating material having an exterior and an interior surface and comprising at least one material from the group consisting of fabric, batting, fiber and felt made of at least one member from the group consisting of ceramic fiber, thread and filament, said method comprising coating said exterior and interior surfaces with a silica precursor, converting said precursor to silica to form a silica coating less than one micron thick, and then coating said silica coated surfaces with a coating less than one micron thick of a silicon containing waterproofing agent.

27. A method according to claim 26 wherein said insulation comprises a multilayered flexible blanket of insulation comprising at least one layer containing of at least one material of from the group ceramic fabric, batting, fiber and felt.

28. A method according to claim 27 wherein at least one of said layers comprises a ceramic fabric which comprises alumina fiber.

29. A method according to claim 27 wherein at least one of said layers comprises alumina.

30. A method according to claim 27 wherein said waterproofed insulation is exposed to a high temperature environment which removes said waterproofing agent, but not said silica coating, and wherein a coating of said waterproofing agent is reapplied to said silica coated surfaces.

31. A waterproofed, porous and flexible thermal insulating material having an exterior and an interior surface and comprising at least one material from the group consisting of fabric, batting, fiber and felt made of at least one member from the group consisting of ceramic fiber, thread and filament, wherein exterior and interior surfaces are coated with a silica coating less than one micron thick and wherein said silica coated surfaces are coated with a coating less than one micron thick of a silicon containing waterproofing agent.

32. A material according to claim 31 having a void volume of at least 90%.

33. A material according to claim comprising alumina and which absorbs less than 25 wt. % water after being immersed in water for fifteen minutes.