Low density microcellular carbon foams and method of preparation

• US 4,832,881 A
• Filed: 06/20/1988
• Issued: 05/23/1989
• Est. Priority Date: 06/20/1988
• Status: Expired due to Fees

• Current Assignee: The United States of America As Represented By The Secretary of Agriculture
• Original Assignee: United States Department of Energy
• Inventors: Sylwester, Alan P., Aubert, James H., Rand, Peter B., Arnold, Charles Jr., Clough, Roger L.
• Primary Examiner(s): Foelak, Morton
• Application Number:
  US07/209,168
• Time in Patent Office: 337 Days
• Field of Search: 264/29.7, 264/29.1, 423/445, 423/449, 502/101, 502/180, 502/416, 502/418, 521/918
• US Class Current: 264/29.7
• CPC Class Codes: B01J 20/20 comprising free carbon; comprising carbon obtained by carbonising processes
• CPC Class Codes: B01J 21/18 Carbon
• CPC Class Codes: B01J 35/56 Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
• CPC Class Codes: C04B 2111/0081 as catalysts or catalyst carriers
• CPC Class Codes: C04B 35/52 based on carbon, e.g. graphite
• CPC Class Codes: C04B 38/0022 obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
• CPC Class Codes: Y10S 521/918 Physical aftertreatment of a cellular product

Abstract

A low density, open-celled microcellular carbon foam is disclosed which is prepared by dissolving a carbonizable polymer or copolymer in a solvent, pouring the solution into a mold, cooling the solution, removing the solvent, and then carbonizing the polymer or copolymer in a high temperature oven to produce the foam. If desired, an additive can be introduced in order to produce a doped carbon foam, and the foams can be made isotropic by selection of a suitable solvent. The low density, microcellular foams produced by this process are particularly useful in the fabrication of inertial confinement fusion targets, but can also be used as catalysts, absorbents, and electrodes.

Claims

1. A method of preparing a low-density, open-celled microcellular carbon foam comprising the steps of:

(a) dissolving a carbonizable polymer or copolymer in a solvent at a temperature sufficient to effect complete dissolution;

(b) pouring the dissolved polymeric or copolymeric solution into a mold;

(c) quenching the solution in order to induce phase separation between the polymer and solvent to form a gelled open-celled foamed structure from the polymer phase wherein the solvent is impregnated into the pores of the foam;

(d) removing the solvent; and

(e) carbonizing the polymer or copolymer in a high temperature oven to obtain an open-celled carbon having a pore size equal to or less than 10 microns.

2. A method according to claim 1 wherein the dissolution step is carried out at a temperature of from about 100°

to 200°

C.

3. A method according to claim 1 wherein an acrylonitrile-based polymer is dissolved in the solvent.

4. A method according to claim 3 wherein the acrylonitrile-based polymer comprised polyacrylonitrile.

5. A method according to claim 1 wherein an acrylonitrile-based copolymer is dissolved in the solvent.

6. A method according to claim 5 wherein the acrylonitrile-based copolymer is polyacrylonitrile-co-maleic anhydride.

7. A method of according to claim 1 wherein the carbonizable polymer is selected from the group consisting of phenolics, guar gums, polyesters, poly(furfuryl alcohol), polyimides, cellulose polymers, polyamides, polyacrylethers, polyphenylenes, polyacenaphthalenes, polytriadiazoles, and polyvinylpyridines.

8. A method according to claim 1 wherein the solvent comprises maleic anhydride.

9. A method according to claim 1 wherein the solvent comprises a mixture of methyl sulfone and cyclohexanol.

10. A method according to claim 9 wherein the solvent comprises 70-90% methyl sulfine with 10-30% cyclohexanol by weight.

11. A method according to claim 1 wherein the solvent comprises aqueous methyl sulfone.

12. A method according to claim 11 wherein the solvent comprises a mixture of 85-95% methyl sulfone with 5-15% water (wt./vol.).

13. A method according to claim 1 wherein the solvent comprises aqueous dimethyl formamide.

14. A method according to claim 13 wherein the solvent comprises a mixture of 75-95% dimethyl formamide and 5-25% water (vol./vol.).

15. A method according to claim 1 wherein the solvent is removed by sublimation under vacuum.

16. A method according to claim 1 wherein the carbonizable polymer or copolymer solution forms into a gel during the cooling step, and wherein the solvent is removed by extraction.

17. A method according to claim 1 wherein the carbonizable polymer or copolymer is carbonized by subjecting the polymer or copolymer after removal of solvent to an oxygen atmosphere for about 12-24 hours at a temperature of from about 180°

-160°

C., then subjecting the polymer or copolymer to a temperature of from about 500°

-2,500°

C. for 6-10 hours in the presence of an inert gas.

18. A method according to claim 17 wherein the inert gas is argon.

19. A method according to claim 1 further comprising the addition of an additive to the microcellular carbon foam.

20. A method according to claim 19 wherein the additive is selected from the group consisting of salts, soluble organic compounds, metal-containing compounds, and particulates.

21. A method according to claim 19 wherein the additive is added to the microcellular foam by dissolving or dispersing the additive in the solution of dissolved polymer or copolymer.

22. A method according to claim 20 wherein the additive is a metal-containing compound.

23. A method according to claim 22 wherein the additive is a crystalline non-volatile organometallic compound.

24. A method according to claim 23 wherein the additive is an acetylacetonate.

25. A method according to claim 24 wherein the additive is palladium acetylacetonate.

26. A method according to claim 22 wherein the additive is selected from the group consisting of ammonium salts, oxalates, carboxylates, nitrates, chlorides, oxides, cycloocatadienyl compounds, and micron to submicron-sized insoluble particles.

27. A method according to claim 1 comprising the steps of

(c) quenching the solution so that liquid phase separation occurs, and continuing to cool the solution until the solvent freezes;

and

(d) removing the solvent by sublimation under vacuum.