Continuous glassy carbon composite materials reinforced with carbon nanotubes and methods of manufacturing same

• US 20080286546A1
• Filed: 03/08/2007
• Published: 11/20/2008
• Est. Priority Date: 05/03/2005
• Status: Abandoned Application

• Current Assignee: Nanocomp Technologies Inc. (Huntsman Corporation)
• Original Assignee: Nanocomp Technologies Inc. (Huntsman Corporation)
• Inventors: Lashmore, David S., Antoinette, Peter L.
• Application Number:
  US11/715,756
• Publication Number:
  US 20080286546A1
• Time in Patent Office: Days
• US Class Current: 428/220
• CPC Class Codes: B01J 21/185 Carbon nanotubes carbon nanotubes per se C01B32/15
• CPC Class Codes: B01J 23/74 Iron group metals
• CPC Class Codes: B01J 23/8474 Niobium
• CPC Class Codes: B01J 23/85 Chromium, molybdenum or tungsten
• CPC Class Codes: B01J 37/0009 Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• CPC Class Codes: B01J 37/20 Sulfiding
• CPC Class Codes: B29C 48/022 characterised by the choice of material
• CPC Class Codes: B29C 48/08 flexible, e.g. films
• CPC Class Codes: B29C 48/832 Heating
• CPC Class Codes: B29C 48/86 at the nozzle zone
• CPC Class Codes: B29C 48/91 Heating, e.g. for cross linking
• CPC Class Codes: B29K 2105/06 containing reinforcements, fillers or inserts
• CPC Class Codes: B29K 2105/162 Nanoparticles
• CPC Class Codes: B32B 19/02 the layer of fibres or particles being impregnated or embedded in a plastic substance
• CPC Class Codes: B32B 5/02 characterised by structural features of a fibrous or filamentary layer layer formed of metallic wires B32B15/02; layer formed of natural mineral fibres B32B19/02; layer formed of wood fibres B32B21/02
• CPC Class Codes: B32B 5/26 another layer next to it also being fibrous or filamentary relative arrangement of fibres or filaments of different layers B32B5/12
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C04B 2235/405 Iron group metals
• CPC Class Codes: C04B 2235/5264 characterised by the diameter of the fibers
• CPC Class Codes: C04B 2235/5288 Carbon nanotubes
• CPC Class Codes: C04B 2235/6021 : Extrusion moulding
• CPC Class Codes: C04B 35/524 : obtained from polymer precursors, e.g. glass-like carbon material
• CPC Class Codes: C04B 35/6267 : Pyrolysis, carbonisation or auto-combustion reactions
• CPC Class Codes: C04B 35/6269 : Curing of mixtures
• CPC Class Codes: C04B 35/83 : Carbon fibres in a carbon matrix
• CPC Class Codes: F41H 5/0471 : Layered armour containing fibre- or fabric-reinforced layers in combination with ceramic layers F41H5/0428, with metal layers F41H5/0457
• CPC Class Codes: Y10T 428/249924 : Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
• CPC Class Codes: Y10T 428/249929 : Fibers are aligned substantially parallel
• CPC Class Codes: Y10T 428/2918 : including free carbon or carbide or therewith [not as steel]

Abstract

A method for manufacturing a carbon composite is provided. The method includes providing a carbon-containing resin material having an appropriate concentration of catalyst particles. Thereafter, the resin material may be extruded through an aperture while being exposed to a high temperature range to permit polymerization of the extruded resin material. A subsequent exposure of the extruded resin material to another elevated temperature range causes carbon in the resin material to couple to the catalyst particles to promote carbon nanotube growth and transformation of the resin material to a reinforced composite material. Reinforced composite materials are also provided.

Claims

17. A composite material comprising:

a substantially continuous sheet; and

an array of substantially continuous carbon nanotubes extending within the sheet along its length.

1. A composite material comprising:

a substantially continuous filament; and

at least one substantially continuous carbon nanotube extending within the filament along its length.

2. A composite material as set forth in claim 1, wherein the filament has a diameter in a range of from about 0.5 microns to about 500 microns.

3. A composite material as set forth in claim 1, wherein the filament has a diameter of less than about 10 microns.

4. A composite material as set forth in claim 1, wherein the filament has a diameter of less than about 2 microns.

5. A composite material as set forth in claim 1, wherein the filament includes a glassy carbon matrix extending substantially the length of the filament.

6. A composite material as set forth in claim 1, wherein the filament is made from a resin material having a glassy carbon precursor.

7. A composite material as set forth in claim 6, wherein the glassy carbon precursor includes one of RESOL resin, furfuryl alcohol, PVA, or other similar materials with a glassy carbon precursor.

8. A composite material as set forth in claim 1, wherein the filament is made from a resin material having a non-glassy carbon precursor, such as pitch.

9. A composite material as set forth in claim 1, wherein the nanotube in the filament exists in an amount ranging from about 1% by volume to about 70% by volume.

10. A composite material as set forth in claim 1, wherein the amount of nanotubes in the filament is about 50% by volume.

11. A composite material as set forth in claim 1, wherein the nanotube includes a catalyst at one of its ends.

12. A composite material as set forth in claim 11, wherein the catalyst includes one of ferrocene;

iron nano-particles;

iron pentacarbonyl;

nano-particles of magnetic transition metals or a compound of magnetic transition metals;

noble metals;

ceramic and intermetallic particles;

fullerenes;

small portions of carbon nanotubes;

or a combination of any of these.

13. A composite material as set forth in claim 12, wherein the magnetic transition metals include one of iron, cobalt, cobalt hexacarbonyl, nickel, nickel hexacarbonyl, molybdenum, or their alloys, or oxides, nitrates or chlorides of these metals, or any combination of the oxides or other reducible salts, or organometallic compounds of these metals.

14. A composite material as set forth in claim 12, wherein the noble metals include gold particles having a diameter in a range of from about 1 nm to about 10 nm.

15. A composite material as set forth in claim 12, wherein the fullerenes include C₆₀.

16. A composite material as set forth in claim 11, wherein the catalyst includes a mixture of fullerene, ferrocene, and thiopene.

18. A composite material as set forth in claim 17, wherein the sheet has a thickness in a range of from about 0.5 microns to about 500 microns.

20. A composite material as set forth in claim 17, wherein the sheet has a thickness of less than about 2 microns.

21. A composite material as set forth in claim 17, wherein the sheet includes a film of a glassy carbon matrix extending substantially the length of the sheet.

22. A composite material as set forth in claim 17, wherein the filament is made from a resin material having a glassy carbon precursor.

23. A composite material as set forth in claim 22, wherein the glassy carbon precursor includes one of RESOL resin, furfuryl alcohol, PVA, or other similar glassy carbon precursor materials.

24. A composite material as set forth in claim 17, wherein the sheet is made from a resin material having a non-glassy carbon precursor, such as pitch.

25. A composite material as set forth in claim 17, wherein the array of nanotubes in the sheet exists in an amount ranging from about 1% by volume to about 70% by volume.

26. A composite material as set forth in claim 17, wherein the array of nanotubes in the sheet is about 50% by volume.

27. A composite material as set forth in claim 17, wherein each nanotube includes a catalyst at one of its ends.

28. A composite material as set forth in claim 27, wherein the catalyst includes one of ferrocene;

iron nano-particles;

iron pentacarbonyl;

nano-particles of magnetic transition metals or a compound of magnetic transition metals;

noble metals;

ceramic and intermetallic particles;

fullerenes;

small portions of carbon nanotubes;

or a combination of any of these.

29. A composite material as set forth in claim 28, wherein the magnetic transition metals include one of iron, cobalt, cobalt hexacarbonyl, nickel, nickel hexacarbonyl, molybdenum, or their alloys, or oxides, nitrates or chlorides of these metals, or any combination of the oxides or other reducible salts, or organometallic compounds of these metals.

30. A composite material as set forth in claim 28, wherein the noble metals include gold particles having a diameter in a range of from about 1 nm to about 10 nm.

31. A composite material as set forth in claim 28, wherein the fullerenes include C₆₀.

32. A composite material as set forth in claim 27, wherein the catalyst includes a mixture of fullerene, ferrocene, and thiophene.

39. A method as set forth in claim 33, wherein, in the step of extruding, the glassy carbon precursor includes one of RESOL resin, furfuryl alcohol, PVA, or other similar glassy carbon precursor materials.

18-1. A composite material as set forth in claim 17, wherein the sheet has a thickness of less than about 10 microns.

33. A method of manufacturing a composite material, the method comprising:

extruding a resin material having a glassy carbon precursor and a catalyst through an aperture;

exposing the resin material as it is being extruded to a first elevated temperature range, so as to polymerize the resin material;

subjecting the polymerized resin material to a second elevated temperature range, so as to promote growth of at least one carbon nanotube from the catalyst and to transform the resin material into a reinforced composite material.

34. A method as set forth in claim 33, wherein the step of extruding includes heating the aperture to a temperature to promote initial polymerization of the resin material as it passes therethrough.

35. A method as set forth in claim 33, wherein the step of extruding includes coupling the aperture to a pressurized source to permit the subsequent extrusion to be performed under pressure.

36. A method as set forth in claim 33, wherein, in the step of extruding, the aperture approximates a geometric shape that provides the extruded resin material with a filamentous shape.

37. A method as set forth in claim 33, wherein, in the step of extruding, the aperture approximates a geometric shape that provides the extruded resin material with a shape of a sheet.

38. A method as set forth in claim 33, wherein the step of extruding includes heating the resin material to a temperature below that at which the resin material can start to polymerize.

40. A method as set forth in claim 33, wherein, in the step of extruding, the catalyst includes one of ferrocene;

iron nano-particles;

iron pentacarbonyl;

nano-particles of magnetic transition metals or a compound of magnetic transition metals;

noble metals;

ceramic and intermetallic particles;

fullerenes;

small portions of carbon nanotubes;

or a combination of any of these.

41. A method as set forth in claim 33, wherein, in the step of exposing, the first temperature range is about 300°

C. or less.

42. A method as set forth in claim 33, wherein, in the step of subjecting, the second temperature range is from about 1000°

C. to about 2000°

C.

43. A method as set forth in claim 33, wherein the step of subjecting occurs in an inert atmosphere.

39-2. A method as set forth in claim 31, wherein the step of exposing includes substantially completing the polymerization of the resin material.