Method for growing continuous carbon fiber and compositions thereof

• US 6,756,026 B2
• Filed: 12/21/2001
• Issued: 06/29/2004
• Est. Priority Date: 08/08/1996
• Status: Expired due to Term

• Current Assignee: Rice University
• Original Assignee: Rice University
• Inventors: Liu, Jie, Smith, Kenneth A., Guo, Ting, Smalley, Richard E., Rinzler, Andrew G., Nikolaev, Pavel, Colbert, Daniel T., Thess, Andreas, Hafner, Jason H., Dai, Hongjie
• Primary Examiner(s): Hendrickson, Stuart L.
• Assistant Examiner(s): Lish, Peter J
• Application Number:
  US10/027,750
• Publication Number:
  US 20020109086A1
• Time in Patent Office: 921 Days
• Field of Search: 423/447.1, 423/447.2, 423/447.3, 423/445.R, 427/249.1, 427/249.3, 427/249.4, 427/585
• US Class Current: 423/447.3
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: B82Y 15/00 Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 35/00 Methods or apparatus for measurement or analysis of nanostructures
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C01B 2202/02 Single-walled nanotubes
• CPC Class Codes: C01B 2202/06 Multi-walled nanotubes
• CPC Class Codes: C01B 2202/08 Aligned nanotubes
• CPC Class Codes: C01B 2202/24 Thermal properties
• CPC Class Codes: C01B 2202/34 Length
• CPC Class Codes: C01B 32/154 Preparation
• CPC Class Codes: C01B 32/162 characterised by catalysts
• CPC Class Codes: C01B 32/174 Derivatisation; Solubilisation; Dispersion in solvents
• CPC Class Codes: G01Q 70/12 Nanotube tips
• CPC Class Codes: G01Q 70/16 Probe manufacture
• CPC Class Codes: G11B 11/007 with reproducing by means directly associated with the tip of a microscopic electrical probe as defined in G11B9/14 details of heads G11B9/1409; disposition or mounting of heads G11B9/1418
• CPC Class Codes: G11B 9/1409 Heads
• CPC Class Codes: G11C 13/025 using fullerenes, e.g. C60, or nanotubes, e.g. carbon or silicon nanotubes
• CPC Class Codes: G11C 2213/81 Array wherein the array conductors, e.g. word lines, bit lines, are made of nanowires
• CPC Class Codes: H01J 2201/30469 Carbon nanotubes (CNTs)
• CPC Class Codes: Y10S 977/70 : Nanostructure
• CPC Class Codes: Y10S 977/75 : Single-walled
• CPC Class Codes: Y10S 977/789 : in array format
• CPC Class Codes: Y10S 977/843 : Gas phase catalytic growth, i.e. chemical vapor deposition
• CPC Class Codes: Y10S 977/845 : Purification or separation of fullerenes or nanotubes
• CPC Class Codes: Y10T 428/249977 : Specified thickness of void-containing component [absolute or relative], numerical cell dimension or density
• CPC Class Codes: Y10T 428/2918 : including free carbon or carbide or therewith [not as steel]

Abstract

This invention relates generally to a method for growing carbon fiber from single-wall carbon nanotube (SWNT) molecular arrays. The carbon fiber which comprises an aggregation of substantially parallel carbon nanotubes may be produced by growth (elongation) of a suitable seed molecular array. The first step is to open the growth end of the SWNTs in the molecular array. Next, a transition metal catalyst is added to the open-ended seed array. In the next step, the SWNT molecular array with catalyst deposited on the open tube ends is subjected to tube growth (extension) conditions. The carbon supply necessary to grow the SWNT molecular array into a continuous fiber is supplied to the SWNT molecular array tip heated to a temperature sufficient to cause growth to any desired length. The continuous carbon fiber can also be grown from more than one separately prepared molecular arrays or templates.

Claims

1. A method for growing continuous carbon fiber comprising:

a) providing an array of single-wall carbon nanotubes in generally parallel orientation;

b) contacting the ends of the single-wall carbon nanotubes with at least one catalytic metal;

c) activating the catalytic metal;

d) contacting a gaseous source of carbon to the array and the catalytic metal;

e) heating at least one of the array, the catalytic metal, and the gaseous source of the carbon;

f) growing the single-wall carbon nanotubes at the ends of the single-wall carbon nanotubes to form a continuous carbon fiber, wherein the fiber comprises the single-wall carbon nanotubes in generally parallel orientation; and

g) recovering the continuous carbon fiber.

2. A. The method of claim 1 further comprising removing end caps from at least some of the ends of the single-wall carbon nanotubes, wherein the end caps are removed by an oxiclative treatment.

3. The method of claim 2 wherein the oxidative treatment comprises a technique selected from the group consisting of oxidative etching, electrochemical oxidative etching and combinations thereof.

4. The method of claim 2 wherein the oxidative treatment comprises the use of a chemical selected from the group consisting of nitric acid, oxygen, carbon dioxide and combinations thereof.

5. The method of claim 2 wherein the oxidative treatment is conducted at a temperature at at most about 500°

C.

6. The method of claim 1 wherein the catalytic metal comprises a metal selected from the group consisting of transition metals, Group VIII metals, metals of the lanthanide series, metals of the actinide series and mixtures thereof.

7. The method of claim 1 wherein the catalytic metal comprises a metal selected from the group consisting of iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt) and mixtures thereof.

8. The method of claim 1 wherein the catalytic metal is deposited on the array.

9. The method of claim 8 wherein the catalytic metal is deposited by a deposition method selected from the group consisting of deposition of a metal vapor in a vacuum, deposition of pre-formed catalyst particles, deposition of a catalyst precursor and combinations thereof.

10. The method of claim 9 wherein the deposition of the metal vapor is done by heating at least one wire comprising the catalytic metal.

11. The method of claim 9 wherein molecular beam epitaxy equipment is used during the deposition method.

12. The method of claim 9 wherein the catalyst precursor is a substance selected from the group consisting of an oxide, salt, metal complex and combinations thereof.

13. The method of claim 1 wherein the activating of the catalytic metal is by heating.

14. The method of claim 1 wherein the activating of the catalyst metal is by heating under reductive conditions.

15. The method of claim 1 wherein the activating of the catalytic metal produces metal atom clusters comprising between about 10 and about 200 metal atoms.

16. The method of claim 15 wherein the metal atom clusters are located at the ends of the single-wall carbon nanotubes.

17. The method of claim 1 wherein the gaseous source of carbon comprises a carbon feedstock selected from the group consisting of hydrocarbons and carbon monoxide.

18. The method of claim 1 wherein growing the single-wall carbon nanotubes comprises elongation of the single-wall carbon nanotubes in the array.

19. The method of claim 17 wherein the hydrocarbon is selected from the group consisting of alkyls, acyls, aryls and aralkyls.

20. The method of claim 17 wherein the hydrocarbon comprises between 1 and about 7 carbon atoms.

21. The method of claim 17 wherein the hydrocarbon is selected from the group consisting of methane, ethane, ethylene, acetylene, acetone, propane, propylene and mixtures thereof.

22. The method of claim 17 wherein the hydrocarbon is ethylene.

23. The method of claim 1 wherein the gaseous source of carbon is carbon monoxide.

24. The method of claim 1 wherein the gaseous source of carbon is at a partial pressure between 0.001 Torr and 10 Torr.

25. The method claim 1 wherein the gaseous source of carbon is at a partial pressure between about 1.0 and about 10 Torr.

26. The method of claim 1 further comprising adding an inert gas to the gaseous source of carbon.

27. The method of claim 26 wherein the inert gas comprises a gas selected from the group consisting of argon and helium.

28. The method of claim 1 wherein the heating is provided by electromagnetic radiation.

29. The method of claim 1 wherein the heating is providing by a laser.

30. The method of claim 1 wherein the heating is localized at the ends of the single-wall carbon nanotubes in the array.

31. The method of claim 1 wherein the heating is at a temperature in a range between about 500°

C. and about 1300°

C.

32. The method of claim 1 wherein the heating is at a temperature in a range between about 500°

C. and about 1200°

C.

33. The method of claim 1 wherein the heating is at a temperature in a range between about 700°

C. and about 1200°

C.

34. The method of claim 1 wherein the heating is at a temperature in a range between about 900°

C. and about 1100°

C.

35. The method of claim 1 wherein the array is a cross section of a previously-grown fiber.

36. The method of claim 35 wherein the array is a cut section of a previously-grown fiber.

37. The method of claim 35 wherein the fullerene caps are removed by oxidative treatment.

38. The method of claim 37 wherein the oxidative treatment comprises a technique selected from the group consisting of oxidative etching electrochemical, oxidating etching and combinations thereof.

39. The method of claim 1 wherein the array comprises:

a) a first plurality of the single-wall carbon nanotubes having a first homogeneous characteristic selected from the group consisting of lengths, diameters, helicities and combinations thereof; and

b) a second plurality of the single-wall carbon nanotubes having a second homogenous characteristic selected from the group consisting of lengths, diameters, helicities and combinations thereof, wherein the first homogeneous characteristic is different than the second homogeneous characteristic.

40. The method of claim 39 wherein the first plurality and the second plurality are in different regions of the continuous carbon fiber.

41. The method of claim 1 wherein at least two arrays are provided.

42. The method of claim 41 wherein at least one of the arrays comprises single-wall carbon nanotubes having a different homogeneous characteristic than the homogeneous characteristic of the single-wall carbon nanotubes of at least one other array, wherein the homogeneous characteristic is selected from the group consisting of lengths, diameters, helicities and combinations thereof.

43. The method of claim 41 wherein the arrays are arranged in cable-like structures.

44. The method of claim 42 wherein the arrays are arranged in cable-like structures.

45. The method of claim 41 wherein a composite fiber of the arrays comprises a central core surrounded by non-metallic single-wall carbon nanotubes, wherein the central core comprises metallic single-wall carbon nanotubes.

46. The method of claim 44 wherein the arrays are arranged to produce a composite fiber wherein an orientation of a first section of the composite fiber is not parallel to an orientation of a second section of composite fiber.

47. The method of claim 1 further comprising using an electric field to align the single-wall carbon nanotubes.