Method for cutting single-wall carbon nanotubes

• US 7,052,666 B2
• Filed: 12/21/2001
• Issued: 05/30/2006
• Est. Priority Date: 08/08/1996
• Status: Expired due to Fees

• Current Assignee: Rice University
• Original Assignee: Rice University
• Inventors: Smalley, Richard E., Liu, Jie, Rinzler, Andrew G., Nikolaev, Pavel, Colbert, Daniel T., Thess, Andreas, Hafner, Jason H., Smith, Kenneth A., Guo, Ting, Dai, Hongjie
• Primary Examiner(s): Hendrickson, Stuart L.
• Assistant Examiner(s): DUNN, COLLEEN P
• Application Number:
  US10/027,671
• Publication Number:
  US 20020096634A1
• Time in Patent Office: 1,621 Days
• Field of Search: 423/447.1, 423/447.2, 423/445.R, 423/445.B, 423/461
• US Class Current: 423/447.1
• 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 cutting single-wall carbon nanotubes (SWNT). In one embodiment, the present invention provides for preparations of homogemeous populations of short carbon nanotube molecules by cutting and annealing (reclosing) the nanotube pieces followed by fractionation. The cutting and annealing processes may be carried out on a purified nanotube bucky paper, on felts prior to purification of nanotubes or on any material that contains single-wall nanotubes. In one embodiment, oxidative etching with concentrated nitric acid is employed to cut SWNTs into shorter lengths. The annealed nanotubes may be disbursed in an aqueous detergent solution or an organic solvent for the fractionation. Closed tubes can also be derivatized to facilitate fractionation, for example, by adding solubilizing moieties to the end caps.

Claims

1. A method for untangling single-wall carbon nanotubes comprising:

a) providing tangled single-wall carbon nanotubes;

b) cutting at least a portion of the single-wall carbon nanotubes to un-tangle at least some of the single-wall carbon nanotubes; and

c) recovering a material comprising the single-wall carbon nanotubes un-tangled by the cutting step.

2. The method of claims 1 wherein the single wall carbon nanotubes are cut by a method selected from the group consisting of irradiation with ions, oxidative attack, sonication, oxidative etching, electron beam cutting, plasma arc cutting and combinations thereof.

3. The method of claim 1 wherein the single-wall carbon nanotubes in the material have a mean length that is shorter than a mean length of the single-wall cargon nanotubes in the tangled single-wall carbon nanotubes.

4. The method of claim 1 where in the material comprises single-wall carbon nanotubes having lengths in the range between about 5 and about 1000 nm.

5. The method of claim 1 wherein the material comprises single-wall carbon nanotubes having lengths in the range between about 50 and 500 nm.

6. The method of claim 1 further comprising forming a suspension of the tangled single-wall carbon nanotubes in a liquid medium.

7. The method of claim 6 wherein the liquid medium comprises a hydrocarbon.

8. The method of claim 6 further comprising refluxing the suspension.

9. The method of claim 6 further comprising sonicating the suspension with acoustic energy.

10. The method of claim 1 wherein the tangled single-wall carbon nanotubes comprise single-wall carbon nanotubes in a form selected from the group consisting of ropes and mats.

11. The method of claim 10 further comprising dispersing the tangled single-wall carbon nanotubes in a medium selected from the group consisting of an aqueous detergent solution and organic solvent.

12. The method of claim 11 where in the dispersing is by sonication in a liquid selected from the group consisting of benzene, toluene, xylene, naphthalne, 1,2-dichloroethane and combinations thereof.

13. The method of claim 1 wherein the recover comprises filtration.

14. A method of modifying single-wall nanotubes comprising the step of removing a fullerene cap at least one end of the single-wall carbon nanotubes.

15. The method of claim 14 wherein the single-wall carbon nanotubes are exposed to an oxidative treatment.

16. The mehod of claim 15 wherein the oxidative treatment comprises a technique selected from the group consisting of oxidative etching, electrochemical oxidative etching and combinations thereof.

17. the method of claim 15 wherein the oxidative treatment comprises the use of a chemical selected from the goup consisting of nitric acid, oxygen, carbon dioxide and combinations thereof.

18. The method of claim 15 where in the oxidative treatment is conducted at a temperature at most about 500°

C.

19. A method for cutting single-wall carbon nantobues comprising:

a) providing a material comprising single-wall carbon nanotubes at least some of which have defects in their side walls;

b) attacking the defects to cut at least a portion of the single wall carbon nanotubes in the material, wherein the single-wall carbon nanotubes in the material are cut by sonication, and wherein the sufficient energy input comprises a frequency of about 40 KHz and a power output of about 20 W; and

c) recovering a product in which a mean length of single-wall carbon nanotubes in the product is less than a mean length of the single-wall carbon nanotubes in the material.

20. A method for cutting single-wall carbon nanotubes comprising:

a) providing a material comprising single-wall carbon nanotubes at least some of which have defects in their side walls;

b) attacking the defects to cut at least a portion of the single wall carbon nanotubes in the material, wherein the single-wall carbon nanotubes in the material are cut by sonication, and wherein the sufficient time is in a range of about 10 minutes and about 24 hours; and

c) recovering a product in which a mean length of single-wall carbon nanotubes in the product is less than a mean length of the single-wall carbon nanotubes in the material.

21. A method for cutting single-wall carbon nanotubes comprising:

a) providing a material comprising single-wall carbon nanotubes at least some of which have defects in their side walls;

b) attacking the defects to cut at least a portion of the single wall carbon nanotubes in the material, wherein the attacking of such defects of the single-wall carbon nanotubes is done by a method selected from the group consisting of sonication of a suspension of single-wall carbon nanotubes at a sufficient energy input and for a sufficient time, oxidation, oxidative etching, free radical attack, chemical reactions, heat pressure, annealing, refluxing and combinations thereof, wherein the single-wall carbon nanotubes in the suspension are cut by sonication of the suspension, and wherein the sufficient energy input comprises a frequency of about 40 KHz and a power output of about 20 W; and

c) recovering a product in which a mean length of single-wall carabon nanotubes in the product is less than a mean length of the single-wall carbon nanotubes in the material.

22. A method for cutting single-wall carbon nanotubes comprising:

a) providing a material comprising single-wall carbon nanotubes at least some of which have defects in their side walls;

b) attacking the defects to cut at least a protion of the single wall cargon nanotubes in the material, wherein the attacking of such defects of the single-wall carbon nanotubes is done by a method selected from the group consisting of sonication of a suspension of single-wall carbon nanotubes at a sufficient energy input and for a sufficient time, oxidation, oxidative etching, free radical attack, chemical reaction, heat, pressure, annealing, refluxing and combinations thereof, wherein the single-wall carbon nanotubes in the suspension are cut by sonication of the suspension, and wherein the sufficient time is in a range of about 10 minutes and about 24 hours; and

c) recovering a product in which a mean length of single-wall carbon nanotubes in the product is less than a mean length of the single-wall carbon nanotubes in the material.