Method for cutting nanotubes

• US 7,008,604 B2
• Filed: 12/28/2001
• Issued: 03/07/2006
• Est. Priority Date: 03/07/1997
• 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): Silverman, Stanley S.
• Assistant Examiner(s): Lish, Peter J.
• Application Number:
  US10/035,075
• Publication Number:
  US 20020094311A1
• Time in Patent Office: 1,530 Days
• Field of Search: 423/447.1, 423/447.2, 423/447.3, 423/445.R, 423/460, 423/461, 977/DIG.1
• US Class Current: 423/447.1
• CPC Class Codes: B01J 19/081 employing particle radiation or gamma-radiation
• CPC Class Codes: B01J 19/087 employing electric or magnetic energy
• CPC Class Codes: B01J 19/10 employing sonic or ultrasonic vibrations
• CPC Class Codes: B01J 19/121 Coherent waves, e.g. laser beams lasers per se H01S3/00
• CPC Class Codes: B01J 19/126 Microwaves
• CPC Class Codes: B01J 19/129 Radiofrequency
• CPC Class Codes: B01J 21/185 Carbon nanotubes carbon nanotubes per se C01B32/15
• CPC Class Codes: B01J 2219/00078 Fingers
• CPC Class Codes: B01J 2219/0892 involving catalytically active material
• CPC Class Codes: B01J 23/74 Iron group metals
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 23/8913 Cobalt and noble metals
• CPC Class Codes: B01J 37/0238 via the gaseous phase-sublimation
• CPC Class Codes: B01J 37/349 making use of flames, plasmas or lasers
• CPC Class Codes: B82B 3/00 Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
• CPC Class Codes: C01B 2202/02 Single-walled nanotubes
• CPC Class Codes: C01B 32/156 After-treatment
• CPC Class Codes: C01B 32/162 characterised by catalysts
• CPC Class Codes: C01B 32/17 Purification
• CPC Class Codes: D01F 9/12 Carbon filaments; Apparatus specially adapted for the manufacture thereof
• CPC Class Codes: D01F 9/127 : by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
• CPC Class Codes: D21H 27/00 : Special paper not otherwise provided for, e.g. made by multi-step processes
• CPC Class Codes: G11B 9/1418 : Disposition or mounting of heads or record carriers G11B17/00 and G11B19/00 take precedence
• CPC Class Codes: G11B 9/1445 : switching at least one head in operating function; Controlling the relative spacing to keep the head operative, e.g. for allowing a tunnel current flow
• CPC Class Codes: G11B 9/1472 : characterised by the form
• CPC Class Codes: G11B 9/149 : characterised by the memorising material or structure
• CPC Class Codes: G11C 13/0014 : comprising cells based on organic memory material
• CPC Class Codes: G11C 13/0019 : comprising bio-molecules
• CPC Class Codes: G11C 13/025 : using fullerenes, e.g. C60, or nanotubes, e.g. carbon or silicon nanotubes
• CPC Class Codes: G11C 2213/16 : Memory cell being a nanotube, e.g. suspended nanotube
• CPC Class Codes: G11C 2213/71 : Three dimensional array
• CPC Class Codes: G11C 2213/81 : Array wherein the array conductors, e.g. word lines, bit lines, are made of nanowires
• CPC Class Codes: H01G 9/2059 : comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
• CPC Class Codes: H01L 31/0352 : characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
• CPC Class Codes: H01L 31/06 : characterised by potential barriers
• CPC Class Codes: H01L 31/18 : Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
• CPC Class Codes: H01M 10/0525 : Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 4/133 : Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/525 : of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/583 : Carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/587 : for inserting or intercalating light metals
• CPC Class Codes: H01M 4/625 : Carbon or graphite
• CPC Class Codes: Y02E 10/542 : Dye sensitized solar cells
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10S 977/70 : Nanostructure
• CPC Class Codes: Y10S 977/742 : Carbon nanotubes, CNTs
• CPC Class Codes: Y10S 977/745 : having a modified surface
• CPC Class Codes: Y10S 977/748 : Modified with atoms or molecules bonded to the surface
• CPC Class Codes: Y10S 977/75 : Single-walled
• CPC Class Codes: Y10S 977/753 : with polymeric or organic binder
• CPC Class Codes: Y10S 977/789 : in array format
• CPC Class Codes: Y10S 977/842 : for carbon nanotubes or fullerenes
• 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: Y10S 977/847 : Surface modifications, e.g. functionalization, coating
• CPC Class Codes: Y10S 977/848 : Tube end modifications, e.g. capping, joining, splicing
• CPC Class Codes: Y10S 977/849 : with scanning probe
• CPC Class Codes: Y10S 977/882 : Assembling of separate components, e.g. by attaching
• CPC Class Codes: Y10S 977/948 : Energy storage/generating using nanostructure, e.g. fuel cell, battery
• CPC Class Codes: Y10T 428/24058 : including grain, strips, or filamentary elements in respective layers or components in angular relation
• CPC Class Codes: Y10T 428/2918 : including free carbon or carbide or therewith [not as steel]
• CPC Class Codes: Y10T 428/292 : In coating or impregnation
• CPC Class Codes: Y10T 428/30 : Self-sustaining carbon mass or layer with impregnant or other layer

Abstract

This invention relates generally to cutting single-wall carbon nanotubes (SWNT). In one embodiment, the present invention provides for preparation of homogeneous 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 producing tubular carbon molecules of about 5 to 500 nm in length, said method comprising the steps of:

(a) providing a single-wall carbon nanotube-containing material;

(b) cutting single-wall nanotube containing-material to form a mixture of tubular carbon molecules having lengths in the range of about 5 to 500 nm;

(c) fractionating said mixture of tubular carbon molecules to form a fraction of said tubular carbon molecules having substantially equal lengths.

2. The method of claim 1 wherein said cutting single-wall nanotubes into tubular carbon molecules comprising the steps of:

(a) forming a substantially two-dimensional target containing single-wall nanotubes of lengths up to about one micron or more; and

(b) irradiating said target with a high-energy beam of high mass ions.

3. The method of claim 2 wherein a high energy beam is produced in a cyclotron and has an energy of from about 0.1 to about 10 GeV.

4. The method of claim 2 wherein said high mass ion has a mass of greater than about 150 AMU.

5. The method of claim 4 wherein said high mass ion is selected from the group consisting of gold, bismuth and uranium.

6. The method of claim of 5 wherein the high mass ion is Au⁺³³.

7. The method of claim 1 wherein said cutting single-wall nanotubes into tubular carbon molecules comprises the steps of:

(a) forming a suspension of single-wall nanotubes in a medium;

(b) sonicating said suspension with acoustic energy.

8. The method of claim 7 wherein said acoustic energy is produced by a device operating at 40 KHz and having an output of 20 W.

9. The method of claim 1 wherein said cutting single-wall nanotubes into tubular carbon molecules comprises refluxing single wall nanotube material in concentrated HNO3.

10. The method of claim 2 further comprising the step of heating the tubular carbon molecules to form a hemispheric fullerene cap on at least one end thereof.

11. The method of claim 1 further comprising the step of reacting said tubular carbon molecules with a material which provides at the reaction conditions at least one substituent on at least one of said ends of said tubular carbon molecule.

12. The method of claim 9 further comprising the step of reacting said tubular carbon molecules with a material which provides at the reaction conditions at least one substituent on at least one of said ends of said tubular carbon molecule.

13. The method of claim 11 wherein said substituent is selected from the group consisting of hydrogen;

alkyl;

acyl;

aryl;

aralkyl;

halogen;

substituted thiol;

unsubstituted thiol;

substituted amino;

unsubstituted amino;

hydroxy; and

OR′

, wherein R′

is selected from the group consisting of alkyl, acyl, aryl, aralkyl, substituted thiol, unsubstituted thiol, substituted amino, unsubstituted amino, a linear carbon chain, and a cyclic carbon chain.

14. The method of claim 13 wherein the linear carbon chain, the cyclic carbon chain, or both, are interrupted by at least one heteroatoms.

15. The method of claim 13 wherein the linear carbon chain, the cyclic carbon chain, or both, are substituted with a moiety selected from the group consisting of at least one ═

O, ═

S, hydroxy, aminoalkyl, amino and a peptide of 2–

8 amino acids.

16. The method of claim 12 wherein the substituent is selected from the group consisting of alkyl;

acyl;

aryl;

aralkyl;

halogen;

substituted thiol;

unsubstituted thiol;

substituted amino;

unsubstituted amino;

hydroxy; and

OR′

, wherein R′

is selected from the group consisting of alkyl, acyl, aryl, aralkyl, halogen, substituted thiol, unsubstituted thiol, substituted amino, unsubstituted amino, a linear carbon chain and a cyclic carbon chain.

17. The method of claim 16 wherein the linear carbon chain, the cyclic carbon chain, or both, are interrupted by at least one heteroatoms.

18. The method of claim 16 wherein the linear carbon chain, the cyclic carbon chain, or both, are substituted with a moiety selected from the group consisting of at least one ═

O, ═

S, hydroxy, aminoalkyl, amino and a peptide of 2–

8 amino acids.

19. The method of claim 1 further comprising annealing the mixture of tubular carbon molecules having lengths in the range of about 5 to 500 nm.

20. A method for producing substantially un-tangled single-wall carbon nanotubes comprising:

(a) providing tangled single-wall carbon nanotubes;

(b) forming a suspension of the tangled single-wall carbon nanotubes in a liquid medium, wherein the liquid medium comprises a solution selected from the group consisting of an aqueous solution, a solution comprising sodium dodecyl sulfate, a solution comprising non-ionic surfactant and combinations thereof;

(c) cutting at least a portion of the single-wall carbon nanotubes to untangle at least some of the single-wall carbon nanotubes; and

(d) recovering material comprising single-wall carbon nanotubes untangled by the cutting step.

21. The method of claim 20 wherein the tangled single-wall carbon nanotubes comprise ropes of single-wall carbon nanotubes.

22. The method of claim 21 wherein the cutting step comprises sonication and wherein at least one of the ropes is cut.

23. The method of claim 20 further comprising fractionating the single-wall carbon nanotubes into at least one fraction of the single-wall carbon nanotubes having a homogeneous characteristic selected from the group consisting of lengths, diameters, helicities and combinations thereof.

24. The method of claim 23 wherein the fractionating step comprises a method selected from the group consisting of field-flow fractionation, light scattering methods and combinations thereof.

25. The method of claim 20 wherein the suspension is a stable colloidal suspension.