Methods for producing composites of single-wall carbon nanotubes and compositions thereof

• US 7,105,596 B2
• Filed: 12/28/2001
• Issued: 09/12/2006
• 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): HENDRICKSON, STUART L
• Application Number:
  US10/033,470
• Publication Number:
  US 20020150524A1
• Time in Patent Office: 1,719 Days
• Field of Search: 252/510, 252/511, 524/495, 977/750, 977/745
• US Class Current: 524/495
• 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 a method for producing composites of single-wall carbon nanotubes (SWNTs) and compositions thereof. In one embodiment, the present invention involves a method of producing a composite material that includes a matrix and a carbon nanotube material embedded within said matrix. In another embodiment, a method of producing a composite material containing carbon nanotube material is disclosed. This method includes the steps of preparing an assembly of a fibrous material; adding the carbon nanotube material to the fibrous material; and adding a matrix material precursor to the carbon nanotube material and the fibrous material.

Claims

1. A composite material comprising:

(a) a matrix, wherein said matrix comprises a polymer; and

(b) a single-wall carbon nanotube material embedded within said matrix, wherein said single-wall carbon nanotube material comprises fibers of greater than 10⁶ single-wall carbon nanotubes.

2. The composite material of claim 1, wherein said polymer comprises a thermosetting polymer.

3. The composite material of claim 2, wherein said thermosetting polymer comprises a polymeric material selected from the group consisting of phthalic/maleic type polyesters, vinyl esters, epoxies, phenolics, cyanates, bismaleimides, and nadic end-capped polyimides.

4. The composite material of claim 1, wherein said polymer comprises a thermoplastic polymer.

5. The composite material of claim 4, wherein said thermoplastic polymer comprises a polymeric material selected from the group consisting of polysulfones, polyamides, polycarbonates, polyphenylene oxides, polysulfides, polyether ether ketone, polyether sulfones, polyamide-imides, polyetherimides, polyimides, polyarylates, and liquid crystalline polyesters.

6. The composite material of claim 1 further comprising an additional fibrous material.

7. The composite material of claim 1 wherein said single-wall carbon nanotube material is derivatized to chemically react with said matrix material.

8. The composite material of claim 1 wherein the single-wall carbon nanotube material comprises single-wall carbon nanotubes having lengths in the range between 5 and 500 nm.

9. A composite material comprising:

(a) a matrix, wherein said matrix comprises a polymer; and

(b) a single-wall carbon nanotube material embedded within said matrix, wherein said single-wall carbon nanotube material is derivatized to chemically react with said matrix material.

10. The composite material of claim 9 further comprising an additional fibrous material.

11. A method for producing a composite material comprising a single-wall carbon nanotube material, wherein said single-wall carbon nanotube material comprises fibers of greater than 10⁶ single-wall carbon nanotubes, and wherein said method comprises:

(a) preparing a matrix material;

(b) combining said single-wall carbon nanotube material with said matrix material; and

(c) forming said composite material.

12. The method of claim 11, wherein said matrix material is a fluid and wherein said single-wall carbon nanotube material is in a pre-formed arrangement.

15. The method of claim 12 wherein the pre-formed arrangement is selected from the group consisting of a bucky paper and a felt.

13. A method of producing a composite material comprising carbon nanotube material, wherein said single-wall carbon nanotube material comprises fibers of greater than 10⁶ single-wall carbon nanotubes, and wherein said method comprises:

(a) preparing an assembly of a fibrous material;

(b) adding said carbon nanotube material to said fibrous material; and

(c) adding a matrix material to said carbon nanotube material and said fibrous material.

14. The method of claim 13, wherein said fibrous materials are arranged in a two-dimensional sheet, and some portion of the said carbon nanotube material is oriented in a direction other than parallel to said sheet.

16. A composite material comprising carbon nanotubes, a fibrous structural constituent and a matrix material, wherein the matrix material comprises a polymer and the fibrous structural constituent comprises carbon, and wherein the carbon nanotubes comprise single-wall carbon nanotube fibers, wherein each of the single-wall carbon nanotube fibers comprises at least 10⁶ individual single-wall carbon nanotubes.

17. The composite material of claim 16, wherein the composite further comprises a second fibrous structural constituent, wherein the second fibrous structural constituent comprises a material selected from the group consisting of cellulose, glass, graphite, silicon oxide, carbon steel, aluminum oxide, beryllium, beryllium oxide, boron, boron carbide, boron nitride, chromium, copper, iron, nickel, silicon carbide, silicon nitride, alumina yarn, alumina-boria-silica, zirconia-silica, zircona, alumina, quartz, molybdenum, stainless steel, titanium boride, tungsten, zirconium oxide and combinations thereof.

18. The composite material of claim 16, wherein the polymer comprises a thermosetting polymer.

19. The composite material of claim 18, wherein the thermosetting polymer comprises a polymeric material selected from the group consisting of phthalic/maleic type polyesters, vinyl esters, epoxies, phenolics, cyanates, bismaleimides and nadic end-capped polyimides.

20. The composite material of claim 16, wherein the polymer comprises a thermoplastic polymer.

21. The composite material of claim 20 wherein the thermoplastic polymer comprises a polymeric material selected from the group consisting of polysulfones, polyamides, polycarbonates, polyphenylene oxides, polysulfides, polyether ether ketones, polyether sulfones, polyamide-imides, polyetherimides, polyimides, polyarylates, liquid crystalline polyesters and combinations thereof.

22. The composite material of claim 16 wherein the carbon nanotubes comprise single-wall carbon nanotubes that have been subjected to a purification process.

23. The composite material of claim 16 wherein the carbon nanotubes comprise single-wall carbon nanotubes in a form selected from the group consisting of felts, bucky papers, cut lengths of single-wall carbon nanotube ropes, cut lengths of single-wall carbon nanotube fibers and combinations thereof.

24. The composite material of claim 16 wherein the composite material further comprises:

(a) a first area wherein a first portion of single-wall carbon nanotubes have a first homogeneous characteristic selected from the group consisting of lengths, diameters, helicities and combinations thereof;

(b) a second area wherein a second portion of single-wall carbon nanotubes have a second homogeneous characteristic selected from the group consisting of lengths, diameters, helicities and combinations thereof; and

(c) wherein the first homogeneous characteristic is different from the second homogeneous characteristic.

25. The composite material of claim 16 wherein the carbon nanotubes comprise chemically-derivatized single-wall carbon nanotubes, chemically-derivatized ropes of single-wall carbon nanotubes, chemically-derivatized fibers and combinations thereof.

26. The composite material of claim 25 wherein the chemically-derivatized single-wall carbon nanotubes have side-wall defects.

27. The composite material of claim 25 wherein the chemically-derivatized single-wall carbon nanotubes have side-wall bonding sites.

28. The composite material of claim 16 further comprising single-wall carbon nanotubes having side-wall modifications capable of an interaction with the matrix material, wherein the interaction is selected from the group consisting of physical, chemical and combinations thereof.

29. A composite material comprising carbon nanotubes, a fibrous structural constituent and a matrix material, wherein the matrix material comprises a polymer, wherein the fibrous structural constituent comprises carbon, and wherein the carbon nanotubes comprise single-wall carbon nanotubes that have a homogeneous characteristic selected from the group consisting of lengths, diameters, helicities and combinations thereof.

30. A composite material comprising carbon nanotubes, a fibrous structural constituent and a matrix material, wherein

(a) the matrix material comprises a polymer,

(b) the fibrous structural constituent comprises carbon,

(c) the carbon nanotubes comprise chemically-derivatized single-wall carbon nanotubes, chemically-derivatized ropes of single-wall carbon nanotubes, chemically-derivatized fibers or combinations thereof,

(d) the chemically-derivatized single-wall carbon nanotubes have side-wall bonding sites, and

(e) at least one of the side-wall defects comprises replacement of at least one carbon atom in the single-wall carbon nanotube lattice with at least one non-carbon atom.

31. The composite material of claim 30 wherein the non-carbon atom is selected from the group consisting of boron, nitrogen, and combinations thereof.

32. A composite comprising derivatized single-wall carbon nanotubes and a polymer, wherein the polymer has at least one pendant group capable of a chemical reaction with the derivatized single-wall carbon nanotubes.

33. The composite of claim 32 wherein the chemical reaction is promoted by photolysis.

34. A method for producing a composite material comprising:

(a) introducing a matrix material, wherein the matrix material comprises a polymer;

(b) combining a carbon nanotube material with the matrix material, wherein the carbon nanotube material comprises a plurality of single-wall carbon nanotubes and wherein the single-wall carbon nanotubes are derivatized to facilitate bonding to other single-wall carbon nanotubes, the matrix material or both; and

(c) subsequently forming the composite material.

35. The method of claim 34 wherein the carbon nanotube material is dispersed in a liquid carrier.

36. The method of claim 35 wherein the liquid carrier comprises a liquid selected from the group consisting of water and an organic solvent.

37. The method of claim 34 wherein the plurality of single-wall carbon nanotubes is aligned by an electric field before the forming step.

38. The method of claim 34 further comprising pre-forming the plurality of single-wall carbon nanotubes into a structure before the combining step.

39. The method of claim 34 further comprising combining a fibrous material with the carbon nanotube material and the matrix material.