Coatings comprising carbon nanotubes and methods for forming same

• US 20030122111A1
• Filed: 03/26/2002
• Published: 07/03/2003
• Est. Priority Date: 03/26/2001
• Status: Active Grant

• Current Assignee: Nano-C, Inc.
• Original Assignee: Eikos, Inc.
• Inventors: Glatkowski, Paul J.
• Granted Patent: US 7,060,241 B2
• Time in Patent Office: Days
• US Class Current: 252/500
• 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 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C08J 2379/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: C08K 2201/013 Additives applied to the surface of polymers or polymer particles
• CPC Class Codes: C08K 3/041 Carbon nanotubes
• CPC Class Codes: C09D 179/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C09D 185/02 containing phosphorus
• CPC Class Codes: C09D 5/24 Electrically-conducting paints conductive materials H01B1/00
• CPC Class Codes: H01B 1/24 the conductive material comprising carbon-silicon compounds, carbon or silicon
• CPC Class Codes: Y10T 428/24994 Fiber embedded in or on the surface of a polymeric matrix
• CPC Class Codes: Y10T 428/249942 Fibers are aligned substantially parallel
• CPC Class Codes: Y10T 428/249945 Carbon or carbonaceous fiber

Abstract

An electrically conductive film is disclosed. According to one embodiment of the present invention, the film includes a plurality of single-walled nanotubes having a particular diameter. The disclosed film demonstrates excellent conductivity and transparency. Methods of preparing the film as well as methods of its use are also disclosed herein.

Claims

1. An electrically conductive film comprising:

a plurality of nanotubes with an outer diameter of less than 3.5 nm.

2. The film of claim 1, wherein said nanotubes have an outer diameter of about 0.5 to 3.5 nm.

3. The film of claim 1, wherein said nanotubes have an outer diameter of about 0.5 to about 1.5 nm.

4. The film of claim 1, wherein said nanotubes are selected from the group consisting of single-walled nanotubes (SWNTs), double-walled nanotubes (DWNTs), multi-walled nanotubes (MWNTs), and mixtures thereof.

5. The film of claim 1, wherein said nanotubes are substantially single-walled nanotubes (SWNTs).

6. The film of claim 1, wherein said nanotubes are present in said film at about 0.001 to about 1% based on weight.

7. The film of claim 1, wherein said nanotubes are present in said film at about 0.05%.

8. The film of claim 1, wherein the film has a surface resistance in the range of less than about 10¹⁰ ohms/square.

9. The film of claim 1, wherein the film has a surface resistance in the range of about 10²-10¹⁰ ohms/square.

10. The film of claim 1, wherein the film has a surface resistance in the range of about 10⁶-10¹⁰ ohms/square.

11. The film of claim 1, wherein the film has a surface resistance in the range of less than about 10³ ohms/square.

12. The film of claim 1, wherein the film has a volume resistances in the range of about 10⁻

2 ohms-cm to about 10¹⁰ ohms-cm.

13. The film of claim 1, further comprising a polymeric material.

14. The film of claim 1, wherein the film is in the form of a solid film, a foam, or a fluid.

15. The film of claim 1, further comprising a polymeric material, wherein the polymeric material comprises a material selected from the group consisting of thermoplastics, thermosetting polymers, elastomers, conducting polymers and combinations thereof.

16. The film of claim 1, further comprising a polymeric material, wherein the polymeric material comprises a material selected from the group consisting of polyethylene, polypropylene, polyvinyl chloride, styrenic, polyurethane, polyimide, polycarbonate, polyethylene terephthalate, cellulose, gelatin, chitin, polypeptides, polysaccharides, polynucleotides and mixtures thereof.

17. The film of claim 1, further comprising a polymeric material, wherein the polymeric material comprises a material selected from the group consisting of ceramic hybrid polymers, phosphine oxides and chalcogenides.

18. The film of claim 1, further comprising a polymeric material wherein the nanotubes are dispersed substantially homogenously throughout the polymeric material.

19. The film of claim 1, further comprising a polymeric material wherein the nanotubes are present in a gradient fashion.

20. The film of claim 1, further comprising a polymeric material wherein the nanotubes are present on a surface of said polymeric material.

21. The film of claim 1, further comprising a polymeric material wherein the nanotubes are formed in an internal layer of said polymeric material.

22. The film of claim 1, further comprising an opaque substrate, wherein the nanotubes are present on a surface of said opaque substrate.

23. The film of claim 1, further comprising an additive selected from the group consisting of a dispersing agent, a binder, a cross-linking agent, a stabilizer agent, a coloring agent, a UV absorbent agent, and a charge adjusting agent.

24. The film of claim 1, wherein the film has a total transmittance of at least about 60%.

25. The film of claim 1, wherein said film has a total light transmittance of about 80% or more.

26. The film of claim 1, wherein said film has a total light transmittance of about 90% or more.

27. The film of claim 1, wherein said film has a total light transmittance of about 95% or more.

28. The film of claim 1, wherein said film has a haze value less than 2.0%.

29. The film of claim 1, wherein said film has a haze value less than 0.1%.

30. The film of claim 1, wherein said film has a thickness between about 0.5 nm to about 1000 microns.

31. The film of claim 1, wherein said film has a thickness between about 0.05 to about 500 microns.

32. The film of claim 1, wherein the nanotubes are oriented.

33. The film of claim 1, wherein the nanotubes are oriented in the plane of the film.

34. The film of claim 1, wherein the nanotubes are oriented, further comprising an additional layer of oriented nanotubes.

35. A method for making an electrically conductive film of claim 1 comprising:

providing a plurality of nanotubes with an outer diameter of less than 3.5 nm;

and forming a film of said nanotubes on a surface of a substrate.

36. The method of claim 35, wherein the step of forming the film comprises a method selected from the group consisting of spray painting, dip coating, spin coating, knife coating, kiss coating, gravure coating, screen printing, ink jet printing, and pad printing.

37. The method of claim 35, wherein said nanotubes have an outer diameter of about 0.5 to 3.5 nm.

38. The method of claim 35, wherein said nanotubes are selected from the group consisting of single-walled nanotubes (SWNTs), double-walled nanotubes (DWNTs), multi-walled nanotubes (MWNTs), and mixtures thereof.

39. The method of claim 35, wherein said nanotubes are substantially single-walled nanotubes (SWNTs).

40. The method of claim 35, wherein the film has a volume resistances in the range of about 10⁻

2 ohms/cm to about 10¹⁰ ohms/cm.

41. The method of claim 35, further comprising orienting the nanotubes.

42. A multi-layered structure comprising:

an electrically conductive film comprising a plurality of nanotubes with an outer diameter of less than 3.5 nm; and

a polymeric layer disposed on at least a portion of said electrically conductive film.

43. The multi-layered structure of claim 42, wherein said nanotubes have an outer diameter of about 0.5 to 3.5 nm.

44. The multi-layered structure of claim 42, wherein said nanotubes are selected from the group consisting of single-walled nanotubes (SWNTs), double-walled nanotubes (DWNTs), multi-walled nanotubes (MWNTs), and mixtures thereof.

45. The multi-layered structure of claim 42, wherein said nanotubes are substantially single-walled nanotubes (SWNTs).

46. The multi-layered structure of claim 42, wherein said nanotubes are present in said film at about 0.001 to about 1% based on weight.

47. The multi-layered structure of claim 42, wherein the film has a volume resistances in the range of about 10⁻

2ohms/cm to about 10¹⁰ ohms/cm.

48. The multi-layered structure of claim 42, wherein the film is in the form of a solid film, a foam, or a fluid.

49. The multi-layered structure of claim 42, further comprising a polymeric material, wherein the polymeric material comprises a material selected from the group consisting of thermoplastics, thermosetting polymers, elastomers, conducting polymers and combinations thereof.

50. The multi-layered structure of claim 42, further comprising a polymeric material, wherein the polymeric material comprises a material selected from the group consisting of ceramic hybrid polymers, phosphine oxides and chalcogenides.

51. The multi-layered structure of claim 42, further comprising a polymeric material wherein the nanotubes are dispersed substantially homogenously throughout the polymeric material.

52. The multi-layered structure of claim 42, further comprising a polymeric material wherein the nanotubes are present in a gradient fashion.

53. The multi-layered structure of claim 42, further comprising a polymeric material wherein the nanotubes are present on a surface of said polymeric material.

54. The multi-layered structure of claim 42, further comprising a polymeric material wherein the nanotubes are formed in an internal layer of said polymeric material.

55. The multi-layered structure of claim 42, further comprising an opaque substrate, wherein the nanotubes are present on a surface of said opaque substrate.

56. The multi-layered structure of claim 42, further comprising an additive selected from the group consisting of a dispersing agent, a binder, a cross-linking agent, a stabilizer agent, a coloring agent, a UV absorbent agent, and a charge adjusting agent.

57. The multi-layered structure of claim 42, wherein the film has a total transmittance of at least about 60%.

58. The multi-layered structure of claim 42, wherein said film has a thickness between about 0.005 to about 1,000 microns.

59. The multi-layered structure of claim 42, wherein the nanotubes are oriented.

60. The multi-layered structure of claim 42, wherein the nanotubes are oriented in the plane of the film.

61. A dispersion of nanotubes comprising a plurality of nanotubes with an outer diameter of less than 3.5 nm.

62. The dispersion of claim 61, wherein said nanotubes have an outer diameter of about 0.5 to 3.5 nm.

63. The dispersion of claim 61, wherein said nanotubes are selected from the group consisting of single-walled nanotubes (SWNTs), double-walled nanotubes (DWNTs), multi-walled nanotubes (MWNTs), and mixtures thereof.

64. The dispersion of claim 61, wherein said nanotubes are substantially single-walled nanotubes (SWNTs).

65. The dispersion of claim 61, further comprising a polymeric material, wherein the polymeric material comprises a material selected from the group consisting of thermoplastics, thermosetting polymers, elastomers, conducting polymers and combinations thereof.

66. The dispersion of claim 61, further comprising a polymeric material, wherein the polymeric material comprises a material selected from the group consisting of ceramic hybrid polymers, and phosphine oxides chalcogenides.

67. The dispersion of claim 61, further comprising a plasticizer, softening agent, filler, reinforcing agent, processing aid, stabilizer, antioxidant, dispersing agent, binder, a cross-linking agent, a coloring agent, a UV absorbent agent, or a charge adjusting agent.

68. The dispersion of claim 61, further comprising conductive organic materials, inorganic materials, or combinations or mixtures thereof.

69. The dispersion of claim 68 wherein the conductive organic materials are selected from the group consisting of buckeyballs, carbon black, fullerenes, nanotubes with an outer diameter of greater than about 3.5 nm, and combinations and mixtures thereof.

70. The dispersion of claim 68 wherein the conductive inorganic materials are selected from the group consisting of aluminum, antimony, beryllium, cadmium, chromium, cobalt, copper, doped metal oxides, iron, gold, lead, manganese, magnesium, mercury, metal oxides, nickel, platinum, silver, steel, titanium, zinc, and combinations and mixtures thereof.

71. The dispersion of claim 61, further comprising a conductive material selected from the group consisting of tin-indium mixed oxide, antimony-tin mixed oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide and combinations and mixtures thereof.

72. The dispersion of claim 61, further comprising conductors, fluids, gelatins, ionic compounds, semiconductors, solids, surfactants, or combinations or mixtures thereof.