Chemical derivatization of single-wall carbon nanotubes to facilitate solvation thereof; and use of derivatized nanotubes to form catalyst-containing seed materials for use in making carbon fibers
Patent 6645455 Issued on November 11, 2003. Estimated Expiration Date: March 16, 2021. Estimated Expiration Date is calculated based on simple USPTO term provisions. It does not account for terminal disclaimers, term adjustments, failure to pay maintenance fees, or other factors which might affect the term of a patent.
This invention is directed to making chemical derivatives of carbon nanotubes and to uses for the derivatized nanotubes, including making arrays as a basis for synthesis of carbon fibers. In one embodiment, this invention also provides a method for preparing single wall carbon nanotubes having substituents attached to the side wall of the nanotube by reacting single wall carbon nanotubes with fluorine gas and recovering fluorine derivatized carbon nanotubes, then reacting fluorine derivatized carbon nanotubes with a nucleophile. Some of the fluorine substituents are replaced by nucleophilic substitution. If desired, the remaining fluorine can be completely or partially eliminated to produce single wall carbon nanotubes having substituents attached to the side wall of the nanotube. The substituents will, of course, be dependent on the nucleophile, and preferred nucleophiles include alkyl lithium species such as methyl lithium. Alternatively, fluorine may be fully or partially removed from fluorine derivatized carbon nanotubes by reacting the fluorine derivatized carbon nanotubes with various amounts of hydrazine, substituted hydrazine or alkyl amine. The present invention also provides seed materials for growth of single wall carbon nanotubes comprising a plurality of single wall carbon nanotubes or short tubular molecules having a catalyst precursor moiety covalently bound or physisorbed on the outer surface of the sidewall to provide the optimum metal cluster size under conditions that result in migration of the metal moiety to the tube end.
Yu, Rongqing et al., "Platinum Deposition on Carbon Nanotubes via Chemical Modification", Jan. 31, 1998, Chem. Mater, 10, pages 718-722.
Iijima, Sumio and Ichihashi Toshinari, "Single-shell carbon nanotubes of 1-nm diameter," Nature, vol. 363, pp. 603-605, Jun. 17, 1993
Li, W.Z., et al., "Large-Scale Synthesis of Aligned Carbon Nanotubes," Science, vol. 274, pp. 1701-1703, Dec. 6, 1996
Ugarte, D., et al., "Nanocapillarity and Chemistry in Carbon Nanotubes," Science, vol. 274, pp. 1897-1899, Dec. 13, 1996
Rao, A.M., et al., "Diameter-Selective Raman Scattering from Vibrational Modes in Carbon Nanotubes," Science, vol. 275, pp. 187-190, Jan. 10, 1997
Charlier, Jean-Christopher, et al., "Microscopic Growth Mechanisms for Carbon Nanotubes," Science, vol. 275, pp. 646649, Jan. 31, 1997
Thess, Andreas, et al., Crystalline Ropes of Metallic Carbon Nanotubes, Science, vol. 273, pp. 483-487
Hamada, Noriaki, et al., "New One-Dimensional Conductors: Graphitic Microtubules," The American Physical Scoiety, vol. 68, No. 10, pp. 1579-1581, Mar. 9 1992
Guo, Ting, et al., "Self-Assembly of Tubular Fullerenes," J. Phys. Chem. 1995, vol. 99, No. 27, pp. 10694-10697
Guo, T., et al., "Catalytic growth of single-walled nanotubes by laser vaporizations," Chemical Physics Letters,vol. 243, pp. 49-54, 1995
Rinzler, A.G., "Unraveling Nanotubes: Field Emission from an Atomic Wire," Science, vol. 269, pp. 1550-1553, Sep. 15, 1995
Guo, T. and Smalley, Richard E., "Production of Single-Walled Carbon Nanotubes Via Laser," Electochemical Society Proceedings, vol. 95, No. 10 pp. 636-647
Thess, Andreas, "Crystalline Ropes of Metallic Carbon Nanotubes," Science, vol. 273, pp. 483-487, Jul. 26, 1996
Ge, Maohui and Sattler, Klaus, "Scanning tunneling microscopy of single-shell nanotubes of carbon," 320 Applied Physics Letters 65, No. 18, Oct. 31, 1994, Woodbury, NY
Dai, Hongjie, et al., "Single-wall nanotubes produced by metal-catalyzed disproportionation of carbon monoxide," Chemical Physics Letters 260, pp. 364-371, 1994
Lambert, J.M., et al., "Improving conditions towards isolating single-shell carbon nanotubes, " Chemical Physics Letters 226, pp. 364-371, 1994
Zhou, Dan, et al., "Single-walled carbon nanotubes growing radially from YC2 particles," 320 Applied Physics Letters, vol. 65, No. 12, Sep. 19, 1994, Woodbury, NY, U.S
Wang, X.K., et al., "Stabale glow discharge for synthesis of carbon nanotubes," Applied Physics Letters, vol. 66, No. 4, Jan. 23, 1995, Woodbury, NY, U.S
Nikolaev, Pavel, et al., "Diameter Doubling of Single-Wall Nanotubes," Chemical Physics Letters, Oct. 24, 1996