Gas-phase nucleation and growth of single-wall carbon nanotubes from high pressure CO

Patent 6761870 Issued on July 13, 2004. Estimated Expiration Date:

November 3, 2019. 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.

Abstract Claims Description Full Text

Patent References

Carbon fibrils, method for producing same and compositions containing same
Patent #: 4663230
Issued on: 05/05/1987
Inventor: Tennent

Process for preparing carbon fibers in gas phase growth
Patent #: 4876078
Issued on: 10/24/1989
Inventor: Arakawa, et al.

Process for producing graphite whiskers
Patent #: 5039504
Issued on: 08/13/1991
Inventor: Kageyama, et al.

Carbon fibrils and method for producing same
Patent #: 5165909
Issued on: 11/24/1992
Inventor: Tennent, et al.

Method for forming carbon fibers
Patent #: 5374415
Issued on: 12/20/1994
Inventor: Alig, et al.

Carbon fibers and method for their production
Patent #: 5424054
Issued on: 06/13/1995
Inventor: Bethune, et al.

Carbon fibrils
Patent #: 5707916
Issued on: 01/13/1998
Inventor: Snyder, et al.

Method for producing encapsulated nanoparticles and carbon nanotubes using catalytic disproportionation of carbon monoxide
Patent #: 5780101
Issued on: 07/14/1998
Inventor: Nolan, et al.

Carbon fibrils
Patent #: 5877110
Issued on: 03/02/1999
Inventor: Snyder, et al.

Method for producing encapsulated nanoparticles and carbon nanotubes using catalytic disproportionation of carbon monoxide and the nanoencapsulates and nanotubes formed thereby
Patent #: 5965267
Issued on: 10/12/1999
Inventor: Nolan, et al.

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Inventors

Assignee

William Marsh Rice University

Application

No. 09830642 filed on 11/03/1999

US Classes:

423/447.3, From gaseous reactants423/447.1, Fiber, fabric, or textile423/445RElemental carbon

Examiners

Primary: Hendrickson, Stuart L.
Assistant: Lish, Peter J

Attorney, Agent or Firm

Foreign Patent References

2 248 230 GB 04/01/1992
06322615 JP 11/01/1994
09188509 JP 07/01/1997
WO 8907163 WO 08/01/1989
WO 9709272 WO 03/01/1997
WO 9805920 WO 02/01/1998
WO 9906618 WO 02/01/1999
WO 0017102 WO 03/01/2000
WO 0073205 WO 12/01/2000

International Class

D01F 912

Abstract

The present invention discloses the process of supplying high pressure (e.g., 30 atmospheres) CO that has been preheated (e.g., to about 1000° C.) and a catalyst precursor gas (e.g., Fe(CO)5) in CO that is kept below the catalyst precursor decomposition temperature to a mixing zone. In this mixing zone, the catalyst precursor is rapidly heated to a temperature that results in (1) precursor decomposition, (2) formation of active catalyst metal atom clusters of the appropriate size, and (3) favorable growth of SWNTs on the catalyst clusters. Preferably a catalyst cluster nucleation agency is employed to enable rapid reaction of the catalyst precursor gas to form many small, active catalyst particles instead of a few large, inactive ones. Such nucleation agencies can include auxiliary metal precursors that cluster more rapidly than the primary catalyst, or through provision of additional energy inputs (e.g., from a pulsed or CW laser) directed precisely at the region where cluster formation is desired. Under these conditions SWNTs nucleate and grow according to the Boudouard reaction. The SWNTs thus formed may be recovered directly or passed through a growth and annealing zone maintained at an elevated temperature (e.g., 1000° C.) in which tubes may continue to grow and coalesce into ropes.

Other References

Kataura et al., “Formation of Thin Single-Wall Carbon Nanotubes by Laser Vaporization of Rh/Pd-Graphite Composite Rod,” Japanese Journal of Applied Physics, vol. 37, pp. L616-L618 (May 15, 1998).
Hafner et al., “Catalytic growth of single-wall carbon nanotubes from metal particles,” Chemical Physics Letters, vol. 296, pp. 195-202 (Oct. 30, 1998).
Dai et al., “Single-wall nanotubes produced by metal-catalyzed disproportionation of carbon monoxide,” Chemical Physics Letters, vol. 260, pp. 471-475 (Sep. 27, 1996).
Cheng et al., “Large-scale and low-cost synthesis of single-walled carbon nanotubes by the catalytic pyrolysis of hydrocarbons,” Applied Physics Letters, vol. 72, No. 25, pp. 3282-3284 (Jun. 22, 1998).
Colomer et al., “Synthesis of single-wall carbon nanotubes by catalytic decomposition of hydrocarbons,” Chemical Communications, pp. 1343-1344 (1999).
Ebbesen et al., “Large-scale synthesis of carbon nanotubes,” Nature, vol. 358, pp. 220-222, (Jul. 16, 1992).
Ebbesen, “Carbon Nanotubes,” Annual Review of Materials Science, vol. 24, pp. 235-264 (1994).
Iijima, “Helical microtubules of graphitic carbon,” Nature, vol. 354, pp. 56-58 (1991).
Iijima et al., “Single-shell carbon nanotubes of 1-nm diameter,” Nature, vol. 363, pp. 603-605 (Jun. 17, 1993).
Bethune et al., “Cobalt-catalysed growth of carbon nanotubes with single-atomic-layer walls,” Nature, vol. 363, pp. 605-607 (Jun. 17, 1993).
Ajayan et al., “Growth morphologies during cobalt-catalyzed single-shell carbon nanotube synthesis,” Chemical Physics Letters, vol. 215, No. 5, pp. 509-517 (Dec. 10, 1993).
Zhou et al., “Single-walled carbon nanotubes growing radially from YC2 particles,” Applied Physics Letters, vol. 65, No. 12, pp. 1593-1595 (Sep. 19,1994).
Seraphin, “Single-Walled Tubes and Encapsulation of Nanocrystals into Carbon Clusters,” Journal of Electrochemical Society, vol. 142, No. 1, pp. 290-297 (Jan. 1995).
Saito et al., “Carbon Nanocapsules Encaging Metals and Carbides,” J. Phys. Chem. Solids, vol. 54, No. 12, pp. 1849-1860 (1993).
Saito et al., “Extrusion of single-wall carbon nanotubes via formation of small particles condensed near an arc evaporation source,” Chemical Physics Letters, vol. 236, pp. 419-426 (Apr. 21, 1995).
Lambert et al., “Improving conditions towards isolating single-shell carbon nanotubes,” Chemical Physics Letters, vol. 226, pp. 364-371 (Aug. 19, 1994).
Journet et al., “Large-scale production of single-walled carbon nanotubes,” Nature, vol. 388, pp. 756-758 (Aug. 21, 1997).
Thess et al., “Crystalline Ropes of Metallic Carbon Nanotubes,” Science, vol. 273, pp. 483-487 (Jul. 26, 1996).
Guo et al., “Catalytic growth of single-walled nanotubes by laser vaporization” Chemical Physics Letters, vol. 243, pp. 49-54 (Sep. 8, 1995).
Wildöer et al., “Electronic structure of atomically resolved carbon nanotubes,” Nature, vol. 391, pp. 59-62 (Jan. 1, 1998).
Odom et al., “Atomic structure and electronic properties of single-walled carbon nanotubes,” Nature, vol. 391, pp. 62-64 (Jan. 1, 1998).
Dresselhaus et al., Science of Fullerenes and Carbon Nanotubes, Academic Press, San Diego, pp. 763-764 (1996).
Endo, “Grow carbon fibers in the vapor phase,” Chemtech, pp. 568-576 (1988).
Tibbetts, “Vapor-Grown Carbon Fibers: Status and Prospects,” Carbon, vol. 27, No. 5, pp. 745-747 (1989).
Sen et al., “Carbon nanotubes by the metallocene route,” Chemical Physics Letters, vol. 267, pp. 276-280 (Mar. 21, 1997).
Dresselhaus, “Carbon Nanotubes,” Journal of Materials Research, vol. 13, No. 9, pp. 2355-2356 (Sep. 1998).
Hernadi et al., “Fe-Catalyzed Carbon Nanotube Formation,” Carbon, vol. 34, No. 10, pp. 1249-1257 (1996).
Colomer et al., “Large-scale synthesis of single-wall carbon nanotubes by catalytic chemical vapor deposition (CCVD) method,” Chemical Physics Letters, vol. 317, pp. 83-89 (Jan. 28, 2000).
Su et al., “A scalable CVD method for the synthesis of single-walled carbon nanotubes with high catalyst productivity,” Chemical Physics Letters, vol. 322, pp. 321-326 (May 26, 2000).
Kitiyanan et al., “Controlled production of single-wall carbon nanotubes by catalytic decomposition of CO in bimetallic Co-Mo catalysts,” Chemical Physics Letters, vol. 317, pp. 497-503 (Feb. 4, 2000).
Cassell et al., “Large Scale CVD Synthesis of Single-Walled Carbon Nanotubes,” J. Phys. Chem. B., vol. 103, pp. 6484-6492 (1999).
Flahaut et al., “Synthesis of single-walled carbon nanotubes using binary (Fe, Co, Ni) alloy nanoparticles prepared in situ by the reduction of oxide solid solutions,” Chemical Physics Letters, vol. 300, pp. 236-242 (Jan. 29, 1999).
Brotons et al., “Catalytic influence of bimetallic phases for the synthesis of single-walled carbon nanotubes,” Journal of Moleular Catalysis A: Chemical, vol. 116, pp. 397-403 (1997).
Fonseca et al., “Synthesis of single- and multi-wall carbon nanotubes over supported catalysts,” Applied Physics A, vol. 67, pp. 11-22 (1998).
Yudasaka et al., “Specific conditions for Ni catalyzed carbon nanotube growth by chemical vapor deposition,” Applied Physics Letters, vol. 67, No. 17, pp. 2477-2479 (Oct. 23, 1995).
Hernadi et al., “Catalytic synthesis of carbon nanotubes using zeolite support,” Zeolites, vol. 17, pp. 416-423 (1996).
Cheng et al., “Bulk morphlogy and diameter distribution of single-walled carbon nanotubes synthesized by catalytic decomposition of hydrocarbons,” Chemical Physics Letters, vol. 289, pp. 602-610 (Jun. 19, 1998).
Govindaraj et al., “Carbon Structures Obtained by the Disproportionation of Carbon Monoxide Over Nickel Catalyst,” Materials Research Bulletin, vol. 33, No. 4, pp. 663-667 (1998).
Chen et al., “Growth of Carbon Nanotubes by Catalytic Decomposition of CH4 or CO on a Ni-MgO Catalyst,” Carbon, vol. 35, No. 10-11, pp. 1495-1501 (1997).
Hatta et al., “Very long graphitic nano-tubules synthesized by plasma-decomposition of benzene,” Chemical Physics Letters, vol. 217, No. 4, pp. 398-402 (Jan. 21, 1994).
Hornyak et al., “Template Synthesis of Carbon Nanotubes,” NanoStructured Materials, vol. 12, pp. 83-88 (1999).
Flahaut et al., “Synthesis of single-walled carbon nanotube-Co-MgO composite powders and extraction of the nanotubes,” Journal of Materials Communications, Chemistry, vol. 10, pp. 249-252 (2000).
Nikolaev et al., “Gas-phase of catalytic growth of single-walled carbon nanotubes from carbon monoxide,” Chemical Physics Letters, vol. 313, pp. 91-97 (Nov. 5, 1999).
Kiang et al., “Carbon Nanotubes with Single-Layer Walls,” Carbon, vol. 33, No. 7, pp. 903-914 (1995).
Cassell et al., “Combinatorial Optimization of Heterogeneous Catalysts Used in the Growth of Carbon Nanotubes,” Langmuir, vol. 17, pp. 260-264 (2001).
Li et al., “Preparation of Monodispersed Fe-Mo Nanoparticles as the Catalyst for CVD Synthesis of Carbon Nanotubes,” Chemical Materials, vol. 13, pp. 1008-1014 (2001).
Tibbetts, “Vapor-Grown Carbon Fibers,” Carbon Fibers Filaments and Composites, Kluwer Academic Publishers pp. 73-94 (1990).
Murayama et al., “A novel form of filamentous graphite,” Nature, vol. 345, No. 6278, pp. 791-793 (Jun. 28, 1990).
Tibbetts, “Growing Carbon Fibers with a Linearly Increasing Temperature Sweep: Experiments and Modeling,” Carbon, vol. 30, No. 3, pp. 399-406 (1992).
Iijima, “Helical microtubules of graphitic carbon,” Nature, vol. 354, No. 6348, pp. 56-58 (Nov. 7, 1991).
Endo et al., “Electrical properties of Fullerene film and fiber constructs,” 18th Annual Meeting of the Japanese Carbon Society, 10 pages (Dec. 4-6, 1991).
Endo et al., “Generation and Structure of Bucky Fibers and Application in Carbon Fiber Formation,” Transactions of the 2nd C60 Symposium in Japan, 17 pages (Jan. 29, 1992).
Iijima et al., “Pentagons, heptagons and negative curvature in graphite microtubule growth,” Nature, vol. 356, No. 6372, pp. 776-778 (Apr. 30, 1992).
Tibbetts et al., “A New Reactor for Growing Carbon Fibers from Liquid- and Vapor-Phase Hydrocarbons,” Carbon, vol. 31, No. 5, pp. 809-814 (1993).
Endo et al., “Vapor Phase Growth of Carbon Nanotube,” 19th Meeting of Japanese Carbon Society, 7 pages (Dec. 2-4, 1992).
Endo et al., “Growth Mechanisms and Structure of Carbon Nanotube,” Transactions of the 4th C60 Symposium in Japan, 4 pages (Jan. 26-27, 1993).
Tibbetts et al., “Physical Properties of Vapor-Grown Carbon Fibers,” Carbon, vol. 31, No. 7, pp. 1039-1047 (1993).
Endo et al., “The Production and Structure of Polyrolytic Carbon Nanotubes (PCNTs),” J. Phys. Chem. Solids, vol. 54, No. 12, pp. 1841-1848 (1993).
Jiao et al., “Preparing Carbon Clusters by Catalytic Disproportionation of Carbon Monoxide,” Recent Advances in the Chemistry and Physics of Fullerenes and Related Materials, Electrochemical Society Proceedings, vol. 95-10, pp. 667-677 (1995).
Qin, “CVD synthesis of carbon nanotubes,” Journal of Materials Science Letters, vol. 16, No. 6, pp. 457-459 (Mar. 15, 1997).
Sen et al., “Metal-Filled and Hollow Carbon Nanotubes Obtained by the Decomposition of Metal-Containing Free Precursor Molecules,” Chemistry of Materials, vol. 9, No. 10, pp. 2078-2081 (1997).
Terrones et al., “Controlled production of aligned-nanotube bundles,” Nature, vol. 388, pp. 52-55 (Jul. 3, 1997).
Bronikowski et al., “Gas-phase production of carbon single-walled nanotubes from monoxide via the HiPco process: A parametric study,” Journal of Vacuum Science & Technology A, Second Series, vol. 19, No. 4, Part II (Jul./Aug. 2001).