EP1252360A4 - Procede de depot en phase vapeur a haut rendement pour la preparation a grande echelle de nanotubes de carbone a paroi simple - Google Patents

Procede de depot en phase vapeur a haut rendement pour la preparation a grande echelle de nanotubes de carbone a paroi simple

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Publication number
EP1252360A4
EP1252360A4 EP01926332A EP01926332A EP1252360A4 EP 1252360 A4 EP1252360 A4 EP 1252360A4 EP 01926332 A EP01926332 A EP 01926332A EP 01926332 A EP01926332 A EP 01926332A EP 1252360 A4 EP1252360 A4 EP 1252360A4
Authority
EP
European Patent Office
Prior art keywords
aerogel
carbon
catalyst
combinations
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01926332A
Other languages
German (de)
English (en)
Other versions
EP1252360A2 (fr
Inventor
Jie Liu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Duke University
Original Assignee
Duke University
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Filing date
Publication date
Application filed by Duke University filed Critical Duke University
Publication of EP1252360A2 publication Critical patent/EP1252360A2/fr
Publication of EP1252360A4 publication Critical patent/EP1252360A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/881—Molybdenum and iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/32—Freeze drying, i.e. lyophilisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/02—Single-walled nanotubes

Definitions

  • the present invention relates, in general, to a vapor phase deposition method for the preparation of single walled carbon nanotubes, where the method employs a metal catalyst on a support. More particularly, the present invention relates to an improved method where the support comprises an aerogel, such as an AI 2 O 3 aerogel or an AI 2 O 3 /SiO 2 aerogel, as compared to prior art methods that employed supports that are powders.
  • the improved method results in far higher yields of single walled carbon nanotubes than the prior art methods.
  • the present invention provides vapor phase method that employs a metal catalyst supported on an aerogel, for instance on AI 2 O 3 aerogel and/or on AI 2 O 3 /SiO 2 aerogel.
  • the catalyst/support employed in the present invention was made by solvent-gel synthesis with subsequent removal of the liquid solvent by drying selected from the group consisting of supercritical drying, freeze drying and combinations thereof, with supercritical drying being preferred.
  • the inventive method involves vapor phase depositing on the catalyst/support a carbon-containing compound.
  • the compound should have a molecular weight of 28 or less, and if the compound has a higher molecular weight, then the compound should be mixed with H 2 .
  • the vapor phase depositing is with sufficient heat for a sufficient time, in order to produce SWCNTs on the aerogel supported catalyst. Then, the SWCNTs may, if desired, be removed from the aerogel supported catalyst. Typically, the SWCNTs are produced in high yield, for instance, about 100% or greater, based on the weight of the catalyst.
  • SWCNTs are obtained in high yields heretofore unobtainable. This yield is far higher than that of the prior art CVD method, which resulted, at best, in a yield of about 40% based on the weight of the catalyst.
  • Figure 1 is a graph showing typical TGA yield curves for (a) as-prepared and (b) purified SWCNT materials in air, made in accordance with the inventive method.
  • Figure 2 is a graph showing weight gain versus reaction time at 900°C with a methane flow at 1158 seem for a SWCNT material prepared by the inventive method.
  • Figures 3a and 3b are, respectively, photographs taken through a microscope showing (a) a SEM image and (b) a TEM image of a SWCNT sample prepared by the inventive method on an AI 2 O 3 aerogel supported Fe/Mo catalyst. The sample was prepared at about 900°C under a CH4 flow. The flow rate was 1158 seem. The reaction time was 30 minutes.
  • the present invention provides single walled carbon nanotubes using a novel vapor phase method in which a particular catalyst/support is employed in deposition of a carbon-containing compound.
  • the present invention provides a dramatic increase in the yield of single walled carbon nanotubes as compared to the prior art method that uses powder for a support.
  • single walled carbon nanotubes is meant what is conventionally known in the art. Moreover, with the inventive method, it is not intended to exclude that a minor amount, for instance ⁇ 1 %, of multi-walled carbon nanotubes may be concurrently produced.
  • a suitable carbon-containing compound may be one that is vapor at STP or may be one that is capable of being converted into vapor at reaction conditions.
  • a sufficient flow rate of the carbon-containing compound should be employed, and may range from about 900 seem to about 1300 seem.
  • a sufficient time may range from about 0.25 hours to about 7 hours.
  • a sufficient temperature may range from about 750°C to about 1000°C.
  • the yield may be about 200%, about 300%, or even higher.
  • a suitable catalyst is any metal catalyst known in the art for making nanotubes.
  • a preferred metal catalyst may be Fe/Mo, Fe/Pt, and combinations thereof.
  • a suitable support is any aerogel as that term is conventionally adopted in the art to mean a gel with air as dispersing agent prepared by drying.
  • the aerogel support could be a powdered support converted to an aerogel by known methods. As discussed in more detail below, the drying may be supercritical drying or may be freeze drying, but it is not intended to include drying that results in a xerogel.
  • a preferred aerogel support may be AI 2 O 3 aerogel support, AI 2 O 3 /SiO 2 aerogel support, and combinations thereof.
  • the yield of the SWCNT material was measured by heating up the prepared SWCNT material under flowing air in a TGA.
  • the total yield of SWCNT material which yield is shown on the vertical axis as a % weight gain, was calculated by the weight loss between 300°C and 700°C, which temperature is shown on the horizontal axis, where the SWCNT material burned in air, divided by the weight left at 700°C, which was presumably the weight of the catalyst and support materials.
  • the inventive method showed a yield of significantly better than the values previously reported values by A. M. Cassell, J. A. Raymakers, J. Kong, H. J. Dai, Journal of Physical Chemistry B 103, 6484-6492 (1999) Kong, Cassell, and Dai, Chemical Physics Letters 292, 4-6 (1998).
  • the quality of the prepared SWCNT was characterized by SEM imaging and TEM imaging. More particularly, as depicted in Figure 3a, the SEM image of the as- prepared SWCNT material showed a tangled web-like network of very clean fibers. The diameters of the fibers appeared to be in the range of about 10 to about 20 nanometers. It is noted that the SEM image was of as-grown materials; no purification was performed before the imaging. Furthermore, as depicted in Figure 3b, the TEM image of the SWCNT material showed that the fibers observed in the SEM image were actually bundles of single walled carbon nanotubes.
  • the diameters of the nanotubes measured from the high resolution TEM images were between about 0.9 and about 2.7 nm. Both the SEM and the TEM images showed the SWCNT materials possessed characteristics similar to those of high quality single walled carbon nanotube materials prepared in the laser method (see, A. Thess et al., Science 273, 483-487 (1996) and T. Guo, P. Nikolaev, A. Thess, D. T. Colbert, and R. E. Smalley, Chemical Physics Letters 243, 49-54 (1995)) and the arc method (see, M. Wang, X.L. Zhao, M. Ohkohchi, and Y. Ando, Fullerene Science & Technology 4, 1027-1039 (1996) and C. Journet et al., Nature 388, 756-758 (1997)).
  • the inventive method reflects that a drying process of the wet gel, as discussed below in the laboratory examples, is a necessary step in preparing the high performance catalysts on aerogel supports, as employed in the inventive method.
  • the drying may be achieved by supercritical drying, such as by CO 2 supercritical drying, or by ethanol supercritical drying, or alternatively, may be achieved by freeze drying, such as by freeze drying using water, and combinations thereof.
  • supercritical drying such as by CO 2 supercritical drying
  • ethanol supercritical drying or alternatively, may be achieved by freeze drying, such as by freeze drying using water, and combinations thereof.
  • freeze drying such as by freeze drying using water, and combinations thereof.
  • it is not intended to include drying that results in a xerogel.
  • Fricke, Aerogels, Springer-Verlag, Berlin, Heidelberg, New York, Tokyo (1986) and N. Husing, U. Schubert, Angew. Chem. Int. Ed. 37, 22-45 (1998) discuss that merely evaporating the liquid solvent at ambient conditions (i.e., about STP) would cause the gel to shrink due to the collapse of the porous structures by the strong forces from surface tension at the liquid/gas interfaces within the pores in the gel, and this shrinkage would significantly reduce the total surface area and pore volume of the dried material, which is normally called xerogel.
  • the liquid solvent in the wet gel is put into the supercritical state, for instance, under a carbon dioxide blanket. Therefore, there are substantially no liquid/gas interfaces in the pores during drying.
  • the original porous structure in the wet gel is thus substantially maintained in the resultant dried catalysts/aerogels. Also, as more and more nanotubes were grown on the surface of the aerogel supported catalyst, the diffusion of the carbon-containing compound, i.e., methane or carbon monoxide in the examples below, to the catalyst/support became more difficult.
  • ASB Aluminum tri-sec-butoxide
  • Fe 2 (SO 4 ) 3 .4H 2 O Fe 2 (SO 4 ) 3 .4H 2 O
  • MoO 2 (acac) 2 bis(actylacetonato)dioxomolybdenum
  • Reagent grade nitric acid, ammonium hydroxide, and ethanol were purchased from VWR Scientific Products.
  • Catalysts/supports were prepared using the solvent-gel technique , as reported in D. J. Suh and J.T. Park, Chemistry of Materials 9, 1903-1905 (1997) followed by supercritical drying. Optionally, some were dried by freeze drying.
  • the resultant was left to age for about 10 hours before the supercritical drying step was performed under the following conditions.
  • the catalyst/support wet gel was sealed in a high-pressure container, which was then cooled to about 0°C and pressurized to fill the container with liquid CO 2 , at about 830 psi (about 59.4 kg/cm 2 ).
  • a solvent exchange step followed, in order to exchange the ethanol liquid solvent in the gel with liquid CO 2 , by flushing the container with liquid CO 2 a few times.
  • the container was warmed up to between about 50°C and about 200°C, which is above the critical temperature (31 °C) of CO 2 , and the pressure was kept between about 1500 psi and 2500 psi (between about 106.4 kg/cm 2 and 176.8 kg/cm 2 ), which is above the critical pressure (1050 psi, 74.8 kg/cm 2 ) of CO 2 .
  • the system was held at these conditions for a short time before the pressure was slowly reduced while the temperature was kept the same.
  • each catalyst (in metal hydroxide form) on aerogel support was calcined at 500° C for 30 minutes, to effect conversion to the metal oxide form. Then before being used for SWCNT growth, conversion to the metal form was effected by reduction under H 2 for 30 minutes at 900° C. The pressure at that stage was about 830 psi (about 59.4 kg/cm 2 ).
  • Each catalyst/support prepared this way was a catalyst supported on a highly porous, very fine, free-flowing aerogel with a surface area of from about 500 m 2 /g to about 600 m 2 /g.
  • some samples were supercritically dried with ethanol or dried with freeze drying as follows.
  • Ethanol supercritical drying A 100 ml high pressure and high temperature container was used. At least 35 ml of the wet gel was added in the container. Before heating, N 2 was used to flush the system to drive the air out. Then the whole system was sealed and heating was started. After the temperature reached 260°C, the system was maintained at that temperature for about 30 minutes before the EtOH was released slowly. The releasing process took about 15 minutes. The, the system was cooled down gradually and the aerogel supported catalyst taken out. The yield of nanotubes for this was similar to the one dried with CO 2 . Freeze drying: The ethanol in the wet gel was replaced by water through solvent exchange.
  • SWCNTs were prepared in a simple vapor phase deposition setup made of a tube furnace and gas flow control units.
  • a catalyst/support sample were put into an alumina boat inside a quartz tube.
  • Each sample was individually heated to reaction temperature, under an Ar flow at a flow rate of about 100 seem, and then, the Ar was switched to H 2 (about 100 seem flow rate) for 30 minutes, before switching to a methane flow (about 1000 seem) for 30 minutes.
  • An individual sample was heated for each temperature of about 800°C, about 850°C, about 900°C, and about 950°C.
  • the reaction was carried out for the desired time before the methane flow was turned off and the Ar flow turned on and the temperature reduced to room temperature. Each resultant was then weighed and characterized. Characterization.
  • TEM imaging was performed on a Philip CM-12 microscope operating at 100 kV.
  • the samples for TEM imaging were prepared by sonicating about 1 mg of material in 10 ml of methanol for 10 minutes and drying a few drops of the suspension on a holy-carbon grid.
  • the yield of the SWCNT material with respect to the catalyst was measured on a thermal gravimetric analyzer (model SDT 2960, purchased from TA Instruments) under flowing air with a heating rate of 5°C/minute.
  • the observed yield, measured by TGA, was 100.2% as depicted in Figure 1.
  • Example I The procedure of Example I was substantially repeated, except this time with a methane flow for about 60 minutes (instead of about 30 minutes) and a temperature of about 900°C (instead of various temperatures of about 800°C about 850°C, about 900°C, and about 950°C) and a flow rate of about 1158 seem (instead of about 1000 seem), during SWCNT growth.
  • the yield measured by TGA was about 200%.
  • a catalyst/support made from the same AI 2 O 3 wet gel, but dried differently to make xerogel was compared.
  • the aerogel supported catalyst showed a yield of about 200% of high purity SWCNT under a methane flow at about 900°C for about 60 minutes, as reported by Example I.
  • the xerogel supported catalyst showed a weight gain of ⁇ 5% under the same conditions.
  • Example I The procedure of Example I was substantially repeated, except this time with CO instead of CH 4 . Also, the temperature of the CO flow was about 850°C, with a CO flow rate of about 1200 seem for about 200 minutes. The result was a yield of about 150%.
  • Example I The procedure of Example I was substantially repeated, except this time with AI 2 O 3 /SiO 2 as the aerogel support, instead of AI 2 O 3 as the aerogel support. Substantially the same results were obtained, except there was more amorphous carbon.
  • Example VI It is believed that more amorphous carbon resulted in Example VI since in a comparison, AI 2 O 3 /SiO 2 aerogel (without any metal catalyst) was tried with methane for 30 minutes at 900°C and this converted the methane to amorphous carbon.

Abstract

La présente invention concerne un procédé amélioré de dépôt en phase vapeur destiné à la préparation de nanotubes de carbone à paroi simple sur un catalyseur métallique supporté sur aérogel. Le rendement total de nanotubes de carbone à paroi simple est souvent égal à au moins 100 % environ, sur la base du poids du catalyseur, pour un temps de réaction d'au moins 30 minutes environ.
EP01926332A 2000-01-07 2001-01-05 Procede de depot en phase vapeur a haut rendement pour la preparation a grande echelle de nanotubes de carbone a paroi simple Withdrawn EP1252360A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US17487400P 2000-01-07 2000-01-07
US174874P 2000-01-07
PCT/US2001/000335 WO2001049599A2 (fr) 2000-01-07 2001-01-05 Procede de depot en phase vapeur a haut rendement pour la preparation a grande echelle de nanotubes de carbone a paroi simple

Publications (2)

Publication Number Publication Date
EP1252360A2 EP1252360A2 (fr) 2002-10-30
EP1252360A4 true EP1252360A4 (fr) 2006-07-26

Family

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Application Number Title Priority Date Filing Date
EP01926332A Withdrawn EP1252360A4 (fr) 2000-01-07 2001-01-05 Procede de depot en phase vapeur a haut rendement pour la preparation a grande echelle de nanotubes de carbone a paroi simple

Country Status (7)

Country Link
EP (1) EP1252360A4 (fr)
JP (1) JP2003520176A (fr)
KR (1) KR20020084087A (fr)
CN (1) CN1418260A (fr)
AU (1) AU5287601A (fr)
CA (1) CA2395807A1 (fr)
WO (1) WO2001049599A2 (fr)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020172767A1 (en) * 2001-04-05 2002-11-21 Leonid Grigorian Chemical vapor deposition growth of single-wall carbon nanotubes
CA2451080C (fr) 2001-07-03 2010-08-31 Facultes Universitaires Notre-Dame De La Paix Supports catalytiques et nanotubes de carbone produits sur ces supports
GB0216654D0 (en) 2002-07-17 2002-08-28 Univ Cambridge Tech CVD Synthesis of carbon nanoutubes
US7214361B2 (en) * 2002-11-26 2007-05-08 Honda Giken Kogyo Kabushiki Kaisha Method for synthesis of carbon nanotubes
US6974492B2 (en) 2002-11-26 2005-12-13 Honda Motor Co., Ltd. Method for synthesis of metal nanoparticles
US6974493B2 (en) 2002-11-26 2005-12-13 Honda Motor Co., Ltd. Method for synthesis of metal nanoparticles
GB2399092B (en) * 2003-03-03 2005-02-16 Morgan Crucible Co Nanotube and/or nanofibre synthesis
JP5098333B2 (ja) * 2004-10-15 2012-12-12 日本碍子株式会社 多孔質構造体の製造方法
US7485600B2 (en) * 2004-11-17 2009-02-03 Honda Motor Co., Ltd. Catalyst for synthesis of carbon single-walled nanotubes
US7871591B2 (en) * 2005-01-11 2011-01-18 Honda Motor Co., Ltd. Methods for growing long carbon single-walled nanotubes
CA2500766A1 (fr) 2005-03-14 2006-09-14 National Research Council Of Canada Methode et appareil de production et de fonctionnalisation en continu de nanotubes de carbone a simple paroi au moyen d'une torche a plasma inductif haute frequence
EP1797950A1 (fr) * 2005-12-14 2007-06-20 Nanocyl S.A. Catalyseur pour la fabrication de nanotubes de carbone à parois multiples
US8163263B2 (en) 2006-01-30 2012-04-24 Honda Motor Co., Ltd. Catalyst for the growth of carbon single-walled nanotubes
JP5055520B2 (ja) * 2006-02-24 2012-10-24 独立行政法人産業技術総合研究所 多孔質構造体及びその製造方法
US8951631B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused metal fiber materials and process therefor
US9005755B2 (en) 2007-01-03 2015-04-14 Applied Nanostructured Solutions, Llc CNS-infused carbon nanomaterials and process therefor
US8951632B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused carbon fiber materials and process therefor
JP5753102B2 (ja) * 2009-02-27 2015-07-22 アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニーＡｐｐｌｉｅｄ Ｎａｎｏｓｔｒｕｃｔｕｒｅｄｓｏｌｕｔｉｏｎｓ， Ｌｌｃ ガス予熱方法を用いた低温ｃｎｔ成長
US20100227134A1 (en) 2009-03-03 2010-09-09 Lockheed Martin Corporation Method for the prevention of nanoparticle agglomeration at high temperatures
US8969225B2 (en) 2009-08-03 2015-03-03 Applied Nano Structured Soultions, LLC Incorporation of nanoparticles in composite fibers
EP2616189B1 (fr) 2010-09-14 2020-04-01 Applied NanoStructured Solutions, LLC Substrats en verre présentant des nanotubes de carbone qui ont grandi sur ceux-ci et procédés pour la production de ceux-ci
US8815341B2 (en) 2010-09-22 2014-08-26 Applied Nanostructured Solutions, Llc Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof
JP6042314B2 (ja) * 2012-12-04 2016-12-14 本田技研工業株式会社 カーボンナノチューブ成長用基板及びその製造方法
JP6041775B2 (ja) * 2013-09-13 2016-12-14 本田技研工業株式会社 カーボンナノチューブ成長用基板及びその製造方法
US11040876B2 (en) * 2017-09-18 2021-06-22 West Virginia University Catalysts and processes for tunable base-grown multiwalled carbon nanotubes
CN112533868B (zh) * 2018-07-31 2023-11-03 株式会社大阪曹達 碳纳米管的制造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4713233A (en) * 1985-03-29 1987-12-15 Allied Corporation Spray-dried inorganic oxides from non-aqueous gels or solutions
US4916108A (en) * 1988-08-25 1990-04-10 Westinghouse Electric Corp. Catalyst preparation using supercritical solvent
JP3285614B2 (ja) * 1992-07-30 2002-05-27 日本碍子株式会社 排ガス浄化用触媒及びその製造方法
US6004436A (en) * 1996-08-16 1999-12-21 The Regents Of The University Of California Processes for the chemical modification of inorganic aerogels
KR100376197B1 (ko) * 1999-06-15 2003-03-15 일진나노텍 주식회사 탄소 소오스 가스 분해용 촉매금속막을 이용한탄소나노튜브의 저온 합성 방법

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MING SU ET AL: "A scalable CVD method for the synthesis of single-walled carbon nanotubes with high catalyst productivity", CHEMICAL PHYSICS LETTERS, NORTH-HOLLAND, AMSTERDAM, NL, vol. 322, no. 5, 26 May 2000 (2000-05-26), pages 321 - 326, XP002210666, ISSN: 0009-2614 *
SOMG X.Y. ET AL: "AEM and HREM evaluation of carbonnanostructures in silica aerogels", 1994, XP002374141, Retrieved from the Internet <URL:http://www.osti.gov/bridge/servlets/purl/10165302-1HhOMG/native/10165302.pdf> [retrieved on 20060327] *

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JP2003520176A (ja) 2003-07-02
AU5287601A (en) 2001-07-16
WO2001049599A3 (fr) 2002-03-07
EP1252360A2 (fr) 2002-10-30
WO2001049599A2 (fr) 2001-07-12
CA2395807A1 (fr) 2001-07-12

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