[go: up one dir, main page]

US20040265212A1 - Synthesis of coiled carbon nanotubes by microwave chemical vapor deposition - Google Patents

Synthesis of coiled carbon nanotubes by microwave chemical vapor deposition Download PDF

Info

Publication number
US20040265212A1
US20040265212A1 US10/729,716 US72971603A US2004265212A1 US 20040265212 A1 US20040265212 A1 US 20040265212A1 US 72971603 A US72971603 A US 72971603A US 2004265212 A1 US2004265212 A1 US 2004265212A1
Authority
US
United States
Prior art keywords
coiled carbon
carbon nanotube
reaction chamber
nanotube
coiled
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.)
Abandoned
Application number
US10/729,716
Other languages
English (en)
Inventor
Vijay Varadan
Jining Xie
Kingsuk Mukhopakhyay
Jitendra Yadev
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.)
Penn State Research Foundation
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to US10/729,716 priority Critical patent/US20040265212A1/en
Publication of US20040265212A1 publication Critical patent/US20040265212A1/en
Assigned to THE PENN STATE RESEARCH FOUNDATION reassignment THE PENN STATE RESEARCH FOUNDATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: XIE, JINING, VARADAN, VIJAY
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof

Definitions

  • the present invention relates to the field of carbon nanotubes. More particularly, the invention relates to mass-produced coiled carbon nanotubes and to a method for their synthesis using microwave chemical vapor deposition (CVD).
  • CVD microwave chemical vapor deposition
  • the present invention relates to coiled carbon nanotubes. Since the discovery of carbon nanotubes by Iijima, coiled carbon nanotubes have become objects of widespread interest. The primary difference between coiled carbon nanotubes and carbon nanocoils lies in the crystalline graphitic structures of the nanotubes. Also, the diameter of coiled carbon nanotubes ( ⁇ 100 nm) is much smaller than the diameter of carbon nanocoils. The coil morphology, together with as well as the extraordinary properties of nanotubes, make coiled carbon nanotubes a promising material for hydrogen storage, field emission, EM absorber and nanotechnology applications in general.
  • Nanotubes prepared from CCVD methods tend to be produced in straight or randomly curled morphologies.
  • accidentally coiled carbon nanotubes were reported in extremely low yield by Hernadi et al. [“Fe-catalyzed carbon nanotube formation” Carbon 34 1249-57, 1996].
  • Amelinckx et al. reported a formation mechanism for catalytically grown helix-shaped graphite nanotubes [“A formation mechanism for catalytically grown helix-shaped graphite nanotubes” Science 265 635-9, 1994]. According to their results, the coil morphology of carbon nanotubes is due to the mismatch between the extrusion velocity and the rate of carbon deposition.
  • CNTs along with coiled carbon nanotubes, are the most promising materials anticipated to impact future nanoscience and nanotechnology. Their unique structural and electronic properties have generated great interest for use in a broad range of nanodevices.
  • a significant amount of work has been done in the past decade to reveal the unique structural, electrical, mechanical, electromechanical and chemical properties of carbon nanotubes and to explore the key applications of this novel material. Most of these applications will require efficient fabrication methods capable of producing pure CNTs, including coiled carbon nanotubes, to meet device requirements.
  • Another advantage of coiled carbon nanotubes is that they are capable of forming in situ semiconductor-metallic or semiconductor-insulator junctions which one can utilize for the fabrication of nanodevices.
  • Coiled carbon nanotubes also have an greater surface area than CNTS which increases their functionalization. Accordingly it is an object of the present invention to provide effective and efficient methods of fabricating CNTs, especially coiled carbon nanotubes, to enable the commercialization of applications using such.
  • the invention is a method for synthesizing coiled carbon nanotubes using a microwave CVD system with inventive processing conditions and specialized catalyst(s).
  • Preferred conditions include the use of acetylene as a hydrocarbon source gas in a microwave CVD system without using an impurity gas and using an iron supported on magnesium carbonate as a catalyst.
  • the invention also includes the resulting coiled carbon nanotubes.
  • FIG. 1 shows a schematic diagram of a conventional thermal filament CVD system.
  • FIG. 2 shows a schematic diagram of a microwave CVD system used in the present invention.
  • FIG. 3 shows an illustration of a coiled carbon nanotube.
  • FIG. 4 shows a flow diagram for the flow control systems.
  • FIG. 5 shows a SEM micrograph of coiled nanotube synthesized using a microwave CVD system in accordance with the present invention.
  • FIG. 6 shows a TEM image of coiled nanotubes obtained from a microwave CVD system in accordance with the present invention.
  • an apparatus designed to perform this method is designated in its entirety by the reference numeral 8 .
  • the method generally involves placing a catalyst 3 inside of a reaction chamber 1 and then heating up the reaction chamber 1 .
  • a quartz reaction tube 2 is used to transport the catalyst in and out of the reaction chamber 1 .
  • the temperature is monitored by a thermocouple 7 .
  • a hydrocarbon source gas 4 such as acetylene
  • the hydrocarbon source gas 4 is then broken down into its elements which interact with the catalyst 3 resulting in the growth of carbon nanotubes.
  • the exhaust gas 6 is removed from the reaction chamber 1 .
  • argon 5 is pumped into the reaction chamber 1 for purging.
  • FIG. 2 shows a microwave CVD system 9 according to a preferred embodiment of the present invention.
  • this method has involved the use of a furnace to heat the reaction chamber 33 .
  • the present invention uses a magnetron 10 in place of a furnace. Although a magnetron 10 capable of producing 750 W is preferred, any commercially-available magnetron may be used.
  • the magnetron 10 creates a microwave field inside the reaction chamber 33 .
  • a known amount of the catalyst and catalyst support 15 are dispersed onto the substrate 34 .
  • the substrate 34 is then loaded into the reaction chamber 33 .
  • the substrate 34 is loaded in and out of the reaction chamber 33 in a quartz container 19 .
  • the magnetron 10 is then switched on to heat the substrate 34 to the reaction temperature.
  • the reaction temperature is set to 700° C.
  • an inert gas 22 at an optimized flow rate, can be used for purging, although the use of an inert gas 22 is not required for the present invention.
  • a hydrocarbon source gas 21 is introduced into the reaction chamber at an optimal flow rate.
  • the advantage of using a microwave field is that it is uniform throughout the reaction chamber 33 . This uniform field allows for a higher quantity of coiled carbon nanotubes with consistent properties to be produced during each reaction.
  • a microwave field can be instantly turned off whereas a reaction chamber heated by a furnace must be allowed to cool to room temperature before any nanotubes can be extracted. This dramatically reduces the lag time between production rounds.
  • a commercially available stub tuner 12 is used prevent any reflected power from flowing into the magnetron 10 .
  • the inventors manually adjusted the stub tuner 12 .
  • a commercially available three-port circulator 13 was used to automatically adjust the stub tuner 12 .
  • the invention may comprise a circulating chiller 14 which cools the magnetron 10 and therefore extends its life.
  • the invention may further comprise a stirrer 27 , which assists in making the microwave field uniform.
  • the stirrer 27 is driven by a motor 28 .
  • the reaction chamber 33 can be made from any number of materials without departing from the scope of the present invention.
  • the reaction chamber is constructed out of aluminum.
  • the reaction chamber is made of steel.
  • the reaction chamber is a cylinder.
  • the inventors used two reaction chambers manufactured by HVS Technologies. The smaller reaction chamber had dimensions of 14′′ in length and 5.75′′ in diameter. The larger reaction chamber had dimensions of 70′′ in length and 35′′ in diameter.
  • the catalyst can be made from various materials without departing from the scope of the present invention, a preferred catalyst is iron. Iron is preferred because it produces the highest yield of coiled carbon nanotubes. Alternatively, other transition metal catalysts can be used; including combinations of transition metals (e.g., bimetallic catalysts). It is important to note here that the indium-tin-iron catalyst disclosed in U.S. Pat. No. 6,583,085 to Nakayama et al. is not preferred for this invention. The presence of tin in the catalyst would cause the catalyst to spark when placed in the microwave field. In addition, the indium-tin-iron catalyst would not be preferred does not easily absorb the microwaves.
  • the specific support used in the method of the present invention is critical.
  • the support must contain pores giving rise to the growth of coiled carbon nanotubes according to the invention as opposed to other formations, such as fibers.
  • the supports must also be able to easily absorb microwaves.
  • Some non-limiting examples include silica, zeolite, and magnesium carbonate (preferred).
  • Preferred pore sizes lie in the range of 0.1 to 10 nm with a surface area of 250-300 m ⁇ m/g.
  • the following are three examples of catalyst supports and catalysts with which they were combined (being just three examples of “supported metal catalyst”).
  • Iron nitrate and magnesium carbonate were weighed 1:1 weight ratio. Iron nitrate was dissolved in water and the resulting solution was added to magnesium carbonate, followed by continuous stirring to obtain a semi-solid mixture. The semi-solid mixture was kept inside an overnight at 500° C. After allowing the mixture to cool to room temperature, the resulting brown color solid was powdered. While the pole size of the magnesium carbonated varied somewhat throughout its surface, a majority were 10 nm in diameter.
  • Iron nitrate and silica were weighed 1:1 weight ratio. Iron nitrate was dissolved in water and the resulting solution was added to silica, followed by continuous stirring to obtain a semi-solid mixture. The semi-solid mixture was kept inside an oven at 120° C. overnight. After allowing the mixture to cool to room temperature, the resulting brown color solid was powdered. As a porous substance, the pore sizes for silica varied throughout its length.
  • zeolite Although commercial grade zeolite may be used.
  • the hydrothermal processing method is described in Cundy, C. et al. [“The Hydrothermal Synthesis of Zeolites: History and Development from the Earliest Days to the Present Time” Chem. Rev. 2003, 103, 663-701]
  • Nickel acetate was dissolved in water and a proper amount of zeolite was added into the solution with a Ni percentage in zeolite of 14.5 wt %.
  • the gel solution was stirred and kept in an oven at 120° C. overnight. After drying, the solid was crushed into a fine powder. While the pore size for zeolite varied throughout its surface, the majority were 1 nm in diameter.
  • the substrate 34 is made of silicon carbide.
  • the hydrocarbon source gas 21 can be any gas containing carbon, in the preferred embodiment the hydrocarbon source gas is acetylene.
  • the inventors found that the optimal flow rate for acetylene is 30 sccm for the smaller reaction chamber (14′′ ⁇ 5.75′′) and 600 sccm for the larger one (70′′ ⁇ 35′′).
  • Other non-limiting examples include methane, ethane and propane.
  • helium is preferred, although any inert gas can be used (such as argon).
  • an impurity gas e.g. thiophene
  • FIG. 4 is a software flow chart for the flow control systems.
  • the temperature of the reaction chamber 33 is monitored by a pyrometer 23 , which in the preferred embodiment is an optical pyrometer 25 .
  • the temperature readings taken by the pyrometer 23 are transmitted to a computer 26 .
  • the computer 26 compares the temperature of the reaction chamber 33 with the set temperature for processing (preferably 700° C.).
  • the computer 26 controls the switching power supply 11 which in turn controls the magnetron 10 . If the reaction chamber temperature is too low, the computer 26 will tell the switching power supply 11 to turn on the magnetron 10 and increase the temperature.
  • the computer 26 will tell the switching power supply 11 to turn off the magnetron 10 .
  • the computer 26 also communicates with the master flow controller 20 which controls the mass flow controllers 24 .
  • the mass flow controllers 24 control the flow rates of the inert 22 and hydrocarbon source gas 21 .
  • FIG. 3 An illustration of a coiled carbon nanotube is shown in FIG. 3.
  • the distance between the coils is substantially uniform throughout the length of each coiled carbon nanotube.
  • the diameter of each coiled carbon nanotube will also be substantially uniform.
  • the coiled carbon nanotube 29 is composed of carbon rings in the shapes of pentagons 32 , hexagons 30 , and heptagons 31 . Depositing the various shapes in specific locations along the surface of the carbon nanotube causes the carbon nanotube to assume a coiled shape.
  • the non-hexagonal/hexagonal ratio of the carbon rings ranges from 0.1:1 to 1:1.
  • a non-hexagonal/hexagonal ratio of 0.1 produces a “loose” coil with a large pitch.
  • a non-hexagonal/hexagonal ratio of 1:1 produces a “tight” coil with a small pitch.
  • the exact morphology of coiled carbon nanotubes will depend on the catalyst/catalyst support that is used and the conditions of the microwave CVD.
  • a scanning electron microscope (SEM 3000N manufactured by Hitachi) was used to investigate the morphology of the coiled carbon nanotubes. Due to the conducting property of carbon nanotubes, no gold coating is necessary for SEM operation.
  • a transmission electron microscope (TEM 420T manufactured by Philips) was used to study the nanostructure of the coiled carbon nanotubes. TEM samples were prepared by ultrasonic vibration of a small amount of material in acetone followed by dropping on a TEM grid (Lacey carbon film on 300 mesh copper grid, Electron Microscopy Science).

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Composite Materials (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Carbon And Carbon Compounds (AREA)
US10/729,716 2002-12-06 2003-12-05 Synthesis of coiled carbon nanotubes by microwave chemical vapor deposition Abandoned US20040265212A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/729,716 US20040265212A1 (en) 2002-12-06 2003-12-05 Synthesis of coiled carbon nanotubes by microwave chemical vapor deposition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US43188802P 2002-12-06 2002-12-06
US10/729,716 US20040265212A1 (en) 2002-12-06 2003-12-05 Synthesis of coiled carbon nanotubes by microwave chemical vapor deposition

Publications (1)

Publication Number Publication Date
US20040265212A1 true US20040265212A1 (en) 2004-12-30

Family

ID=32507816

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/729,716 Abandoned US20040265212A1 (en) 2002-12-06 2003-12-05 Synthesis of coiled carbon nanotubes by microwave chemical vapor deposition

Country Status (3)

Country Link
US (1) US20040265212A1 (fr)
AU (1) AU2003300816A1 (fr)
WO (1) WO2004052973A2 (fr)

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030138561A1 (en) * 2002-01-14 2003-07-24 Zhen-Yu Juang Thermal cracking chemical vapor deposition method for synthesizing nano-carbon material
US20070275499A1 (en) * 2006-05-26 2007-11-29 Reed Roeder Corderman Nonostructure arrays and methods of making same
US20080004396A1 (en) * 2006-02-14 2008-01-03 Lg Chem, Ltd. Rigid random coils and composition comprising the same
US20090000192A1 (en) * 2005-06-24 2009-01-01 Washington State University Research Foundation Apparatus with high surface area nanostructures for hydrogen storage, and methods of storing hydrogen
US20090032741A1 (en) * 2007-07-25 2009-02-05 Nanocomp Technologies, Inc. Systems and Methods for Controlling Chirality of Nanotubes
US20100000754A1 (en) * 2008-05-07 2010-01-07 Nanocomp Technologies, Inc. Carbon nanotube-based coaxial electrical cables and wiring harness
US20100015033A1 (en) * 2005-05-20 2010-01-21 Clemson University Process for preparing carbon nanostructures with tailored properties and products utilizing same
US20100215915A1 (en) * 2005-06-24 2010-08-26 Washington State University Method for manufacture and coating of nanostructured components
US20110005808A1 (en) * 2009-07-10 2011-01-13 Nanocomp Technologies, Inc. Hybrid Conductors and Method of Making Same
US20110053020A1 (en) * 2007-11-09 2011-03-03 Washington State University Research Foundation Catalysts and related methods
US8679444B2 (en) 2009-04-17 2014-03-25 Seerstone Llc Method for producing solid carbon by reducing carbon oxides
US8722171B2 (en) 2011-01-04 2014-05-13 Nanocomp Technologies, Inc. Nanotube-based insulators
US8999285B2 (en) 2005-07-28 2015-04-07 Nanocomp Technologies, Inc. Systems and methods for formation and harvesting of nanofibrous materials
US9061913B2 (en) 2007-06-15 2015-06-23 Nanocomp Technologies, Inc. Injector apparatus and methods for production of nanostructures
US9090472B2 (en) 2012-04-16 2015-07-28 Seerstone Llc Methods for producing solid carbon by reducing carbon dioxide
US9198232B2 (en) 2008-05-07 2015-11-24 Nanocomp Technologies, Inc. Nanostructure-based heating devices and methods of use
US9221685B2 (en) 2012-04-16 2015-12-29 Seerstone Llc Methods of capturing and sequestering carbon
US9236669B2 (en) 2007-08-07 2016-01-12 Nanocomp Technologies, Inc. Electrically and thermally non-metallic conductive nanostructure-based adapters
US9475699B2 (en) 2012-04-16 2016-10-25 Seerstone Llc. Methods for treating an offgas containing carbon oxides
US9586823B2 (en) 2013-03-15 2017-03-07 Seerstone Llc Systems for producing solid carbon by reducing carbon oxides
US9598286B2 (en) 2012-07-13 2017-03-21 Seerstone Llc Methods and systems for forming ammonia and solid carbon products
US9604848B2 (en) 2012-07-12 2017-03-28 Seerstone Llc Solid carbon products comprising carbon nanotubes and methods of forming same
US9650251B2 (en) 2012-11-29 2017-05-16 Seerstone Llc Reactors and methods for producing solid carbon materials
US9718691B2 (en) 2013-06-17 2017-08-01 Nanocomp Technologies, Inc. Exfoliating-dispersing agents for nanotubes, bundles and fibers
US9731970B2 (en) 2012-04-16 2017-08-15 Seerstone Llc Methods and systems for thermal energy recovery from production of solid carbon materials by reducing carbon oxides
US9779845B2 (en) 2012-07-18 2017-10-03 Seerstone Llc Primary voltaic sources including nanofiber Schottky barrier arrays and methods of forming same
US9783416B2 (en) 2013-03-15 2017-10-10 Seerstone Llc Methods of producing hydrogen and solid carbon
US9783421B2 (en) 2013-03-15 2017-10-10 Seerstone Llc Carbon oxide reduction with intermetallic and carbide catalysts
US9796591B2 (en) 2012-04-16 2017-10-24 Seerstone Llc Methods for reducing carbon oxides with non ferrous catalysts and forming solid carbon products
US9896341B2 (en) 2012-04-23 2018-02-20 Seerstone Llc Methods of forming carbon nanotubes having a bimodal size distribution
US10086349B2 (en) 2013-03-15 2018-10-02 Seerstone Llc Reactors, systems, and methods for forming solid products
US10100402B2 (en) 2011-10-07 2018-10-16 International Business Machines Corporation Substrate holder for graphene film synthesis
US10115844B2 (en) 2013-03-15 2018-10-30 Seerstone Llc Electrodes comprising nanostructured carbon
US10581082B2 (en) 2016-11-15 2020-03-03 Nanocomp Technologies, Inc. Systems and methods for making structures defined by CNT pulp networks
US10815124B2 (en) 2012-07-12 2020-10-27 Seerstone Llc Solid carbon products comprising carbon nanotubes and methods of forming same
US11279836B2 (en) 2017-01-09 2022-03-22 Nanocomp Technologies, Inc. Intumescent nanostructured materials and methods of manufacturing same
US11434581B2 (en) 2015-02-03 2022-09-06 Nanocomp Technologies, Inc. Carbon nanotube structures and methods for production thereof
CN116332159A (zh) * 2023-03-28 2023-06-27 北京科技大学 一种超声辅助催化裂解碳氢化合物制备碳纳米管的方法和装置
US11752459B2 (en) 2016-07-28 2023-09-12 Seerstone Llc Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7777478B2 (en) 2006-06-08 2010-08-17 University Of Dayton Touch and auditory sensors based on nanotube arrays

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5413866A (en) * 1990-10-23 1995-05-09 Baker; R. Terry K. High performance carbon filament structures
US6232980B1 (en) * 1998-03-18 2001-05-15 Silicon Graphics, Inc. System and method for generating planar maps of three-dimensional surfaces
US6231980B1 (en) * 1995-02-14 2001-05-15 The Regents Of The University Of California BX CY NZ nanotubes and nanoparticles
US6232706B1 (en) * 1998-11-12 2001-05-15 The Board Of Trustees Of The Leland Stanford Junior University Self-oriented bundles of carbon nanotubes and method of making same
US6333016B1 (en) * 1999-06-02 2001-12-25 The Board Of Regents Of The University Of Oklahoma Method of producing carbon nanotubes
US20020127170A1 (en) * 2000-09-22 2002-09-12 Eun-Hwa Hong Method of synthesizing carbon nanotubes and apparatus used for the same
US6455021B1 (en) * 1998-07-21 2002-09-24 Showa Denko K.K. Method for producing carbon nanotubes
US20030010279A1 (en) * 2001-07-11 2003-01-16 Yoshikazu Nakayama And Daiken Chemical Co., Ltd. Method for mass-producing carbon nanocoils
US6558645B2 (en) * 1999-12-31 2003-05-06 Yoshikazu Nakayama Method for manufacturing carbon nanocoils
US6576341B1 (en) * 1998-04-09 2003-06-10 Horcom Limited Composition
US6583085B1 (en) * 2000-04-29 2003-06-24 Yoshikazu Nakayama Method for manufacturing indium-tin-iron catalyst for use in production of carbon nanocoils
US6597090B1 (en) * 1998-09-28 2003-07-22 Xidex Corporation Method for manufacturing carbon nanotubes as functional elements of MEMS devices

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5413866A (en) * 1990-10-23 1995-05-09 Baker; R. Terry K. High performance carbon filament structures
US6231980B1 (en) * 1995-02-14 2001-05-15 The Regents Of The University Of California BX CY NZ nanotubes and nanoparticles
US6232980B1 (en) * 1998-03-18 2001-05-15 Silicon Graphics, Inc. System and method for generating planar maps of three-dimensional surfaces
US6576341B1 (en) * 1998-04-09 2003-06-10 Horcom Limited Composition
US6455021B1 (en) * 1998-07-21 2002-09-24 Showa Denko K.K. Method for producing carbon nanotubes
US6597090B1 (en) * 1998-09-28 2003-07-22 Xidex Corporation Method for manufacturing carbon nanotubes as functional elements of MEMS devices
US6232706B1 (en) * 1998-11-12 2001-05-15 The Board Of Trustees Of The Leland Stanford Junior University Self-oriented bundles of carbon nanotubes and method of making same
US6333016B1 (en) * 1999-06-02 2001-12-25 The Board Of Regents Of The University Of Oklahoma Method of producing carbon nanotubes
US6558645B2 (en) * 1999-12-31 2003-05-06 Yoshikazu Nakayama Method for manufacturing carbon nanocoils
US6583085B1 (en) * 2000-04-29 2003-06-24 Yoshikazu Nakayama Method for manufacturing indium-tin-iron catalyst for use in production of carbon nanocoils
US20020127170A1 (en) * 2000-09-22 2002-09-12 Eun-Hwa Hong Method of synthesizing carbon nanotubes and apparatus used for the same
US20030010279A1 (en) * 2001-07-11 2003-01-16 Yoshikazu Nakayama And Daiken Chemical Co., Ltd. Method for mass-producing carbon nanocoils

Cited By (64)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030138561A1 (en) * 2002-01-14 2003-07-24 Zhen-Yu Juang Thermal cracking chemical vapor deposition method for synthesizing nano-carbon material
US7226643B2 (en) * 2002-01-14 2007-06-05 National Science Council Thermal pyrolysising chemical vapor deposition method for synthesizing nano-carbon material
US20100015033A1 (en) * 2005-05-20 2010-01-21 Clemson University Process for preparing carbon nanostructures with tailored properties and products utilizing same
US7754183B2 (en) 2005-05-20 2010-07-13 Clemson University Research Foundation Process for preparing carbon nanostructures with tailored properties and products utilizing same
US7771512B2 (en) * 2005-06-24 2010-08-10 Washington State University Research Foundation Apparatus with high surface area nanostructures for hydrogen storage, and methods of storing hydrogen
US20090000192A1 (en) * 2005-06-24 2009-01-01 Washington State University Research Foundation Apparatus with high surface area nanostructures for hydrogen storage, and methods of storing hydrogen
US8404212B2 (en) 2005-06-24 2013-03-26 Washington State University Research Foundation Apparatus with high surface area nanostructures for hydrogen storage, and methods of storing hydrogen
US20100276304A1 (en) * 2005-06-24 2010-11-04 Washington State University Research Foundation Apparatus with high surface area nanostructures for hydrogen storage, and methods of storing hydrogen
US20100215915A1 (en) * 2005-06-24 2010-08-26 Washington State University Method for manufacture and coating of nanostructured components
US11413847B2 (en) 2005-07-28 2022-08-16 Nanocomp Technologies, Inc. Systems and methods for formation and harvesting of nanofibrous materials
US10029442B2 (en) 2005-07-28 2018-07-24 Nanocomp Technologies, Inc. Systems and methods for formation and harvesting of nanofibrous materials
US8999285B2 (en) 2005-07-28 2015-04-07 Nanocomp Technologies, Inc. Systems and methods for formation and harvesting of nanofibrous materials
US8236269B2 (en) * 2006-02-14 2012-08-07 Lg Chem, Ltd. Rigid random coils and composition comprising the same
US20080004396A1 (en) * 2006-02-14 2008-01-03 Lg Chem, Ltd. Rigid random coils and composition comprising the same
US20090214851A1 (en) * 2006-05-26 2009-08-27 General Electric Company Nanostructure arrays
US20070275499A1 (en) * 2006-05-26 2007-11-29 Reed Roeder Corderman Nonostructure arrays and methods of making same
US7488671B2 (en) 2006-05-26 2009-02-10 General Electric Company Nanostructure arrays and methods of making same
US9061913B2 (en) 2007-06-15 2015-06-23 Nanocomp Technologies, Inc. Injector apparatus and methods for production of nanostructures
WO2009048672A3 (fr) * 2007-07-25 2009-05-28 Nanocomp Technologies Inc Systèmes et procédés de modulation de la chiralité de nanotubes
US8057777B2 (en) 2007-07-25 2011-11-15 Nanocomp Technologies, Inc. Systems and methods for controlling chirality of nanotubes
US20090032741A1 (en) * 2007-07-25 2009-02-05 Nanocomp Technologies, Inc. Systems and Methods for Controlling Chirality of Nanotubes
US9236669B2 (en) 2007-08-07 2016-01-12 Nanocomp Technologies, Inc. Electrically and thermally non-metallic conductive nanostructure-based adapters
US20110053020A1 (en) * 2007-11-09 2011-03-03 Washington State University Research Foundation Catalysts and related methods
US20100000754A1 (en) * 2008-05-07 2010-01-07 Nanocomp Technologies, Inc. Carbon nanotube-based coaxial electrical cables and wiring harness
US8847074B2 (en) 2008-05-07 2014-09-30 Nanocomp Technologies Carbon nanotube-based coaxial electrical cables and wiring harness
US9198232B2 (en) 2008-05-07 2015-11-24 Nanocomp Technologies, Inc. Nanostructure-based heating devices and methods of use
US9396829B2 (en) 2008-05-07 2016-07-19 Nanocomp Technologies, Inc. Carbon nanotube-based coaxial electrical cables and wiring harness
US8679444B2 (en) 2009-04-17 2014-03-25 Seerstone Llc Method for producing solid carbon by reducing carbon oxides
US9556031B2 (en) 2009-04-17 2017-01-31 Seerstone Llc Method for producing solid carbon by reducing carbon oxides
US10500582B2 (en) 2009-04-17 2019-12-10 Seerstone Llc Compositions of matter including solid carbon formed by reducing carbon oxides
US8354593B2 (en) 2009-07-10 2013-01-15 Nanocomp Technologies, Inc. Hybrid conductors and method of making same
US20110005808A1 (en) * 2009-07-10 2011-01-13 Nanocomp Technologies, Inc. Hybrid Conductors and Method of Making Same
US8722171B2 (en) 2011-01-04 2014-05-13 Nanocomp Technologies, Inc. Nanotube-based insulators
US10145627B2 (en) 2011-01-04 2018-12-04 Nanocomp Technologies, Inc. Nanotube-based insulators
US10704140B2 (en) 2011-10-07 2020-07-07 International Business Machines Corporation Substrate holder for graphene film synthesis, and uses thereof
US10100402B2 (en) 2011-10-07 2018-10-16 International Business Machines Corporation Substrate holder for graphene film synthesis
US9475699B2 (en) 2012-04-16 2016-10-25 Seerstone Llc. Methods for treating an offgas containing carbon oxides
US10106416B2 (en) 2012-04-16 2018-10-23 Seerstone Llc Methods for treating an offgas containing carbon oxides
US9090472B2 (en) 2012-04-16 2015-07-28 Seerstone Llc Methods for producing solid carbon by reducing carbon dioxide
US9731970B2 (en) 2012-04-16 2017-08-15 Seerstone Llc Methods and systems for thermal energy recovery from production of solid carbon materials by reducing carbon oxides
US9221685B2 (en) 2012-04-16 2015-12-29 Seerstone Llc Methods of capturing and sequestering carbon
US9637382B2 (en) 2012-04-16 2017-05-02 Seerstone Llc Methods for producing solid carbon by reducing carbon dioxide
US9796591B2 (en) 2012-04-16 2017-10-24 Seerstone Llc Methods for reducing carbon oxides with non ferrous catalysts and forming solid carbon products
US9896341B2 (en) 2012-04-23 2018-02-20 Seerstone Llc Methods of forming carbon nanotubes having a bimodal size distribution
US9604848B2 (en) 2012-07-12 2017-03-28 Seerstone Llc Solid carbon products comprising carbon nanotubes and methods of forming same
US10815124B2 (en) 2012-07-12 2020-10-27 Seerstone Llc Solid carbon products comprising carbon nanotubes and methods of forming same
US10358346B2 (en) 2012-07-13 2019-07-23 Seerstone Llc Methods and systems for forming ammonia and solid carbon products
US9598286B2 (en) 2012-07-13 2017-03-21 Seerstone Llc Methods and systems for forming ammonia and solid carbon products
US9779845B2 (en) 2012-07-18 2017-10-03 Seerstone Llc Primary voltaic sources including nanofiber Schottky barrier arrays and methods of forming same
US9993791B2 (en) 2012-11-29 2018-06-12 Seerstone Llc Reactors and methods for producing solid carbon materials
US9650251B2 (en) 2012-11-29 2017-05-16 Seerstone Llc Reactors and methods for producing solid carbon materials
US9783416B2 (en) 2013-03-15 2017-10-10 Seerstone Llc Methods of producing hydrogen and solid carbon
US10115844B2 (en) 2013-03-15 2018-10-30 Seerstone Llc Electrodes comprising nanostructured carbon
US10322832B2 (en) 2013-03-15 2019-06-18 Seerstone, Llc Systems for producing solid carbon by reducing carbon oxides
US9783421B2 (en) 2013-03-15 2017-10-10 Seerstone Llc Carbon oxide reduction with intermetallic and carbide catalysts
US9586823B2 (en) 2013-03-15 2017-03-07 Seerstone Llc Systems for producing solid carbon by reducing carbon oxides
US10086349B2 (en) 2013-03-15 2018-10-02 Seerstone Llc Reactors, systems, and methods for forming solid products
US9718691B2 (en) 2013-06-17 2017-08-01 Nanocomp Technologies, Inc. Exfoliating-dispersing agents for nanotubes, bundles and fibers
US11434581B2 (en) 2015-02-03 2022-09-06 Nanocomp Technologies, Inc. Carbon nanotube structures and methods for production thereof
US11752459B2 (en) 2016-07-28 2023-09-12 Seerstone Llc Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same
US11951428B2 (en) 2016-07-28 2024-04-09 Seerstone, Llc Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same
US10581082B2 (en) 2016-11-15 2020-03-03 Nanocomp Technologies, Inc. Systems and methods for making structures defined by CNT pulp networks
US11279836B2 (en) 2017-01-09 2022-03-22 Nanocomp Technologies, Inc. Intumescent nanostructured materials and methods of manufacturing same
CN116332159A (zh) * 2023-03-28 2023-06-27 北京科技大学 一种超声辅助催化裂解碳氢化合物制备碳纳米管的方法和装置

Also Published As

Publication number Publication date
WO2004052973A2 (fr) 2004-06-24
WO2004052973A3 (fr) 2004-09-23
AU2003300816A8 (en) 2004-06-30
AU2003300816A1 (en) 2004-06-30

Similar Documents

Publication Publication Date Title
US20040265212A1 (en) Synthesis of coiled carbon nanotubes by microwave chemical vapor deposition
JP5102633B2 (ja) 長いカーボン単層ナノチューブを成長させるための方法
JP5065898B2 (ja) 狭小な直径分布のカーボン単層ナノチューブの合成
JP6328611B2 (ja) 非鉄触媒で炭素酸化物を還元するための方法および構造
Nikolaev Gas-phase production of single-walled carbon nanotubes from carbon monoxide: a review of the HiPco process
JP2010137222A (ja) 金属ナノ触媒およびその製造方法、ならびにこれを用いて製造されたカーボンナノチューブの成長形態の調節方法
EP1649929B1 (fr) Procede de preparation d'une nanobobine de carbone
JP5059589B2 (ja) 窒化ホウ素ナノ繊維及びその製造方法
CN103695864A (zh) 碳包覆钴金属纳米颗粒的制备方法
CN113044831A (zh) 一种氮掺杂碳纳米管阵列的制备方法
Dhore et al. Synthesis and characterization of high yield multiwalled carbon nanotubes by ternary catalyst
Varadan et al. Synthesis of carbon nanocoils by microwave CVD
JP2015151277A (ja) 気相法微細炭素繊維の製造方法
Donato et al. Influence of carbon source and Fe-catalyst support on the growth of multi-walled carbon nanotubes
JP5364904B2 (ja) カーボンナノファイバー集合体の製造方法
Shukrullah et al. Effect of CVD process temperature on activation energy and structural growth of MWCNTs
Schur et al. Synthesis of carbon nanostructures in gaseous and liquid medium
He et al. Study of aluminum powder as transition metal catalyst carrier for CVD synthesis of carbon nanotubes
CN100369806C (zh) 合成单一形貌氮化硼纳米管的方法
Santhosh et al. Growth of carbon nanotubes using MgO supported Mo-Co catalysts by thermal chemical vapor deposition technique
KR20150039072A (ko) 탄소나노튜브 및 그 제조방법
JP2004324004A (ja) カーボン繊維及びその製造方法
Taleshi et al. Effect of sudden initiation and temperature on growth and diameter of carbon nanotubes synthesized by CVD method
WO2022047600A1 (fr) Méthode de préparation de nanotubes de carbone à parois multiples
CN116443859B (zh) 一种Sigma相催化剂和高选择性合成单壁碳纳米管的方法

Legal Events

Date Code Title Description
AS Assignment

Owner name: THE PENN STATE RESEARCH FOUNDATION, PENNSYLVANIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:VARADAN, VIJAY;XIE, JINING;REEL/FRAME:018427/0306;SIGNING DATES FROM 20060711 TO 20061019

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION