CN1504407A - Process for preparing nano-carbon tubes - Google Patents

Process for preparing nano-carbon tubes Download PDF

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Publication number
CN1504407A
CN1504407A CNA021521093A CN02152109A CN1504407A CN 1504407 A CN1504407 A CN 1504407A CN A021521093 A CNA021521093 A CN A021521093A CN 02152109 A CN02152109 A CN 02152109A CN 1504407 A CN1504407 A CN 1504407A
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China
Prior art keywords
carbon nanotube
substrate
make
nanotube according
carbon nano
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Granted
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CNA021521093A
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Chinese (zh)
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CN1290763C (en
Inventor
范守善
刘亮
姜开利
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Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Priority to CNB021521093A priority Critical patent/CN1290763C/en
Priority to US10/410,069 priority patent/US20040105807A1/en
Priority to JP2003168328A priority patent/JP2004182581A/en
Publication of CN1504407A publication Critical patent/CN1504407A/en
Priority to JP2006234173A priority patent/JP2006347878A/en
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Publication of CN1290763C publication Critical patent/CN1290763C/en
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    • 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
    • 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
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
    • 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
    • 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
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • 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
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • D01F9/1271—Alkanes or cycloalkanes
    • 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
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • D01F9/1271—Alkanes or cycloalkanes
    • D01F9/1272—Methane
    • 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
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • D01F9/1273—Alkenes, alkynes
    • D01F9/1275—Acetylene
    • 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
    • C01B2202/08—Aligned nanotubes
    • 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
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/34—Length

Abstract

The invention provides a process for preparing carbon nano tube, which comprises the steps of, (1) providing a substrate, (2) depositing catalyst substrate on the substrate, (3) making the catalyst contact the carbon source gas at a predetermined temperature for a given period of time, thus making the carbon nano tube array of a specific length grow out substantially perpendicular to the substrate, (4) taking down the obtained carbon nano tube from the substrate. Compared with the prior art, the present invention realizes a uniform carbon nano tube preparation length, a controlled length and easiness for dispersion.

Description

A kind of method of producing carbon nanotube
[technical field]
The invention relates to a kind of method of producing carbon nanotube.
[background technology]
Carbon nanotube has unusual physical and chemical performance, as the metal of uniqueness or semi-conductor electroconductibility, high physical strength, hydrogen storage ability, adsorptive power and stronger microwave absorption capacity etc., the beginning of the nineties is once the very big attention of finding to be subjected at once physics, chemistry and material supply section educational circles and new high-tech industry department.Carbon nanotube will be realized industrial application, at first must solve low-cost a large amount of preparation problems of carbon nanotube.Carbon nanotube is since 1991 are found, and its preparation technology has obtained broad research.At present, three kinds of main preparation methods are arranged, i.e. arc discharge method, laser ablation method and chemical Vapor deposition process.In the product that arc discharge method and laser ablation method make, carbon nanotube all with the coexistence of the carbon product of other form, the separation and purification difficulty, yield is lower, and is difficult to mass-producing.The third chemical Vapor deposition process, by the carbon nanotube of Sweet natural gas preparation have that technology is easy, cost is low, the nanotube scale is easy to control, length big, yield is than advantages such as height, and important researching value is arranged.Can be applicable to aspects such as field emission display, electron tube, nanoelectronics and high strength composite.
But the method for any a large amount of preparations at present all can not be controlled the length of carbon nanotube in the product, and the carbon nanotube of producing often is entangled with agglomeratingly, is difficult to disperse, and is unfavorable for the practical application in fields such as carbon nanotube emission on the scene, composite reinforcing material.Therefore, provide a kind of production length unanimity, length controlled, it is real in necessary not have the method for being entangled with easy dispersed carbon nano tube.
[summary of the invention]
For solve in the prior art can not controlling carbon nanotube length, and the carbon nanotube of producing is entangled with agglomeratingly, is difficult to the dispersive problem, the invention provides a kind of production length unanimity, length controlled does not have the method for being entangled with easy dispersed carbon nano tube.
For solving this technical problem, the invention provides a kind of method of producing carbon nanotube, it comprises step:
(1) provides a substrate;
(2) deposited catalyst in substrate;
(3) under preset temperature, make catalyzer contact certain hour with carbon source gas and make the carbon nano pipe array of length-specific be basically perpendicular to substrate to grow;
(4) carbon nanotube with gained takes off from substrate.
Further improvement of the present invention is to place dispersion soln to carry out ultra-sonic dispersion the gained carbon nanotube after above-mentioned steps (4).
Compared with prior art the present invention utilizes chemical gaseous phase depositing process, has realized preparation length unanimity in the mode of carbon nano pipe array, and length controlled does not have and is entangled with easy dispersed carbon nano tube.
[description of drawings]
Fig. 1 is the synoptic diagram of deposited catalyst of the present invention in substrate;
Fig. 2 is the synoptic diagram of catalyzer of the present invention after anneal;
Fig. 3 is that the substrate that the present invention will have a catalyzer places Reaktionsofen to feed the synoptic diagram of reactant gases carbon nano-tube;
Fig. 4 is the present invention scrapes carbon nanotube from substrate a synoptic diagram;
Fig. 5 is that carbon nano-pipe array of the present invention is listed in the transmission electron microscope photo after the ultrasonication in the dispersion soln;
Fig. 6 is that carbon nano-pipe array of the present invention is listed in the transmission electron microscope photo after the ultrasonication in the dispersion soln, and wherein carbon nanotube is dispersed into and is single carbon nanotube;
Fig. 7,8,9 and 10 is respectively the carbon nano pipe array of different heights of the present invention.
[embodiment]
The present invention utilizes chemical Vapor deposition process, realizes production length unanimity in the mode of carbon nano pipe array, and length controlled does not have and is entangled with easy dispersed carbon nano tube.Preparation process is as follows:
(1) sees also Fig. 1, provide a silicon chip or quartz plate as repeatedly used substrate 3;
(2) with the method for electron beam evaporation plating, sputter or liquid coating catalyzer 1 is deposited on the single or double of substrate 3, makes it form the thick metal catalytic agent film 11 of 4～10nm, catalyzer 1 can be selected iron, nickel, cobalt etc.;
(3) see also Fig. 2,, under the air atmosphere, catalyst film 11 is carried out 8～12 hours anneal, make it be punctured into discrete nano-scale particle 12 300 ℃～500 ℃ of temperature;
(4) see also Fig. 3, Reaktionsofen 4 is put in the multi-disc substrate 3 that will have granules of catalyst 12 simultaneously into;
(5) feed shielding gas (not indicating), simultaneously Reaktionsofen 4 is heated to 600～1000 ℃;
(6) feed shielding gas and carbon source gas (not indicating) then, shielding gas can be argon, nitrogen or helium etc., and carbon source gas can be acetylene, methane, ethene etc.;
(7) after about 15 seconds～40 minutes, highly certain carbon nano-pipe array is listed in substrate surface and grows;
(8) Reaktionsofen 4 is cooled to room temperature;
(9) see also Fig. 4, take out substrate 3, carbon nanotube 5 can scrape with blade 6, and equally also available filament or high pressure gas are blown down, and 3 of substrates directly regrow or clean, plated film is standby once more.
Optionally the carbon nanotube 5 of gained can be placed on ethanol, 1-2 ethylene dichloride etc. and disperse ultra-sonic dispersion in the solution.
Because the carbon nanotube 5 in the array is basic for being arranged in parallel, nothing is entangled with, and can obtain disperseing fabulous single-root carbon nano-tube easily.Shown in Fig. 5,6, carbon nanotube 5 of the present invention does not have substantially is entangled with, but ultra-sonic dispersion becomes single carbon nanotube or minor diameter tube bank.
In addition, by the control growing condition: as reaction times and temperature of reaction, the carbon nano pipe array of the needed certain height of can growing, the carbon nanotube 5 that obtains thus will have needed precise length, shown in Fig. 7,8,9 and 10.
Embodiment one:
Growth length is the carbon nano pipe array of 10 μ m: deposit the thick iron catalyst film of 5nm at the bottom of the porous silicon-base; the substrate that will deposit iron then 400 ℃ of annealing 10 hours in air; substrate is placed in the central reaction chamber of sending into the silica tube Reaktionsofen in the quartz reaction boat then; under the protection of argon gas; after Reaktionsofen is heated to 690 ℃, feed ethylene gas, reacted 15 seconds; with the Reaktionsofen cool to room temperature, getting length is the carbon nano pipe array of 10 μ m then.
Embodiment two:
Growth length is the carbon nano pipe array of 100 μ m: deposit the thick iron catalyst film of 5nm at the bottom of the porous silicon-base; the substrate that will deposit iron then 400 ℃ of annealing 10 hours in air; substrate is placed in the central reaction chamber of sending into the silica tube Reaktionsofen in the quartz reaction boat then; under the protection of argon gas; after Reaktionsofen is heated to 690 ℃, feed ethylene gas, reacted 5 minutes; with the Reaktionsofen cool to room temperature, getting length is the carbon nano pipe array of 100 μ m then.
Embodiment three:
Growth length is the carbon nano pipe array of 500 μ m: deposit the thick iron catalyst film of 5nm at the bottom of the porous silicon-base; the substrate that will deposit iron then 400 ℃ of annealing 10 hours in air; substrate is placed in the central reaction chamber of sending into the silica tube Reaktionsofen in the quartz reaction boat then; under the protection of argon gas; after Reaktionsofen is heated to 710 ℃, feed ethylene gas, reacted 10 minutes; with the Reaktionsofen cool to room temperature, getting length is the carbon nano pipe array of 500 μ m then.
Through the experiment conclusive evidence, the density of carbon nano pipe array can reach 0.1g/cm 3With the array computation of the 100 μ m height of growing, can place the long carbon nanotubes of 100 μ m that the Reaktionsofen of (single face plating catalyzer) at the bottom of 30 4-inch (25.4mm) silicon wafer-based can once be produced about 2.4 grams simultaneously, about about 5 minutes consuming time of process of growth.

Claims (10)

1. method of producing carbon nanotube is characterized in that comprising step:
(1) provides a substrate;
(2) deposited catalyst in substrate;
(3) under preset temperature, make catalyzer contact certain hour with carbon source gas and make length-specific
Carbon nano pipe array is basically perpendicular to substrate and grows;
(4) carbon nanotube with gained takes off from substrate.
2. the method for production carbon nanotube according to claim 1 is characterized in that placing dispersion soln to carry out ultra-sonic dispersion the gained carbon nanotube after step (4).
3. the method for production carbon nanotube according to claim 1 is characterized in that catalyzer used in step (2) is iron, cobalt or nickel.
4. the method for production carbon nanotube according to claim 3, it is characterized in that step (2) comprises the film that makes catalyzer form 4～10nm in substrate, then under 300 ℃～500 ℃ of temperature, catalyst film is carried out 8～12 hours anneal, make film oxidation be punctured into discrete nano-scale particle.
5. the method for production carbon nanotube according to claim 1 is characterized in that preset temperature is 600～1000 ℃ in step (3).
6. the method for production carbon nanotube according to claim 5 is characterized in that carbon source gas can be selected acetylene, methane or ethene in step (3).
7. the method for production carbon nanotube according to claim 5 is characterized in that step (3) comprises the feeding shielding gas.
8. the method for production carbon nanotube according to claim 1 is characterized in that it highly is that the carbon nano pipe array of 10 μ m is basically perpendicular to substrate and grows that step (3) is included in that 690 ℃ of temperature make ethene contact with iron catalyst to make in 15 seconds.
9. the method for production carbon nanotube according to claim 1 is characterized in that it highly is that the carbon nano pipe array of 100 μ m is basically perpendicular to substrate and grows that step (3) is included in that 690 ℃ of temperature make ethene contact with iron catalyst to make in 5 minutes.
10. the method for production carbon nanotube according to claim 1 is characterized in that it highly is that the carbon nano pipe array of 500 μ m is basically perpendicular to substrate and grows that step (3) is included in that 710 ℃ of temperature make ethene contact with iron catalyst to make in 10 minutes.
CNB021521093A 2002-11-29 2002-11-29 Process for preparing nano-carbon tubes Expired - Lifetime CN1290763C (en)

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CNB021521093A CN1290763C (en) 2002-11-29 2002-11-29 Process for preparing nano-carbon tubes
US10/410,069 US20040105807A1 (en) 2002-11-29 2003-04-08 Method for manufacturing carbon nanotubes
JP2003168328A JP2004182581A (en) 2002-11-29 2003-06-12 Method for producing carbon nanotube
JP2006234173A JP2006347878A (en) 2002-11-29 2006-08-30 Method for manufacturing carbon nanotube

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CN1290763C CN1290763C (en) 2006-12-20

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* Cited by examiner, † Cited by third party
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CN100368080C (en) * 2005-08-29 2008-02-13 天津大学 Process for preparing carbon nano tube and carbon onion by Ni/Al catalyst chemical gas phase deposition
CN100391831C (en) * 2004-09-20 2008-06-04 三星Sdi株式会社 Method of preparing carbon nanocages
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US8367506B2 (en) 2007-06-04 2013-02-05 Micron Technology, Inc. High-k dielectrics with gold nano-particles
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US20090081441A1 (en) * 2007-09-20 2009-03-26 Lockheed Martin Corporation Fiber Tow Comprising Carbon-Nanotube-Infused Fibers
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WO2010141113A2 (en) * 2009-02-13 2010-12-09 Babcock & Wilcox Technical Services Y-12, Llc Nano-material and method of fabrication
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MX2011010864A (en) 2009-04-17 2011-11-01 Seerstone Llc Method for producing solid carbon by reducing carbon oxides.
US9111658B2 (en) 2009-04-24 2015-08-18 Applied Nanostructured Solutions, Llc CNS-shielded wires
JP2012525012A (en) 2009-04-24 2012-10-18 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 CNT leaching EMI shielding composite and coating
WO2010129234A2 (en) 2009-04-27 2010-11-11 Lockheed Martin Corporation Cnt-based resistive heating for deicing composite structures
US20110171469A1 (en) * 2009-11-02 2011-07-14 Applied Nanostructured Solutions, Llc Cnt-infused aramid fiber materials and process therefor
AU2010321534B2 (en) 2009-11-23 2015-03-26 Applied Nanostructured Solutions, Llc Ceramic composite materials containing carbon nanotube-infused fiber materials and methods for production thereof
AU2010321536A1 (en) 2009-11-23 2012-04-19 Applied Nanostructured Solutions, Llc CNT-tailored composite space-based structures
EP2513250A4 (en) 2009-12-14 2015-05-27 Applied Nanostructured Sols Flame-resistant composite materials and articles containing carbon nanotube-infused fiber materials
US9167736B2 (en) 2010-01-15 2015-10-20 Applied Nanostructured Solutions, Llc CNT-infused fiber as a self shielding wire for enhanced power transmission line
WO2011146151A2 (en) 2010-02-02 2011-11-24 Applied Nanostructured Solutions, Llc Fiber containing parallel-aligned carbon nanotubes
EP2543052B1 (en) 2010-03-02 2019-11-27 Applied NanoStructured Solutions, LLC Electrical devices containing carbon nanotube-infused fibers and methods for production thereof
WO2011109480A2 (en) 2010-03-02 2011-09-09 Applied Nanostructed Solution, Llc Spiral wound electrical devices containing carbon nanotube-infused electrode materials and methods and apparatuses for production thereof
CA2712051A1 (en) * 2010-08-12 2012-02-12 The Governors Of The University Of Alberta Method of fabricating a carbon nanotube array
US8780526B2 (en) 2010-06-15 2014-07-15 Applied Nanostructured Solutions, Llc Electrical devices containing carbon nanotube-infused fibers and methods for production thereof
US9017854B2 (en) 2010-08-30 2015-04-28 Applied Nanostructured Solutions, Llc Structural energy storage assemblies and methods for production thereof
JP2014508370A (en) 2010-09-23 2014-04-03 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 CNT-infused fibers as self-shielding wires for reinforced transmission lines
US8609189B2 (en) 2011-09-28 2013-12-17 King Abdulaziz University Method of forming carbon nanotubes from carbon-rich fly ash
US9085464B2 (en) 2012-03-07 2015-07-21 Applied Nanostructured Solutions, Llc Resistance measurement system and method of using the same
JP2015514669A (en) 2012-04-16 2015-05-21 シーアストーン リミテッド ライアビリティ カンパニー Method for producing solid carbon by reducing carbon dioxide
CN104284861A (en) 2012-04-16 2015-01-14 赛尔斯通股份有限公司 Methods for treating offgas containing carbon oxides
NO2749379T3 (en) 2012-04-16 2018-07-28
CN104302576B (en) 2012-04-16 2017-03-08 赛尔斯通股份有限公司 For catching and sealing up for safekeeping carbon and the method and system for reducing the quality of oxycarbide in waste gas stream
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
US9656246B2 (en) * 2012-07-11 2017-05-23 Carbice Corporation Vertically aligned arrays of carbon nanotubes formed on multilayer substrates
US10815124B2 (en) 2012-07-12 2020-10-27 Seerstone Llc Solid carbon products comprising carbon nanotubes and methods of forming same
CN107651667A (en) 2012-07-12 2018-02-02 赛尔斯通股份有限公司 Solid carbon product comprising CNT with and forming method thereof
MX2015000580A (en) 2012-07-13 2015-08-20 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
JP6389824B2 (en) 2012-11-29 2018-09-12 シーアストーン リミテッド ライアビリティ カンパニー Reactor and method for producing solid carbon material
ES2663666T3 (en) 2013-02-28 2018-04-16 N12 Technologies, Inc. Nanostructure film cartridge based dispensing
US9783416B2 (en) 2013-03-15 2017-10-10 Seerstone Llc Methods of producing hydrogen and solid carbon
WO2014151119A2 (en) 2013-03-15 2014-09-25 Seerstone Llc Electrodes comprising nanostructured carbon
EP3113880A4 (en) 2013-03-15 2018-05-16 Seerstone LLC Carbon oxide reduction with intermetallic and carbide catalysts
WO2014151138A1 (en) 2013-03-15 2014-09-25 Seerstone Llc Reactors, systems, and methods for forming solid products
WO2014151898A1 (en) 2013-03-15 2014-09-25 Seerstone Llc Systems for producing solid carbon by reducing carbon oxides
JP2015145317A (en) * 2014-01-31 2015-08-13 ヤマハ株式会社 Device for producing carbon nanotube
JP2015160747A (en) * 2014-02-25 2015-09-07 ヤマハ株式会社 Carbon nano-tube production apparatus
JP2015174775A (en) * 2014-03-12 2015-10-05 ヤマハ株式会社 Production apparatus of carbon nanotube
WO2015191897A1 (en) 2014-06-11 2015-12-17 Georgia Tech Research Corporation Polymer-based nanostructured materials with tunable properties and methods of making thereof
US11447391B2 (en) * 2015-06-23 2022-09-20 Polyvalor, Limited Partnership Method of growing a graphene coating or carbon nanotubes on a catalytic substrate
EP3463826B1 (en) 2016-05-31 2023-07-05 Massachusetts Institute of Technology Composite articles comprising non-linear elongated nanostructures and associated methods
US10791651B2 (en) 2016-05-31 2020-09-29 Carbice Corporation Carbon nanotube-based thermal interface materials and methods of making and using thereof
WO2018022999A1 (en) 2016-07-28 2018-02-01 Seerstone Llc. Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same
TWI755492B (en) 2017-03-06 2022-02-21 美商卡爾拜斯有限公司 Carbon nanotube-based thermal interface materials and methods of making and using thereof
CN108735969B (en) 2017-04-24 2020-09-29 清华大学 Lithium ion battery cathode and flexible lithium ion battery
CN108735979B (en) * 2017-04-24 2020-12-04 清华大学 Preparation method of lithium ion battery cathode
US20190085138A1 (en) 2017-09-15 2019-03-21 Massachusetts Institute Of Technology Low-defect fabrication of composite materials
US11031657B2 (en) 2017-11-28 2021-06-08 Massachusetts Institute Of Technology Separators comprising elongated nanostructures and associated devices and methods, including devices and methods for energy storage and/or use
US10707596B2 (en) 2018-09-21 2020-07-07 Carbice Corporation Coated electrical connectors and methods of making and using thereof
US20210063099A1 (en) 2019-08-28 2021-03-04 Carbice Corporation Flexible and conformable polymer-based heat sinks and methods of making and using thereof
USD906269S1 (en) 2019-08-28 2020-12-29 Carbice Corporation Flexible heat sink
USD904322S1 (en) 2019-08-28 2020-12-08 Carbice Corporation Flexible heat sink
USD903610S1 (en) 2019-08-28 2020-12-01 Carbice Corporation Flexible heat sink
CN114646689A (en) * 2020-12-17 2022-06-21 清华大学 Secondary electron probe and secondary electron detector

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5872422A (en) * 1995-12-20 1999-02-16 Advanced Technology Materials, Inc. Carbon fiber-based field emission devices
DE69727671T2 (en) * 1996-05-15 2004-09-30 Hyperion Catalysis International, Inc., Cambridge RIGID, POROUS CARBON STRUCTURES, METHOD FOR THE PRODUCTION AND USE THEREOF AND PRODUCTS CONTAINING THESE STRUCTURES
US6129901A (en) * 1997-11-18 2000-10-10 Martin Moskovits Controlled synthesis and metal-filling of aligned carbon nanotubes
US6863942B2 (en) * 1998-06-19 2005-03-08 The Research Foundation Of State University Of New York Free-standing and aligned carbon nanotubes and synthesis thereof
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
US6599961B1 (en) * 2000-02-01 2003-07-29 University Of Kentucky Research Foundation Polymethylmethacrylate augmented with carbon nanotubes
JP4483152B2 (en) * 2001-11-27 2010-06-16 富士ゼロックス株式会社 Hollow graphene sheet structure, electrode structure, manufacturing method thereof, and device

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100391831C (en) * 2004-09-20 2008-06-04 三星Sdi株式会社 Method of preparing carbon nanocages
US7518045B2 (en) 2004-09-20 2009-04-14 Samsung Sdi Co., Ltd. Method of preparing carbon nanocages
CN101039873B (en) * 2004-11-10 2010-04-21 尼康股份有限公司 Carbon nanotube aggregate and process for producing the same
CN100368080C (en) * 2005-08-29 2008-02-13 天津大学 Process for preparing carbon nano tube and carbon onion by Ni/Al catalyst chemical gas phase deposition
CN1948142B (en) * 2005-10-12 2010-09-08 王洋 Preparation method of carbon nano-tube array and its application in preparing antenna array
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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
US9573812B2 (en) 2007-01-03 2017-02-21 Applied Nanostructured Solutions, Llc CNT-infused metal fiber materials and process therefor
US8951631B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused metal fiber materials and process therefor
US9574300B2 (en) 2007-01-03 2017-02-21 Applied Nanostructured Solutions, Llc CNT-infused carbon fiber materials and process therefor
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US9023477B2 (en) 2007-08-24 2015-05-05 Tsinghua University Thermally conductive pad with an array of carbon nanotubes and method for making the same
CN102741161B (en) * 2008-04-16 2014-06-25 日本瑞翁株式会社 Equipment and method for producing orientated carbon nano-tube aggregates
CN101591015B (en) * 2008-05-28 2013-02-13 清华大学 Preparation method of banded carbon nano tube film
US8236389B2 (en) 2008-05-28 2012-08-07 Tsinghua University Method for making carbon nanotube films
TWI412491B (en) * 2008-06-13 2013-10-21 Hon Hai Prec Ind Co Ltd Method for making carbon nanotube strip-shaped film
US10138128B2 (en) 2009-03-03 2018-11-27 Applied Nanostructured Solutions, Llc System and method for surface treatment and barrier coating of fibers for in situ CNT growth
US8969225B2 (en) 2009-08-03 2015-03-03 Applied Nano Structured Soultions, LLC Incorporation of nanoparticles in composite fibers
CN102648088A (en) * 2009-11-02 2012-08-22 应用纳米结构方案公司 CNT-infused metal fiber materials and process therefor
CN102639771A (en) * 2009-11-02 2012-08-15 应用纳米结构方案公司 CNT-infused ceramic fiber materials and process therefor
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US8784937B2 (en) 2010-09-14 2014-07-22 Applied Nanostructured Solutions, Llc Glass substrates having carbon nanotubes grown thereon and methods for production thereof
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
CN102249216A (en) * 2011-06-10 2011-11-23 电子科技大学 Method for affecting growth morphology of carbon nanotubes by controlling hydrolysis degree
CN102530828A (en) * 2012-01-09 2012-07-04 重庆大学 Surface-enhanced Raman scattering active substrate based on carbon nanometer pipe arrays and metal nanometer particles
CN104071767A (en) * 2013-03-25 2014-10-01 苏州捷迪纳米科技有限公司 Treating method for carbon nanotube growth substrate
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