CN1290763C - Process for preparing nano-carbon tubes - Google Patents

Process for preparing nano-carbon tubes Download PDF

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Publication number
CN1290763C
CN1290763C CNB021521093A CN02152109A CN1290763C CN 1290763 C CN1290763 C CN 1290763C CN B021521093 A CNB021521093 A CN B021521093A CN 02152109 A CN02152109 A CN 02152109A CN 1290763 C CN1290763 C CN 1290763C
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carbon nanotube
substrate
make
carbon
nanotube according
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CNB021521093A
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CN1504407A (en
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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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    • 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
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Thermal Sciences (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
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Abstract

The present invention provides a method for producing a carbon nanometer tube, which comprises the steps: (1) a substrate is provided; (2) a catalyst is deposited on the substrate; (3) under the preset temperature, the catalyst is in contact with carbon source gas for a certain time, and thus, a carbon nanometer tube array with a specific length grows up basically vertical to the substrate; (4) the obtained carbon nanometer tube is taken from the substrate. Compared with the prior art, the method for producing a carbon nanometer tube uses a chemical vapor phase deposition method and a mode of the carbon nanometer tube array to prepare a carbon nanometer tube with consistent length, controllable length, no tanglement and easy 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) in substrate, deposit the thick catalyzer of 4～10nm, then under 300 ℃～500 ℃ of temperature, and catalyzer carried out 8～12 hours anneal, make it be punctured into discrete nano-scale particle;
(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 (9)

1. method of producing carbon nanotube is characterized in that comprising step:
(1) provides a substrate;
(2) in substrate, deposit the thick catalyzer of 4～10nm, then under 300 ℃～500 ℃ of temperature, and catalyzer carried out 8～12 hours anneal, make it be punctured into discrete nano-scale particle;
(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.
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 1 is characterized in that preset temperature is 600～1000 ℃ in step (3).
5. the method for production carbon nanotube according to claim 4 is characterized in that carbon source gas is acetylene, methane or ethene in step (3).
6. the method for production carbon nanotube according to claim 4 is characterized in that step (3) comprises the feeding shielding gas.
7. 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.
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 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.
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 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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