CN1328161C - Nano carbon tube and preparation method thereof - Google Patents
Nano carbon tube and preparation method thereof Download PDFInfo
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- CN1328161C CN1328161C CNB2004100273787A CN200410027378A CN1328161C CN 1328161 C CN1328161 C CN 1328161C CN B2004100273787 A CNB2004100273787 A CN B2004100273787A CN 200410027378 A CN200410027378 A CN 200410027378A CN 1328161 C CN1328161 C CN 1328161C
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Abstract
The present invention relates to a carbon nano tube and a preparation method thereof. The carbon nano tube is composed of more than two single isotopic elements which are mixed, wherein the isotopic element mixing ratio of the mixed composition displays periodic or non-periodic variation in a tube length direction. The preparation method of the present invention makes different isotopic elements of carbon participate in reaction alternately according to predetermined concentration and a predetermined sequence. In a chemical vapor deposition method, carbon source gas containing different isotopic elements is alternately introduced during the reaction to make different isotopic elements participate in the reaction. In an arc discharge method, power sources between the anodes of different isotopic elements are switched during the reaction to make different isotopic elements participate in the reaction. In a laser ablation method, lasers are irradiated alternatively on different isotopic targets during the reaction to make different isotopic elements participate in the reaction.
Description
[technical field]
The present invention relates to a kind of nano material and its preparation method, particularly a kind of carbon nanotube and its preparation method.
[background technology]
Carbon nanotube is a kind of new one-dimensional nano material of just finding the early 1990s.The special construction of carbon nanotube has determined it to have special nature, as high-tensile and high thermal stability; Along with the variation of carbon nanotube spiral way, carbon nanotube can present metallicity or semi-metal etc.Machinery and electrical properties just because of the carbon nanotube uniqueness, it has broad application prospects at interdisciplinary fields such as Materials science, chemistry, physics, can be used as feds, white light source, lithium secondary battery, hydrogen storage battery, cathode tube or transistorized electron emission source etc.
The preparation method of existing carbon nanotube mainly is at Nature by S.Iijima in 1991,354,56, disclosed arc discharge method on the Helical microtubules of graphitic carbon, people such as T.W.Ebbesen were at Nature in 1992,358,220, disclosed laser ablation method and people such as W.Z.Li in 1996 are at Science on the Large-scale Synthesis of Carbon Nanotubes, 274,1701, disclosed chemical Vapor deposition process etc. on the Large-ScaleSynthesis of Aligned Carbon Nanotubes.
The isotropic substance marker method is the strong instrument of research nano material growth mechanism and nano-scale isotropic substance knot, it is to utilize in the building-up process of nano material, to contain a certain element-specific (generally is light element, as carbon, boron, nitrogen or oxygen) isotopic reactant make it participate in reaction according to predetermined concentration (with the form of pure substance or mixture) and order, thereby prepare the nano material of the isotropic substance sign of growth in situ.
Yet, all do not relate in above-mentioned three kinds of methods that prepare carbon nanotube and be mixed with the synthetic of isotopic carbon nanotube.
[summary of the invention]
In sum, be mixed with isotopic carbon nanotube for overcoming not exist in the prior art, technical problem to be solved by this invention provides a kind of isotopic carbon nanotube that is mixed with.
Do not have the preparation method who is mixed with isotopic carbon nanotube in the prior art for overcoming, technical problem to be solved by this invention provides a kind of preparation method who is mixed with the isotropic substance carbon nanotube.
The technical scheme that the present invention solves the problems of the technologies described above is: the isotopic carbon nanotube that is mixed with that provides is made up of two or more single isotropic substance mixing, and wherein, this isotropic substance blending ratio of mixing composition changes along pipe range direction periodicity or aperiodicity.
For preparing the above-mentioned isotopic carbon nanotube that is mixed with, first kind of preparation method provided by the invention comprises the steps: to provide and contains the monoisotopic first carbon source gas, the second carbon source gas and the 3rd carbon source gas; The substrate that deposits catalyzer on it is provided; Utilize chemical Vapor deposition process, the isotropic substance of the carbon that the first carbon source gas provides is reacted and the first carbon nanotube fragment that reaction is generated is deposited in this substrate; After the reaction scheduled time, carbon source is switched on the second carbon source gas, utilize chemical Vapor deposition process equally, the isotropic substance of the carbon that the second carbon source gas provides is reacted, the second carbon nanotube fragment of generation grows on the first carbon nanotube fragment; After the reaction scheduled time, carbon source is switched on the 3rd carbon source gas, utilize chemical Vapor deposition process equally, the isotropic substance of the carbon that the 3rd carbon source gas provides is reacted, the 3rd carbon nanotube fragment that generates grows on the second carbon nanotube fragment, thereby obtains being mixed with multiple isotopic carbon nanotube.The chemical Vapor deposition process working temperature is 500～1100 ℃.
For preparing the above-mentioned isotopic carbon nanotube that is mixed with, second kind of preparation method provided by the invention comprises the steps: to provide and contains monoisotopic first carbon source, second carbon source and the 3rd carbon source, respectively as anode; Provide one with the negative electrode of first carbon source, second carbon source and the corresponding setting of the 3rd carbon source; Make first carbon source and this negative electrode generation arc-over, the isotropic substance of the carbon that first carbon source provides is reacted and make reaction and generate the first carbon nanotube fragment; After the reaction scheduled time, carbon source is switched to second carbon source, make second carbon source and this negative electrode generation arc-over, the isotropic substance of the carbon that second carbon source provides is reacted, the second carbon nanotube fragment of generation grows on the first carbon nanotube fragment; After the reaction scheduled time, carbon source is switched to the 3rd carbon source, make the 3rd carbon source and this negative electrode generation arc-over, the isotropic substance of the carbon that the 3rd carbon source provides is reacted, the 3rd carbon nanotube fragment that generates grows on the second carbon nanotube fragment, thereby obtain being mixed with isotopic carbon nanotube, be deposited on this negative electrode.
For preparing the above-mentioned isotopic carbon nanotube that is mixed with, the third preparation method provided by the invention comprises the steps: to provide and contains monoisotopic first carbon source, second carbon source and the 3rd carbon source; The carbon nanotube collection device is provided; First carbon source, second carbon source and the 3rd carbon source and this carbon nanotube collection device are put into reaction chamber, and make the carbon nanotube collection device place a side of first carbon source, second carbon source and the 3rd carbon source; With pulsed laser irradiation first carbon source that places first carbon source, second carbon source and the 3rd carbon source opposite side, the first carbon nanotube fragment that makes the isotropic substance of the carbon that first carbon source provides react and reaction is generated; After the reaction scheduled time, with pulsed laser irradiation second carbon source, the isotropic substance of the carbon that second carbon source provides is reacted, the second carbon nanotube fragment of generation grows on the first carbon nanotube fragment; After the reaction scheduled time, with pulsed laser irradiation the 3rd carbon source, the isotropic substance of the carbon that the 3rd carbon source provides is reacted, the 3rd carbon nanotube fragment that generates grows on the second carbon nanotube fragment, thereby obtain being mixed with multiple isotopic carbon nanotube, be deposited on this carbon nanotube collection device.
Compared with prior art, method provided by the invention can prepare the carbon nanotube by different carbon isotope alternating growths, thereby the pattern of methods such as available Raman spectrum or second ion mass spectroscopy record carbon isotope growth in situ, and then the growth mechanism of research carbon nanotube, the synthetic monodimension nanometer material that contains the isotropic substance heterojunction of also available method provided by the invention simultaneously.
[description of drawings]
Fig. 1 is the synoptic diagram that the present invention is mixed with isotopic carbon nanotube.
Fig. 2 utilizes first method preparation of the present invention to be mixed with isotropic substance carbon nanotube equipment therefor synoptic diagram.
Fig. 3 utilizes second method preparation of the present invention to be mixed with isotropic substance carbon nanotube equipment therefor synoptic diagram.
Fig. 4 utilizes the third method preparation of the present invention to be mixed with isotropic substance carbon nanotube equipment therefor synoptic diagram.
[embodiment]
The present invention is described in further detail below in conjunction with accompanying drawing.
See also Fig. 1, of the present invention be mixed with isotopic carbon nanotube 40 be by
12The carbon nanotube fragment 402 that C forms, by
13The carbon nanotube fragment 403 that C forms and by
14The carbon nanotube fragment 404 that C forms is mixed and is formed, and carbon nanotube fragment 402,403 and 404 blending ratios change along pipe range direction periodicity or aperiodicity.To be mixed with the length of isotopic carbon nanotube 40 be 10～1000 μ m to Zhi Bei this in a preferred embodiment of the invention, and the diameter of pipe is 0.5～50nm.
First kind provided by the invention to prepare the method that is mixed with the isotropic substance carbon nanotube be chemical Vapor deposition process, sees also Fig. 2, and its concrete steps are as follows:
(1) provide respectively by
12C,
13C and
14The ethylene gas that C forms;
(2) provide substrate 132, it is the iron film 134 that 5nm uses as catalyzer that these substrate 132 upper surfaces deposit a bed thickness, and reaction chamber 110 is put in this substrate 132 that deposits catalyzer iron film 134;
(3) by exhaust channel 116 reaction chamber 110 is vacuumized after, feeding pressure by gas input channel 118 again is 1 atmospheric argon gas, reaches 700 ℃ by Reaktionsofen reacting by heating chambers 110 106 to its temperature simultaneously;
(4) open valve 112, feeding flows by gas input channel 102 is 120sccm, flow velocity be 1.2cm/s by
12The ethylene gas that C forms, reaction generate by
12The carbon nanotube fragment that C forms (figure does not show) is deposited on this catalyzer iron film 134;
(5) after the reaction scheduled time, valve-off 112 is opened valve 113, and feeding flows by gas input channel 103 is 120sccm, flow velocity be 1.2cm/s by
13The ethylene gas that C forms, by
13The carbon nanotube fragment that C forms (figure does not show) continued growth in step (4) generate by
12On the carbon nanotube fragment that C forms;
(6) after the reaction scheduled time, valve-off 113 is opened valve 114, and feeding flows by gas input channel 104 is 120sccm, flow velocity be 1.2cm/s by
14The ethylene gas that C forms, by
14The carbon nanotube fragment that C forms (figure does not show) continued growth in step (5) generate by
13On the carbon nanotube fragment that C forms;
(7) after the continuation reaction scheduled time, reaction chamber 110 is cooled to room temperature, on catalyzer iron film 134, obtains being mixed with multiple isotopic carbon nanotube.
Be understandable that, can obtain the isotopic carbon nanotube of being mixed with of periodic arrangement in step (6) back repeating step (4), (5) and (6) in present method, perhaps repeating step (4), (5) and (6) can obtain the isotopic carbon nanotube of being mixed with of no periodic array at random after step (6); Also can use cobalt, nickel and alloy thereof, or other appropriate catalyst replaces iron to use as catalyzer; Also can use other hydrocarbon polymer, replace ethene to use, also can adopt helium, nitrogen or hydrogen etc. to replace argon gas to use as protection gas as carbon source gas as methane, acetylene, propadiene etc.
Second kind provided by the invention to prepare the method that is mixed with the isotropic substance carbon nanotube be arc discharge method, sees also Fig. 3, and its concrete steps are as follows:
(1) with Ni (mass percent concentration 0～13%) and/or Y
2O
3The catalyst fines of (mass percent concentration 0～48%) and diameter be 5 μ m by
12High-purity carbon powder particle that C forms depresses to the carbon-point 202 that diameter is 10mm at 3500 normal atmosphere, use the same method make one by
13The carbon-point 203 that C forms and one by
14The carbon-point 204 that C forms, carbon-point 202,203 and 204 usefulness, two insulation pastes 206 are sticked together, link to each other with the positive pole 214 in arc-over source respectively and use as anode, in addition, also carbon-point 202,203 and the insulation of 204 low coverages can be placed, link to each other with the positive pole 214 in arc-over source respectively and use as anode;
(2) link to each other with the negative pole 215 in arc-over source as negative electrode 208 uses with common pure carbon rod;
(3) relative and put step (1) and (2) prepared anode and negative electrode 208, at a distance of 1.5～2mm, put in the arc-over reaction chamber 210, and after by exhaust channel 216 arc-over reaction chamber 210 being vacuumized, be by force the helium of 100～500Torr by gas input channel 218 logical entrance pressures again;
(4) electric switch 212 is connected carbon-points 202, carry out arc-over with the electric current of 100A, sparking voltage is 20～40V, reaction generate by
12The carbon nanotube fragment that C forms (figure does not show);
(5) after the reaction scheduled time, electric switch 212 is connected carbon-points 203, carry out arc-over with the electric current of 100A, sparking voltage is 20～40V, by
13The carbon nanotube fragment that C forms (figure does not show) continued growth in step (4) generate by
12On the carbon nanotube fragment that C forms;
(6) after the reaction scheduled time, electric switch 212 is connected carbon-points 204, carry out arc-over with the electric current of 100A, sparking voltage is 20～40V, by
14The carbon nanotube fragment that C forms (figure does not show) continued growth in step (5) generate by
13On the carbon nanotube fragment that C forms, the isotopic carbon nanotube that is mixed with that reaction generates is deposited on this negative electrode 208;
(7) after the continuation reaction scheduled time, constantly the anode that consumes lasting formation under deposition on the negative electrode 208 is mixed with isotopic carbon nanotube.
Be understandable that, can obtain the isotopic carbon nanotube of being mixed with of periodic arrangement in step (6) back repeating step (4), (5) and (6) in present method, perhaps repeating step (4), (5) and (6) can obtain the isotopic carbon nanotube of being mixed with of no periodic array at random after step (6); Also can become carbon-point with the carbon dust compound suppressing with pure cobalt powder or pure nickel powder or other appropriate catalyst; Also can adopt argon gas, nitrogen or hydrogen etc. to replace helium to use as protection gas; Also can connect power supply in rotary manner with containing different isotopic anodes; Also can on the electric arc reaction chamber, be equipped with cold water pipe in order to avoid because the heat that arc-over produces is too high.
The method that the third preparation provided by the invention is mixed with the isotropic substance carbon nanotube is a laser ablation method, sees also Fig. 4, and its concrete steps are as follows:
(1) with mix cobalt powder (mass percent concentration 2.8%) and nickel (mass percent concentration 2.8%) powder with by
12The high pure carbon powder that C forms is pressed into the laser radiation target 302 of composite carbon piece as laser ablation method, uses the same method and makes a target 303 and a target 304 of being made up of 14C of being made up of 13C respectively;
(2) provide carbon nanotube collection device 308;
(3) the carbon nanotube collection device 308 of prepared target 302,303,304 of step (1) and step (2) is put into laser ablation reaction chamber 310, and make carbon nanotube collection device 308 place a side of target 302,303,304;
(4) after laser ablation reaction chamber 310 being vacuumized and by exhaust channel 316, be by force the argon gas of 50～760Torr by gas input channel 318 logical entrance pressures again;
(5) with well heater 306 the hit zone at 302,303,304 places of laser ablation reaction chamber 310 is heated to 1000～1200 ℃;
(6) utilize wavelength that condenser lens 312 will place target 302,303,304 opposite sides to focus on the target 302 for the energy of 532nm, the single laser pulse pulsed laser beam 314 for 250mJ, the diameter of point of irradiation is 5mm, reaction generate by
12The carbon nanotube fragment that C forms (figure does not show);
(7) after the irradiation scheduled time, the position of regulating condenser lens 312 focuses on laser beam 314 on another piece target 303, by
13The carbon nanotube fragment that C forms (figure does not show) continued growth in step (6) generate by
12On the carbon nanotube fragment that C forms;
(8) after the irradiation scheduled time, the position of regulating condenser lens 312 focuses on laser beam 314 on another piece target 304, by
14The carbon nanotube fragment that C forms (figure does not show) continued growth in step (6) generate by
13On the carbon nanotube fragment that C forms, the isotopic carbon nanotube that is mixed with that reaction generates is deposited on this carbon nanotube collection device 308;
(9) continue the reaction scheduled time after, with collection device 308 that laser beam 314 relative ends are placed on continue to deposit and be mixed with isotopic carbon nanotube.
Be understandable that, can obtain the isotopic carbon nanotube of being mixed with of periodic arrangement in step (8) back repeating step (6), (7) and (8) in present method, perhaps repeating step (6), (7) and (8) can obtain the isotopic carbon nanotube of being mixed with of no periodic array at random after step (8); Also can be pressed into the laser radiation target of target with pure cobalt powder or pure nickel powder or other appropriate catalyst and carbon dust composite powder as laser ablation method; Also can adopt helium, nitrogen or hydrogen etc. to replace argon gas to use as protection gas; The mode that also can utilize mobile laser source or exchange two target position shines laser source on another piece target.
Method provided by the invention can prepare the carbon nanotube by different carbon isotope alternating growths, thereby the pattern of methods such as available Raman spectrum or second ion mass spectroscopy record carbon isotope growth in situ, and then the growth mechanism of research carbon nanotube, the synthetic monodimension nanometer material that contains the isotropic substance heterojunction of also available method provided by the invention simultaneously.
Although specifically show and introduced the present invention in conjunction with preferred embodiment, but the those skilled in the art should understand, can make various variations to the present invention in the form and details, and can not break away from the spirit and scope of the present invention that appended claims limits.
Claims (26)
1. carbon nanotube is characterized in that this carbon nanotube is mixed by three kinds of single isotropic substances to form, and wherein, the isotropic substance blending ratio of this mixings composition is periodicity or aperiodicity variation along the pipe range direction.
2. carbon nanotube as claimed in claim 1 is characterized in that carbon nanotube is made up of 12C, 13C and 14C.
3. carbon nanotube as claimed in claim 1, the length that it is characterized in that this carbon nanotube are 10～1000 μ m.
4. carbon nanotube as claimed in claim 1, the diameter that it is characterized in that this carbon nanotube is 0.5～50nm.
5. the preparation method of carbon nanotube as claimed in claim 1 is characterized in that comprising the steps:
Provide and contain the monoisotopic first carbon source gas, the second carbon source gas and the 3rd carbon source gas;
The substrate that deposits catalyzer on it is provided;
Utilize chemical Vapor deposition process, the isotropic substance of the carbon that the first carbon source gas provides is reacted and the first carbon nanotube fragment that reaction is generated is deposited in this substrate;
After the reaction scheduled time, carbon source is switched on the second carbon source gas, utilize chemical Vapor deposition process equally, the isotropic substance of the carbon that the second carbon source gas provides is reacted, the second carbon nanotube fragment of generation grows on the first carbon nanotube fragment;
After the reaction scheduled time, carbon source is switched on the 3rd carbon source gas, utilize chemical Vapor deposition process equally, the isotropic substance of the carbon that the 3rd carbon source gas provides is reacted, the 3rd carbon nanotube fragment that generates grows on the second carbon nanotube fragment, thereby obtains being mixed with multiple isotopic carbon nanotube.
6. the preparation method of carbon nanotube as claimed in claim 5 is characterized in that this catalyzer comprises cobalt, nickel or its alloy or iron.
7. the preparation method of carbon nanotube as claimed in claim 5 is characterized in that the chemical Vapor deposition process working temperature is 500～1100 ℃.
8. the preparation method of carbon nanotube as claimed in claim 5 is characterized in that this first carbon source gas, the second carbon source gas and the 3rd carbon source gas are hydrocarbon gas.
9. the preparation method of carbon nanotube as claimed in claim 8 is characterized in that hydrocarbon gas comprises methane, ethene, acetylene or propadiene.
10. the preparation method of carbon nanotube as claimed in claim 5 is characterized in that feeding in the reaction process shielding gas.
11. the preparation method of carbon nanotube as claimed in claim 10 is characterized in that this protective gas comprises helium, argon gas, nitrogen or hydrogen.
12. the preparation method of carbon nanotube as claimed in claim 1 is characterized in that comprising the steps:
Provide and contain monoisotopic first carbon source, second carbon source and the 3rd carbon source, respectively as anode;
Provide one with the negative electrode of first carbon source, second carbon source and the corresponding setting of the 3rd carbon source;
Make first carbon source and this negative electrode generation arc-over, the isotropic substance of the carbon that first carbon source provides is reacted and make reaction and generate the first carbon nanotube fragment;
After the reaction scheduled time, carbon source is switched to second carbon source, make second carbon source and this negative electrode generation arc-over, the isotropic substance of the carbon that second carbon source provides is reacted, the second carbon nanotube fragment of generation grows on the first carbon nanotube fragment;
After the reaction scheduled time, carbon source is switched to the 3rd carbon source, make the 3rd carbon source and this negative electrode generation arc-over, the isotropic substance of the carbon that the 3rd carbon source provides is reacted, the 3rd carbon nanotube fragment that generates grows on the second carbon nanotube fragment, thereby obtain being mixed with isotopic carbon nanotube, be deposited on this negative electrode.
13. the preparation method of carbon nanotube as claimed in claim 12 is characterized in that first carbon source, second carbon source and the 3rd carbon source are to suppress first carbon-point, second carbon-point and the 3rd carbon-point that forms respectively with by the high pure carbon powder of single isotopics by catalyst fines.
14. the preparation method of carbon nanotube as claimed in claim 12, the discharging current that it is characterized in that arc-over is 100A.
15. the preparation method of carbon nanotube as claimed in claim 13 is characterized in that this catalyst fines comprises nickel and/or yttrium oxide powder.
16. the preparation method of carbon nanotube as claimed in claim 13 is characterized in that this first carbon-point, second carbon-point and the 3rd carbon-point are that the diameter that compacting forms under 3500 normal atmosphere is the carbon-point of 10mm.
17. the preparation method of carbon nanotube as claimed in claim 13 is characterized in that this first carbon-point, second carbon-point and the 3rd carbon-point stick together with insulation paste or the low coverage insulation is placed.
18. the preparation method of carbon nanotube as claimed in claim 12 is characterized in that feeding in the reaction process protective gas.
19. the preparation method of carbon nanotube as claimed in claim 18 is characterized in that this protective gas is helium, argon gas, nitrogen or hydrogen.
20. the preparation method of carbon nanotube as claimed in claim 1 is characterized in that comprising the steps:
Provide and contain monoisotopic first carbon source, second carbon source and the 3rd carbon source;
The carbon nanotube collection device is provided;
First carbon source, second carbon source and the 3rd carbon source and this carbon nanotube collection device are put into reaction chamber, and make the carbon nanotube collection device place a side of first carbon source, second carbon source and the 3rd carbon source;
With pulsed laser irradiation first carbon source that places first carbon source, second carbon source and the 3rd carbon source opposite side, the first carbon nanotube fragment that makes the isotropic substance of the carbon that first carbon source provides react and reaction is generated;
After the reaction scheduled time, with pulsed laser irradiation second carbon source, the isotropic substance of the carbon that second carbon source provides is reacted, the second carbon nanotube fragment of generation grows on the first carbon nanotube fragment;
After the reaction scheduled time, with pulsed laser irradiation the 3rd carbon source, the isotropic substance of the carbon that the 3rd carbon source provides is reacted, the 3rd carbon nanotube fragment that generates grows on the second carbon nanotube fragment, thereby obtain being mixed with multiple isotopic carbon nanotube, be deposited on this carbon nanotube collection device.
21. the preparation method of carbon nanotube as claimed in claim 20, the temperature that it is characterized in that first carbon source, second carbon source and the 3rd carbon source region is 1000～1200 ℃.
22. the preparation method of carbon nanotube as claimed in claim 20 is characterized in that first carbon source, second carbon source and the 3rd carbon source are to suppress the first target piece, the second target piece and the 3rd target piece that forms respectively with by the high pure carbon powder of single isotopics by catalyst fines.
23. the preparation method of carbon nanotube as claimed in claim 22 is characterized in that this catalyst fines comprises nickel and/or cobalt dust.
24. the preparation method of carbon nanotube as claimed in claim 20, it is characterized in that using to be wavelength be the energy of 532nm, the single laser pulse pulse laser as 250mJ.
25. the preparation method of carbon nanotube as claimed in claim 20 is characterized in that feeding in the reaction process protective gas.
26. the preparation method of carbon nanotube as claimed in claim 25 is characterized in that this protective gas comprises helium, argon gas, nitrogen or hydrogen.
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| CNB2004100273787A CN1328161C (en) | 2004-05-20 | 2004-05-20 | Nano carbon tube and preparation method thereof |
| US11/118,588 US7713583B2 (en) | 2002-11-27 | 2005-04-29 | Method for forming isotope-doped light element nanotube |
| US11/904,958 US7479325B2 (en) | 2002-11-27 | 2007-09-28 | Isotope-doped carbon nanotube |
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| CN102115026A (en) * | 2009-12-31 | 2011-07-06 | 清华大学 | One-dimensional nano-structure, preparation method thereof and method for marking by using one-dimensional nano-structure |
| US8491863B2 (en) * | 2010-09-28 | 2013-07-23 | Tsinghua University | Method for making carbon nanotube array |
| US8609061B2 (en) * | 2010-09-28 | 2013-12-17 | Tsinghua University | Carbon nanotube array and method for making same |
| TWI417412B (en) * | 2010-10-07 | 2013-12-01 | Hon Hai Prec Ind Co Ltd | A carbon nanotube array and method for making the same |
| TWI417413B (en) * | 2010-10-07 | 2013-12-01 | Hon Hai Prec Ind Co Ltd | Method for making carbon nanotube array |
| US8715609B2 (en) * | 2010-12-14 | 2014-05-06 | The Boeing Company | Augmented reactor for chemical vapor deposition of ultra-long carbon nanotubes |
| CN112875680B (en) * | 2021-01-21 | 2022-10-14 | 电子科技大学 | Preparation method of flaky Fe-based alloy catalytic growth carbon nanotube array |
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| CN1356260A (en) * | 2001-09-26 | 2002-07-03 | 复旦大学 | Process for preparing nano carbon tubes arranged in array |
| JP2003034514A (en) * | 2001-07-17 | 2003-02-07 | National Institute Of Advanced Industrial & Technology | Carbon material with controlled isotope ratio and method for manufacturing the same |
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| JP2003034514A (en) * | 2001-07-17 | 2003-02-07 | National Institute Of Advanced Industrial & Technology | Carbon material with controlled isotope ratio and method for manufacturing the same |
| CN1356260A (en) * | 2001-09-26 | 2002-07-03 | 复旦大学 | Process for preparing nano carbon tubes arranged in array |
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