CN100358803C - Method of growing carbon nanometer pipe on carbon cloth base - Google Patents
Method of growing carbon nanometer pipe on carbon cloth base Download PDFInfo
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- CN100358803C CN100358803C CNB2006100429332A CN200610042933A CN100358803C CN 100358803 C CN100358803 C CN 100358803C CN B2006100429332 A CNB2006100429332 A CN B2006100429332A CN 200610042933 A CN200610042933 A CN 200610042933A CN 100358803 C CN100358803 C CN 100358803C
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Abstract
The present invention discloses a method for growing carbon nanometer tubes on a carbon cloth as a substrate, which is used for growing carbon nanometer tubes. The method comprises the following steps: a piece of graphite paper and 1K of carbon cloth are taken, the graphite paper is spread in a graphite mould, and the carbon cloth is spread on the graphite paper; Ni powder and sublimed S powder are proportionally and evenly mixed and are spread and scattered on the carbon cloth, and the graphite mould is put in a high temperature furnace; after the condition that air in the high-temperature furnace is exhausted is confirmed, high-purity Ar gas is introduced, and the high-temperature furnace is heated to 1050 to 1300 DEG C within 1 to 2 hours; natural gas is introduced, and the high-temperature furnace is maintained to 1050 to 1300 DEG C for 1 to 4 hours under the protection of the Ar gas; after the furnace temperature drops to room temperature, the Ar gas is cut off, the graphite mould is taken out after the furnace is opened, and black sediments on the carbon cloth are the carbon nanometer tubes. The method adopts the Ni powder and the sublimed S powder as catalysts, and the natural gas is catalyzed and pyrolyzed so as to directly grow the carbon nanometer tubes on the carbon cloth. The Ni powder, the sublimed S powder and the carbon cloth as a substrate are used when purchased, the catalysts do not need to be previously prepared, the substrate does not need to be pretreated, and the technological operation of growing the carbon nanometer tubes is completed by one step.
Description
Technical field
The present invention relates to a kind of method of carbon nano-tube, particularly the method for carbon nano-tube in the carbon cloth substrate.
Background technology
Document " Direct growth of carbon nanotubes on the surface of ceramic fibers; Carbon; 2005; 43:855-894. " discloses a kind of method with the injection carbon nano-tube, this method is a raw material with the mixed solution of dimethylbenzene-ferrocene, ferrocene catalytic pyrolysis dimethylbenzene, the carbon nanotube of growth alignment on SiC and aluminum fiber.Because raw material adopts injection, speed feeding with 0.05ml/min, need to rely on the gas mixture bubbling of nitrogen and hydrogen simultaneously, the mixed solution of dimethylbenzene-ferrocene is carried into reaction zone, the liquid amount of feed is very little, need to rely on the mixed gas bubbling to bring in, process is influenced greatly by human factor, and is restive.
Document " The growth of multi-walled carbon nanotubes with different morphologies oncarbon fibers; Carbon; 2005; 43:651-673. " discloses the catalytic pyrolysis of a kind of p-Xylol-ferrocene solution, the method for the carbon nanotube of growth variform on carbon fiber.The mixed solution of raw material dimethylbenzene-ferrocene is brought reaction zone in by the gas mixture of nitrogen and hydrogen, complicated operating process by intermittent infusion.
Document " Synthesis and characterization of in situ grown carbon nanofiber/nanotubereinforced carbon/carbon composites; Carbon; 2005; 43:2397-2429. " discloses a kind of method of utilizing catalytic pyrolysis growth in situ carbon nanofiber, carbon nanotube on carbon fiber, at first with carbon fiber at rare H
2SO
4, HNO
3Carry out acidification in the mixed solution, repeatedly washing, drying.Adopt original position coprecipitation method deposition Ni-Al (4: 1) catalyzer more thereon, the mixed gas of catalytic pyrolysis propylene and hydrogen then, growth in situ carbon nanofiber, carbon nanotube on carbon fiber.The deficiency of this method is: (1) will carry out acidification to the substrate carbon fiber.(2) will prepare catalyzer in advance, step is numerous and diverse.
Summary of the invention
To prepare catalyzer in advance and will carry out pretreated deficiency in order to overcome prior art substrate, the invention provides a kind of in the carbon cloth substrate method of carbon nano-tube, adopting commercially available material is catalyzer, and Sweet natural gas is a carbon source, direct growth carbon nanotube on carbon cloth.
The present invention solves the technical scheme that its technical problem takes: a kind of in the carbon cloth substrate method of carbon nano-tube, it is characterized in that, comprise the steps:
1) gets graphite paper and 1K carbon cloth, graphite paper is tiled in the graphite jig, carbon cloth then is tiled on the graphite paper, according to Ni: S=1: 1～1: 0.2 weight ratio with the Ni powder and chemical pure distillation S powder mixes and spreading on carbon cloth, graphite jig is put into High Temperature Furnaces Heating Apparatus;
2) check that with ordinary method the resistance to air loss of High Temperature Furnaces Heating Apparatus is intact after, open off-gas pump, drain air in the High Temperature Furnaces Heating Apparatus;
3) after air drains in confirming High Temperature Furnaces Heating Apparatus, feed high-purity Ar gas, Ar airshed 0.05～0.4m
3/ h was warming up to 1050～1300 ℃ simultaneously in 1～2 hour;
4) feed Sweet natural gas, flow is 0.1～0.4m
3/ h, the Ar airshed is 0.4～2.8m
3/ h was in 1050～1300 ℃ of constant temperature 1～4 hour;
5) cut off the electricity supply, reduce to room temperature with stove, it is 0.05～0.4m that temperature-fall period still keeps the Ar airshed
3/ h;
6) after furnace temperature is reduced to room temperature, close Ar gas, graphite jig is taken out in blow-on, and the black deposit on the carbon cloth is a carbon nanotube.
Described Ni powder particles is 200～400 orders.
The invention has the beneficial effects as follows: owing to adopt Ni powder and distillation S powder is catalyzer, the catalytic pyrolysis Sweet natural gas, direct carbon nano-tube on carbon cloth, catalyst n i powder and distillation S powder and substrate carbon cloth are all purchased promptly and are used, do not need to prepare in advance catalyzer, also do not need pre-treatment is carried out in substrate, the carbon source Sweet natural gas is cheap and easy to get, and one step of technological operation of carbon nano-tube finishes.
Description of drawings
Fig. 1 (a) is the multi-walled carbon nano-tubes stereoscan photograph of the method growth of carbon nano-tube in the carbon cloth substrate
Fig. 1 (b) is the multi-walled carbon nano-tubes transmission electron microscope photo of the method growth of carbon nano-tube in the carbon cloth substrate
Embodiment
Embodiment 1:
(1) get graphite paper and 1K carbon cloth, graphite paper is tiled in the graphite jig, and carbon cloth then is tiled on the graphite paper, and the size of graphite paper, carbon cloth is advisable with the full graphite jig that just in time tiles.Take by weighing 200 order Ni powder 1g, chemical pure distillation S powder 1g, make it to mix and spreading on carbon cloth, graphite jig is put into High Temperature Furnaces Heating Apparatus;
(2) check the resistance to air loss of High Temperature Furnaces Heating Apparatus with ordinary method;
(3) open vacuum pump, get rid of air in the stove, logical Ar30 minute, aforesaid operations was three times repeatedly, guarantees that furnace air drains;
(4) after air drains in confirming High Temperature Furnaces Heating Apparatus, feed high-purity Ar gas, making the Ar flow is 0.4m
3/ h is warming up to 1300 ℃ in 1 hour;
(5) feed Sweet natural gas, flow is 0.1m
3/ h, Ar flow are 0.4m
3/ h was in 1300 ℃ of constant temperature 1 hour;
(6) cut off the electricity supply, reduce to room temperature with stove, it is 0.4m that temperature-fall period still keeps the Ar airshed
3/ h.
(7) after furnace temperature is reduced to room temperature, close Ar gas, graphite jig is taken out in blow-on, and one deck black deposit is arranged on the carbon cloth.
Through scanning electron microscope observation is carried out in this black deposit direct sampling, the gained carbon nanotube is a multi-walled carbon nano-tubes.Fig. 1 (a) is the stereoscan photograph of the multi-walled carbon nano-tubes of growing on carbon cloth with the inventive method, can obviously find out, the pipe that obtains for discrete, caliber uniformly diameter less than the pipe of 100nm.Fig. 1 (b) is the transmission electron microscope photo of the multi-walled carbon nano-tubes of growing on carbon cloth with the inventive method, can find out obviously that the carbon nanotube that obtains is straight multi-walled pipes.
Embodiment 2:
(1) get graphite paper and 1K carbon cloth, graphite paper is tiled in the graphite jig, and carbon cloth then is tiled on the graphite paper, and the size of graphite paper, carbon cloth is advisable with the full graphite jig that just in time tiles.Take by weighing 300 order Ni powder 1g, chemical pure distillation S powder 0.8g, make it to mix and spreading on carbon cloth, graphite jig is put into High Temperature Furnaces Heating Apparatus;
(2) check the resistance to air loss of High Temperature Furnaces Heating Apparatus with ordinary method;
(3) open vacuum pump, get rid of air in the stove, logical Ar30 minute, aforesaid operations was three times repeatedly, guarantees that furnace air drains;
(4) after air drains in confirming High Temperature Furnaces Heating Apparatus, feed high-purity Ar gas, the Ar airshed is 0.3m
3/ h is warming up to 1100 ℃ in 1 hour;
(5) feed Sweet natural gas, flow is 0.2m
3/ h, Ar flow are 1.5m
3/ h was in 1100 ℃ of constant temperature 2 hours;
(6) cut off the electricity supply, reduce to room temperature with stove, it is 0.3m that temperature-fall period still keeps the Ar airshed
3/ h.
(7) after furnace temperature is reduced to room temperature, close Ar gas, graphite jig is taken out in blow-on, and one deck black deposit is arranged on the carbon cloth.
Embodiment 3:
(1) get graphite paper and 1K carbon cloth, graphite paper is tiled in the graphite jig, and carbon cloth then is tiled on the graphite paper, and the size of graphite paper, carbon cloth is advisable with the full graphite jig that just in time tiles.Take by weighing 300 order Ni powder 1g, chemical pure distillation S powder 0.6g, make it to mix and spreading on carbon cloth, graphite jig is put into High Temperature Furnaces Heating Apparatus;
(2) check the resistance to air loss of High Temperature Furnaces Heating Apparatus with ordinary method;
(3) open vacuum pump, get rid of air in the stove, logical Ar30 minute, aforesaid operations was three times repeatedly, guarantees that furnace air drains;
(4) after air drains in confirming High Temperature Furnaces Heating Apparatus, feed high-purity Ar gas, the Ar airshed is 0.1m
3/ h is warming up to 1050 ℃ in 1.5 hours;
(5) feed Sweet natural gas, flow is 0.3m
3/ h, the Ar airshed is 2.5m
3/ h was in 1050 ℃ of constant temperature 3 hours;
(6) cut off the electricity supply, reduce to room temperature with stove, it is 0.1m that temperature-fall period still keeps the Ar airshed
3/ h.
(7) after furnace temperature is reduced to room temperature, close Ar gas, graphite jig is taken out in blow-on, and one deck black deposit is arranged on the carbon cloth.
Embodiment 4:
(1) get graphite paper and 1K carbon cloth, graphite paper is tiled in the graphite jig, and carbon cloth then is tiled on the graphite paper, and the size of graphite paper, carbon cloth is advisable with the full graphite jig that just in time tiles.Take by weighing 400 order Ni powder 1g, chemical pure distillation S powder 0.2g, make it to mix and spreading on carbon cloth, graphite jig is put into High Temperature Furnaces Heating Apparatus;
(2) check the resistance to air loss of High Temperature Furnaces Heating Apparatus with ordinary method;
(3) open vacuum pump, get rid of air in the stove, logical Ar30 minute, aforesaid operations was three times repeatedly, guarantees that furnace air drains;
(4) after air drains in confirming High Temperature Furnaces Heating Apparatus, feed high-purity Ar gas, Ar airshed 0.05m
3/ h was warming up to 1200 ℃ simultaneously in 2 hours;
(5) feed Sweet natural gas, flow is 0.4m
3/ h, the Ar airshed is 2.8m
3/ h was in 1200 ℃ of constant temperature 4 hours;
(6) cut off the electricity supply, reduce to room temperature with stove, it is 0.05m that temperature-fall period still keeps the Ar airshed
3/ h;
(7) after furnace temperature is reduced to room temperature, close Ar gas, graphite jig is taken out in blow-on, and the black deposit of carbon cloth is a carbon nanotube.
Claims (2)
1, a kind of in the carbon cloth substrate method of carbon nano-tube, it is characterized in that, comprise the steps:
1) gets graphite paper and 1K carbon cloth, graphite paper is tiled in the graphite jig, carbon cloth then is tiled on the graphite paper, according to Ni: S=1: 1～1: 0.2 weight ratio with the Ni powder and chemical pure distillation S powder mixes and spreading on carbon cloth, graphite jig is put into High Temperature Furnaces Heating Apparatus;
2) check that with ordinary method the resistance to air loss of High Temperature Furnaces Heating Apparatus is intact after, open off-gas pump, drain air in the High Temperature Furnaces Heating Apparatus;
3) after air drains in confirming High Temperature Furnaces Heating Apparatus, feed high-purity Ar gas, Ar airshed 0.05～0.4m
3/ h was warming up to 1050～1300 ℃ simultaneously in 1～2 hour;
4) feed Sweet natural gas, flow is 0.1～0.4m
3/ h, the Ar airshed is 0.4～2.8m
3/ h was in 1050～1300 ℃ of constant temperature 1～4 hour;
5) cut off the electricity supply, reduce to room temperature with stove, it is 0.05～0.4m that temperature-fall period still keeps the Ar airshed
3/ h;
6) after furnace temperature is reduced to room temperature, close Ar gas, graphite jig is taken out in blow-on, and the black deposit on the carbon cloth is a carbon nanotube.
2, according to claim 1 in the carbon cloth substrate method of carbon nano-tube, it is characterized in that: described Ni powder particles is 200～400 orders.
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| CNB2006100429332A CN100358803C (en) | 2006-06-07 | 2006-06-07 | Method of growing carbon nanometer pipe on carbon cloth base |
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| CN102173407B (en) * | 2010-12-29 | 2012-07-04 | 华中科技大学 | Preparation method of flexible carbon nanoparticle and application of method |
| CN103086353B (en) * | 2013-01-11 | 2014-12-10 | 北京大学 | Single-walled carbon nanotube array with chiral selective orientation and method for representing chiral structure thereof |
| CN105948777B (en) * | 2016-06-14 | 2019-03-29 | 西北工业大学 | A kind of density is 0.5~0.8g/cm3Carbon/carbon compound material preparation method |
| CN110182848A (en) * | 2019-06-11 | 2019-08-30 | 上海大学 | A kind of high-temperature stability 1T phase molybdenum disulfide nano structure and its preparation method and application |
| CN111276330A (en) * | 2020-03-17 | 2020-06-12 | 宁波市江北九方和荣电气有限公司 | Self-healing high-voltage dry capacitor |
| CN112661134B (en) * | 2020-12-31 | 2022-10-28 | 西北工业大学 | Method for preparing pyrolytic carbon from acetaldehyde precursor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1517458A (en) * | 2003-01-13 | 2004-08-04 | 中国科学院金属研究所 | Method of preparing carbon fiber and nanometer carbon pipe |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1517458A (en) * | 2003-01-13 | 2004-08-04 | 中国科学院金属研究所 | Method of preparing carbon fiber and nanometer carbon pipe |
Non-Patent Citations (2)
| Title |
|---|
| "金镍复合膜上碳纳米管的定向生长及生长过程中金的作用". 陈淑霞等.物理学报，第54卷第7期. 2005 * |
| 高质量碳纳米管的低温制备方法. 袁泽明等.真空与低温，第12卷第1期. 2006 * |
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Effective date of registration: 20221104 Address after: No. 25, Yangbei Road, Luoshe Town, Huishan District, Wuxi City, Jiangsu Province, 214154 Patentee after: Wuxi Bozhi Composite Materials Co.,Ltd. Address before: 710072 No. 127 Youyi West Road, Shaanxi, Xi'an Patentee before: Northwestern Polytechnical University |
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