CN1168348A - Preparation process of gas-phase grown nanometer carbon fibre - Google Patents
Preparation process of gas-phase grown nanometer carbon fibre Download PDFInfo
- Publication number
- CN1168348A CN1168348A CN 96115390 CN96115390A CN1168348A CN 1168348 A CN1168348 A CN 1168348A CN 96115390 CN96115390 CN 96115390 CN 96115390 A CN96115390 A CN 96115390A CN 1168348 A CN1168348 A CN 1168348A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- carbon
- gas
- fiber
- carbon fibre
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The said preparation process features that carbon source and catalyst in gas phase are mixed fully before fed at homogeneous speed into reaction area, which is in an angle to horizontal line varying in 0-60 deg. The feeding amount of low-smelting point small-molecule hydrocarbon and/or CO and CO2 as carbon source is 0.0004-0.0012 gram equivalent carbon per sq cm per min; that of H2, N2 or He as diluent and carrier is 35 cm/min; and that of organic compound of Fe, Ni or Co as catalyst is 0.0000007-0.0000025 gram equivalent catalyst/hr. The present invention can produce high-purity nanometer carbon fibre at low cost and in large amount.
Description
The present invention relates to the manufacturing technology of carbon fiber, a kind of technology with chemical gas-phase method raised growth high-purity nm carbon fiber is provided especially.
Carbon fiber is that more a kind of fibre product is used in the material field, can be used as the wild phase of matrix material, obtains very high specific tenacity and specific modulus.The production method of at present general carbon fiber is the method that polyacrylonitrile fibril carries out preoxidation, carbonization.The aircraft industry field and civilian aspect as at high-performance sports equipment such as tennis racket, Veronicastrum Herbs etc. are widely used.Be difficult for being accepted because this carbon fiber is expensive comparatively speaking by more common purposes.For the people that reduce cost place hope on the development and the exploitation of asphalt base carbon fiber, maintain an equal level with polyacrylonitrile carbon fiber but up to the present the price of the asphalt-based carbon fiber of better performances is basic, sometimes height slightly also.Gas-phase growth of carbon fibre is different from above-mentioned polyacrylonitrile-radical and asphalt base carbon fiber, and it is discontinuous fiber, is a kind of of pyrolysis product under the hydrocarbon gas high temperature.Chemical Vapor deposition process also is a kind of method for preparing material commonly used, the pyrolytic graphite in the carbon material, and carbon/carbon compound material, and diamond film all can prepare in this way.When having transition metal such as iron, cobalt, nickel and their alloy to exist in the reaction atmosphere, in the pyrolysis product of hydrocarbon gas a large amount of fibers can appear.Because this fiber growth raw material is easy to get, equipment is simple, have the potential low cost, this in addition fibrous texture regularity height has higher intensity and modulus, and good conductivity, be easy to greying, thereby be a kind of discontinuous carbon fiber that has suitable exploitation to be worth, as doing antistatic toughener, the electric double layer capacitance electrode, cell active materials etc.The preparation method of gas-phase growth of carbon fibre can divide two kinds, a kind of is the base catalyst method, the fine particle that is catalyzer is applied on the matrix, as pottery, on the graphite boat, when catalyzer is under suitable temperature and the atmospheric condition is the catalytic growth carbon fiber, common this method through 1～2 hour reaction times after, can obtain long for several centimetres, the longest is 30 centimetres gas-phase growth of carbon fibre, diameter is 7～10 μ m, because fiber is only grown on the face that is distributed with catalyzer of growing space in this method, thereby output seldom, such gas-phase growth of carbon fibre cost is very high, is difficult to be used.Another kind method is the flowing catalyst method, generally believes that this method can reduce the manufacturing cost of gas-phase growth of carbon fibre greatly, has very high commercial value.In this method, the general organometallic compound that dissolves in organic solvent that adopts of catalyzer is made into certain density solution, and import Reaktionsofen, and pass to other reactant gases, diluent gas, device is as Fig. 1.Its product is collected at the place, air outlet.It is resulting good that the fiber quality that this method obtains can not show a candle to front matrix method, and diameter thickness is extremely inhomogeneous, is generally 0.1～1.5 μ m, 0.1～5 μ m, 50～100nm.And always be attended by more non-fiber product in the product, as the particulate state carbon black.In order to improve carbon source-fiber transformation efficiency, normal a spot of sulfur-bearing composition such as the H of adding in the reaction atmosphere
2S, thiophene etc. also have the NH of adding
3, thereby the product fiber can look thicker in the extremely short time.In the flowing catalyst method in the past, catalyzer supply amount and reaction atmosphere are difficult for reaching best fit, thereby may be because of catalyst excess, make catalyst particle size excessive, can't the catalytic growth carbon fiber, or the not enough carbon source surplus of catalytic amount, granules of catalyst is covered and inactivation, the growth of catalyzed carbon fiber effectively too early by RESEARCH OF PYROCARBON.In addition, this vertical heater flowing catalyst method, come with some shortcomings, 1. fiber growth time in stove is too short, general maximum have only tens seconds, 2. the reaction pair conditional fluctuation is too responsive, once the improper reaction compartment of condition has a large amount of non-fibrous particles, just being difficult to recover all is the state of fiber product again; 3. reaction compartment always is in and is full of the particulate low density state that floats, and is unfavorable for making full use of of reaction compartment and thermal source.
The object of the present invention is to provide a kind of method of nano-scale carbon fiber of vapor phase growth, can produce the high-purity high-quality carbon nano fiber at low cost, in large quantities.
The invention provides a kind of method of gas-phase grown nanometer carbon fibre, it is characterized in that: carbon source and catalyzer be thorough mixing under gaseous state, at the uniform velocity imports reaction zone, and angle is 0～60 ° of variation between reaction zone and sea line, wherein carbon source is low melting point small molecules hydrocarbon polymer and/or CO, CO
2, be 4 * 10 for amount
-4～1.2 * 10
-3Gram equivalent carbon/centimetre
2Minute; Carrier gas and carrier gas are hydrogen, and helium or nitrogen are 10～35 cm per minute for amount, and catalyzer is Fe, and the organic compound of Ni or Co is 3 * 10 for amount
-7～2.5 * 10
-6The gram equivalent catalyzer/centimetre hour.When catalyzer is Fe, during Co, from 780～820 ℃ to 1000～1300 ℃ of used heating-up times of end reaction temperature be 20～40 minutes.When catalyzer is Ni, from 380～420 ℃ to 600～800 ℃ of used heating-up times of end reaction temperature be 20～40 minutes.In general, when catalyst particle size moderate (2～20nm) time, in the hydrocarbon atmosphere of heat, when reactant gases is adsorbed in particle surface, can decomposite carbon atom, be subjected to certain power become to making, the free carbon atom is dissolved in the catalyst particles plastochondria, and in thermograde, to bilateral transfer, and then separate out crystalline carbon under the promotion of concentration gradient, constantly the carrying out and to grow carbon fiber in a side of granules of catalyst of this process, when granules of catalyst is coated by carbon, its active disappearance, not regrowth of fiber, the fiber surface pyrolysis that hydrocarbon gas is growing under the high temperature, deposition makes fiber long thick.Thereby characteristics of the present invention be 1. the placement angular setting by the conversion boiler tube growth time of fiber 2. utilize ever-increasing fiber to provide reaction surface to improve the transformation efficiency of product, 3. by restriction to initial reaction temperature and temperature rise, improve the final purity of product, detailed process is as follows: organometallic compound is with gasiform form and unstripped gas, carrier gas mixes, enter boiler tube jointly, organometallic compound will decompose at a lower temperature, atoms metal dissociates, cause temperature at this moment is far below the temperature of metal gasification, thereby the free atoms metal is once colliding, will no longer separate because of huge gravitation, when the metallic molecule of some amount is met (they also can follow the arrangement of lattice to a certain extent) a certain size particle, can and carbon source special effect takes place, just hydrocarbons decompose, and can dissolve degradation production one carbon, separate out the growth fiber at opposite side.If condition is suitable, fiber can quickish speed growth, if carbon source is sufficient and don't make catalyst deactivation, fiber can be longer, become the mobile obstacle mutually, in addition, long fiber can not be as the particulate that freely floats, under the effect of gravity, the tendency that the whereabouts is arranged himself, thereby just have a considerable amount of fiber product, stay in the stove, do not flow out, and then stop fiber afterwards to continue to flow through with atmosphere.All at last fiber product all can be stayed in the stove.Because catalyzer constantly enters, constantly generate new seed, the quantity of fiber is increasing, fill in very densely in reaction zone at last, because of last fiber stops more for a long time in the high-temperature zone, diameter is chap to a certain extent also, but because of fiber number too big, be assigned on the every fiber the carbon amount very little, thereby Fibre diameter still obtains much smaller than the matrix method.By embodiment in detail the present invention is described in detail below in conjunction with accompanying drawing.
Accompanying drawing 1 is a flow method grown carbon fiber apparatus structure synoptic diagram
Accompanying drawing 2 is the embodiment of the invention 1 used reaction unit figure
Accompanying drawing 3 embodiment 1 products therefrom, transmission electron microscope photo * 13500
Accompanying drawing 4 embodiment 1 products therefrom, transmission electron microscope photo * 105000
Accompanying drawing 5 embodiment 2 used reaction unit structural representations
Accompanying drawing 6 embodiment 2 products therefrom stereoscan photographs
Accompanying drawing 7 embodiment 5 used reaction unit structural representations
Embodiment 1
As Fig. 2 C
2H
2Flow: 14cm/min, H
2Flow: 22cm/minFe (C
5H
5)
2: take by weighing 0.0001g
Reaction zone rises to 900 ℃ with 20 ℃/minute more earlier to be rapidly heated 800 ℃, and 10 ℃/minute to 950 ℃, 5 ℃/minute rise to the final reaction temperature at 1100 ℃, keep 1 hour.
The product slabbing, disperseing the back to observe under transmission electron microscope is as Fig. 3, and 4 fibers are very thin, and diameter is many between 20～50nm, and non-fibrous material is few in the product.
Embodiment 2
Device is as Fig. 5
With Fe (CO)
5Be made into the benzole soln of 0.08% (wt).
C
6H
6+ H
2Flow: 22cm/min (20 ℃)
Hydrogen flowing quantity: 5cm/min
Temperature-rise period is with example 1, and the end reaction temperature kept 1 hour at 1180 ℃
It is block that product is, and observes under scanning electronic microscope, as Fig. 6.
As seen block product is by fibrous at microscopically, and Fibre diameter is 100～200nm.There is not carbon black in the product.
Embodiment 3
Device is as Fig. 5, and raw material changes reaction gas flow speed, C with example 2
6H
6+ H
2Flow 30cm/min (20 ℃), hydrogen is 7cm/min, and the reaction zone temperature-rise period is with example 1, and the end reaction temperature remains on 1200 ℃, the result: have a large amount of fibers to generate, Fibre diameter is 100～200nm.
Embodiment 4
Device is with embodiment 3
Ni (CO) is used in idleization agent instead
4, be made into the benzole soln of 0.03% (wt).
C
6H
6+ H
2Flow 10ml/cm
2Min (20 ℃), hydrogen is 3ml/cm
2The min reaction zone is rapidly heated to 500 ℃, with 20 ℃/minute, rises to 600 ℃, rises to 650 ℃ with 10 ℃/minute, rises to 700 ℃ with 5 ℃/minute.Temperature of reaction remains on 700 ℃.
The result: first villous shape material is blown out, and fine hair was no longer blown out afterwards.Length has extremely loose fibre fluff, Fibre diameter 20～50nm in the stove.
Embodiment 5
Device is seen Fig. 7
Take by weighing Fe (C
5H
5)
20.003g
C
6H
6+ H
2Flow be 20cm/min (20 ℃), H
2Flow be the 4cm/min temperature-rise period with embodiment 1, temperature of reaction be parked in 1200 ℃ 30 minutes, after extract boiler tube out 1cm, with the speed of 5 ℃/min furnace temperature is risen to 1300 ℃ again and kept again 0.5 hour.
The fiber of growing in the stove is formed piece and is filled up the vitellarium as a result, and diameter is from 20～30nm.
Claims (3)
1. the preparation method of a gas-phase grown nanometer carbon fibre, it is characterized in that: carbon source and catalyzer be thorough mixing under gaseous state, at the uniform velocity imports reaction zone, and angle is 0～60 ° of variation between reaction zone and sea line, wherein carbon source is low melting point small molecules hydrocarbon polymer and/or CO, CO
2, be 4 * 10 for amount
-4～1.2 * 10
-3Gram equivalent carbon/centimetre
2Minute; Carrier gas and carrier gas are hydrogen, and helium or nitrogen are 10～35 cm per minute for amount, and catalyzer is Fe, and the organic compound of Ni or Co is 3 * 10 for amount
-7～2.5 * 10
-6The gram equivalent catalyzer/hour.
2. by the preparation method of the described gas-phase grown nanometer carbon fibre of claim 1, it is characterized in that: when catalyzer is Fe, during Co class catalyzer, from 780～820 ℃ to 1000～1300 ℃ of used heating-up times of end reaction temperature be 20～40 minutes.
3. by the preparation method of the described gas-phase grown nanometer carbon fibre of claim 1, it is characterized in that: when catalyzer is Ni, from 380～420 ℃ to 600～800 ℃ of used heating-up times of end reaction temperature be 20～40 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115390A CN1061706C (en) | 1996-06-19 | 1996-06-19 | Preparation process of gas-phase grown nanometer carbon fibre |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115390A CN1061706C (en) | 1996-06-19 | 1996-06-19 | Preparation process of gas-phase grown nanometer carbon fibre |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1168348A true CN1168348A (en) | 1997-12-24 |
| CN1061706C CN1061706C (en) | 2001-02-07 |
Family
ID=5122650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96115390A Expired - Fee Related CN1061706C (en) | 1996-06-19 | 1996-06-19 | Preparation process of gas-phase grown nanometer carbon fibre |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1061706C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0945402A1 (en) * | 1998-03-25 | 1999-09-29 | Research Institute of Innovative Technology for the Earth | Method for producing carbon |
| CN1297474C (en) * | 2000-06-02 | 2007-01-31 | 俄克拉何马大学董事会 | Method and appts. for producing carbon nanotubes |
| CN100337909C (en) * | 2005-03-16 | 2007-09-19 | 清华大学 | Growth method carbon nanotube array |
| CN100376477C (en) * | 2005-03-18 | 2008-03-26 | 清华大学 | Growth appts. of carson nanotube array and growth method of multi-wall carbon nanotube array |
| CN100423160C (en) * | 2001-03-27 | 2008-10-01 | 佳能株式会社 | Catalyst for forming carbon fibre, its making method and electronic transmitter |
| CN101864635A (en) * | 2010-05-25 | 2010-10-20 | 大连理工大学 | Method for manufacturing high-strength viscose-based active carbon fiber fabrics |
| CN101939256A (en) * | 2009-03-05 | 2011-01-05 | 昭和电工株式会社 | Carbon fiber agglomerates and process for production of same |
| CN101974803B (en) * | 2004-06-08 | 2012-10-17 | 昭和电工株式会社 | Vapor-grown carbon fiber, production method thereof and composite material containing the same |
| CN103014917A (en) * | 2012-12-24 | 2013-04-03 | 青岛科技大学 | Preparation method of multi-branched carbon fiber |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0680210B2 (en) * | 1988-09-12 | 1994-10-12 | 日本鋼管株式会社 | Carbon fiber manufacturing method |
| JPH02127523A (en) * | 1988-11-08 | 1990-05-16 | Mitsui Eng & Shipbuild Co Ltd | Carbon fiber of vapor growth |
-
1996
- 1996-06-19 CN CN96115390A patent/CN1061706C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0945402A1 (en) * | 1998-03-25 | 1999-09-29 | Research Institute of Innovative Technology for the Earth | Method for producing carbon |
| CN1297474C (en) * | 2000-06-02 | 2007-01-31 | 俄克拉何马大学董事会 | Method and appts. for producing carbon nanotubes |
| CN100423160C (en) * | 2001-03-27 | 2008-10-01 | 佳能株式会社 | Catalyst for forming carbon fibre, its making method and electronic transmitter |
| CN101974803B (en) * | 2004-06-08 | 2012-10-17 | 昭和电工株式会社 | Vapor-grown carbon fiber, production method thereof and composite material containing the same |
| CN100337909C (en) * | 2005-03-16 | 2007-09-19 | 清华大学 | Growth method carbon nanotube array |
| CN100376477C (en) * | 2005-03-18 | 2008-03-26 | 清华大学 | Growth appts. of carson nanotube array and growth method of multi-wall carbon nanotube array |
| CN101939256A (en) * | 2009-03-05 | 2011-01-05 | 昭和电工株式会社 | Carbon fiber agglomerates and process for production of same |
| CN101939256B (en) * | 2009-03-05 | 2013-02-13 | 昭和电工株式会社 | Carbon fiber agglomerates and process for production of same |
| CN101864635A (en) * | 2010-05-25 | 2010-10-20 | 大连理工大学 | Method for manufacturing high-strength viscose-based active carbon fiber fabrics |
| CN103014917A (en) * | 2012-12-24 | 2013-04-03 | 青岛科技大学 | Preparation method of multi-branched carbon fiber |
| CN103014917B (en) * | 2012-12-24 | 2014-09-24 | 青岛科技大学 | Preparation method of multi-branched carbon fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1061706C (en) | 2001-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Inagaki et al. | Materials science and engineering of carbon: fundamentals | |
| JP3850380B2 (en) | Carbon nanotube matrix growth method | |
| Nikolaev et al. | Gas-phase catalytic growth of single-walled carbon nanotubes from carbon monoxide | |
| Bronikowski et al. | Gas-phase production of carbon single-walled nanotubes from carbon monoxide via the HiPco process: A parametric study | |
| Rakov | Methods for preparation of carbon nanotubes | |
| CN100526217C (en) | Preparation method of quasi one-dimensional boron nitride nanostructure | |
| Jiao et al. | Single-walled tubes and encapsulated nanoparticles: comparison of structural properties of carbon nanoclusters prepared by three different methods | |
| CN1061706C (en) | Preparation process of gas-phase grown nanometer carbon fibre | |
| Fan et al. | Tailoring the diameters of vapor-grown carbon nanofibers | |
| CN101857460A (en) | Preparation method of carbon nano tube array for spinning | |
| CN103446804A (en) | Carbon nanotube air filtering material with gradient structure and preparation method thereof | |
| Zhang et al. | Layered growth of aligned carbon nanotube arrays by pyrolysis | |
| DE102008023229B4 (en) | A method for producing carbon nanotubes on a carrier substrate, carbon nanotubes produced by the method and their use | |
| US10421061B2 (en) | Preparation method of alumina-carbon nano tube composite powder material | |
| CN115340084A (en) | Method for preparing carbon nano tube by hydrogen-free chemical vapor deposition | |
| CN110229709B (en) | Preparation and application of SiC-doped onion-shaped graphitized carbon sphere nano composite material | |
| Ding et al. | Symmetry-related growth of carbon nanocoils from Ni–P based alloy particles | |
| CN110040718B (en) | Preparation method of thiacalixarene-based multi-walled carbon nanotube derived from 16 nuclear molecular cluster | |
| Chen et al. | Carbon nanotubes grown over Fe− Mo− Mg− O composite catalysts | |
| CN1522956A (en) | Process for preparing nanometer carbon microballoon by arc discharging technology | |
| EP2455337B1 (en) | Process for fabrication and surface modification of colloidal carbon spheres in supercritical media | |
| CN1172847C (en) | Array nanotube, mfg. method and use thereof | |
| Huang et al. | Substrate morphology induced self-organization into carbon nanotube arrays, ropes, and agglomerates | |
| WO2015047129A1 (en) | Method for producing a nanostructured carbon material based on carbon black | |
| KR20190122336A (en) | Carbon nanotube fiber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhang Ronghui Inventor after: Cheng Huiming Inventor after: Shen Zuhong Inventor before: Zhang Puhui Inventor before: Cheng Huiming Inventor before: Shen Zuhong |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: ZHANG PUHUI; CHENG HUIMING; SHEN ZUHONG TO: ZHANG RONGHUI; CHENG HUIMING; SHEN ZUHONG |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SHENYANG JINNA NEW MATERIALS CO., LTD. Free format text: FORMER OWNER: METAL INST., CHINESE ACADEMY OF SCIENCES Effective date: 20020524 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20020524 Address after: The 110179 century Hunnan Industrial Road in Shenyang city in Liaoning province high tech Zone No. 1 Patentee after: Jinna New Material Co., Ltd., Shenyang Address before: Shenhe District Shenyang 110015 Liaoning Province Cultural Road No. 72 Patentee before: Institute of metal research, Chinese Academy of Sciences |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20010207 Termination date: 20110619 |