CN101476176A - Method for gas-phase growth of carbon fibre - Google Patents
Method for gas-phase growth of carbon fibre Download PDFInfo
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- CN101476176A CN101476176A CNA200910104869XA CN200910104869A CN101476176A CN 101476176 A CN101476176 A CN 101476176A CN A200910104869X A CNA200910104869X A CN A200910104869XA CN 200910104869 A CN200910104869 A CN 200910104869A CN 101476176 A CN101476176 A CN 101476176A
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Abstract
The invention provides a method for preparing vapor-grown carbon fiber which includes steps as follows: placing a matrix into a reacting chamber and filling with carbon source precursor gas; heating the matrix using microwave for making the matrix temperature in 900 to 1300 DEG. C; the carbon source precursor gas pyrolyzing on the matrix surface with the temperature for growing carbon fibre. The method uses microwave for heating, gets help from polar material acted by microwave, has characteristics of self heating and rapid heating speed, activation of non-heat effect of microwave to material reaction and inductivity of process change, reduces activation energy, changes reaction dynamics, accordingly promotes reaction selectly, and improves direction reaction activation, is easy to grow vapor-grown carbon fibre on the matrix surface.
Description
Technical field
The present invention relates to the preparation method of material with carbon element, relate in particular to a kind of method of gas-phase growth of carbon fibre.
Background technology
At present, the method for gas-phase growth of carbon fibre mainly contains two kinds: matrix method and spray process or flowing catalyst method.So-called matrix method is that graphite or pottery are made matrix, impose catalyst granules and do " seed ", high temperature feeds hydrocarbon compound gas down, also is mixed with hydrogen simultaneously, and hydrocarbon gas decomposes and separates out fibrous carbon in a side of catalyst granules under the effect of catalyst then.Rodrigue sprays the superfine catalyst powder on matrix, the high temperature degradation hydrocarbon gas is prepared the gas-phase growth of carbon fibre of 50nm～80nm.This base catalyst method can be prepared high-quality gas-phase growth of carbon fibre.But the preparation of superfine catalyst particle is difficulty very, sprays inhomogeneously on matrix, and gas-phase growth of carbon fibre only grows having on the matrix of catalyst, thereby output is not high.
Tibbetts has successfully prepared the gas-phase growth of carbon fibre of 50nm～100nm in a vertical stove with spray process or flowing catalyst method.Though this method provides the possibility of a large amount of preparation gas-phase growth of carbon fibre, but because the ratio of catalyst and hydrocarbon compound gas is difficult to optimize, the iron distribution of particles is inhomogeneous in the sprinkling process, and the catalyst granules that sprays is difficult to exist with nanoscale form, and the gas-phase growth of carbon fibre of preparation always generates with a large amount of carbon blacks.
Summary of the invention
In view of this, the method that is necessary to provide a kind of reactivity height and is easy to grow the gas-phase growth of carbon fibre of carbon fiber at matrix surface.
A kind of method of gas-phase growth of carbon fibre may further comprise the steps:
Matrix is placed reaction cavity, and charge into carbon source precursor gas;
Adopt microwave that matrix is heated, make substrate temperature between 900 ℃ to 1300 ℃;
Carbon source precursor gas has the matrix surface pyrolysis of described temperature, and vapor phase growth goes out carbon fiber.
Compared with prior art, the method of described gas-phase growth of carbon fibre adopts the method for heating using microwave, be subjected to microwave action by polar substances, non-thermal effect with the fast characteristics of spontaneous heating and firing rate and microwave is to the activation of substance reaction and the inductivity of process change, reduced activation energy, change kinetics, thereby optionally promoted reaction and improve the orientation reaction activity, be easy to the matrix surface gas-phase growth of carbon fibre.
Description of drawings
Fig. 1 is the installation drawing that method adopted of the gas-phase growth of carbon fibre of the embodiment of the invention.
Fig. 2 is that device among Fig. 1 is along the cross section internal structure schematic diagram of A-B line.
Fig. 3 is the method flow schematic diagram of the gas-phase growth of carbon fibre of the embodiment of the invention.
Fig. 4 is the embodiment of the invention one, two and the three ESEM schematic diagrames at the carbon fiber of alumina base surface vapor phase growth.
Fig. 5 is the ESEM schematic diagram of the embodiment of the invention four at the gas-phase carbon fiber of carbon/carbon composite material base surface vapor phase growth.
Fig. 6 is the ESEM schematic diagram of the embodiment of the invention five at the carbon fiber of silicon carbide-based surface vapor phase growth.
Fig. 7 is the ESEM schematic diagram of the CNT of the embodiment of the invention six vapor phase growths.
The specific embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with drawings and Examples.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
See also Fig. 1, be the installation drawing that method adopted of the embodiment of the invention.This device is a microwave-heating chemical vapor deposition method device 10, comprises microwave cavity 12 and the reaction cavity 14 that places in the microwave cavity 12.Reaction cavity 14 shown in Figure 1 is quartz ampoules 14.When device 10 work, be loaded with matrix 16 in the quartz ampoule 14, have gap 15 between matrix 16 and the quartz ampoule 14, pass through with supplied gas.Microwave cavity 12 has gas access 18 and outlet 19, wherein enters the mouth 18 directly to be connected with the mouth of pipe of quartz ampoule 14, exports 19 and is opened on the sidewall of microwave cavity 12.
As shown in Figure 2, the matrix 16 in the present embodiment is a cylinder coaxial with quartz ampoule 14, has annular gap 15 between matrix 16 peripheries of cylindrical shape and the quartz ampoule 14, evenly pass through with supplied gas, and at matrix 16 outer surface grown carbon fibers.
See also Fig. 1 and 3, with the method flow of gas-phase growth of carbon fibre of the explanation embodiment of the invention, it may further comprise the steps:
(1) matrix 16 is placed reaction cavity, promptly in the quartz ampoule 14, and charge into carbon source precursor gas;
(2) adopt 17 pairs of matrixes 16 of microwave to heat, substrate temperature is remained between 900 ℃ to 1300 ℃;
(3) carbon source precursor gas is in the matrix 16 surperficial pyrolysis with this temperature, and vapor phase growth goes out carbon fiber.
In step (2), not only matrix 16 is heated, also carbon source precursor gas is heated simultaneously, mainly utilize microwave to polar substances, be that the firing rate that has of carbon source precursor gas is fast, the non-thermal effect of the characteristics of inner heating and microwave is to the activation of substance reaction and the inductivity of process change, reduces the required activation energy of carbon source precursor gas pyrolysis, change kinetics, optionally promote reaction and improve the orientation reaction activity.Finally make carbon source precursor gas in matrix 16 surperficial pyrolysis, gas-phase growth of carbon fibre, i.e. step (3).
In addition, gas is about 0.1-0.5 second in the holdup time on matrix 16 surfaces, and the concrete holdup time can be controlled by flow velocity.In the delay process of gas, gas is not having under the condition of catalyst, by the introducing of electromagnetic field, and the design in flow field, the regulation and control of gas flow and concentration, the structural design of matrix 16 realizes gas-phase carbon fiber growth or array growth.Thereby the method for the gas-phase growth of carbon fibre of the embodiment of the invention at the matrix surface grown carbon fiber, adopts the non-catalytic growth pattern for directly.Wherein, carbon fiber mainly comprises CNT, and certainly by the change condition, also can grow solid carbon fiber and/or hollow carbon fiber is CNT.
Below be the method exemplifying embodiment of gas-phase growth of carbon fibre of the present invention, to describe the concrete operations technology of this method in detail.
Embodiment one
As shown in Figure 1, earlier matrix 16 is placed in the quartz ampoule 14, matrix 16 feeds the preceding body gas of carbon source with the gap 15 of quartz ampoule 14.Present embodiment adopts the matrix of aluminium oxide material, and methane gas is a carbon source precursor gas, and nitrogen is carrier gas and diluent, their mist 18 is fed from entering the mouth, the holdup time of gas is 0.5s, adopts the microwave source that is positioned at the upper and lower part, forms microwave 17 and adds hot basal body 16, heating reaches the pyrolysis temperature of presoma namely for methane gas, temperature maintenance is at 1300 ℃, and the pyrolytic deposition through 1 hour can make carbon fiber, as shown in Figure 4, carbon fiber has array format.
Embodiment two
As shown in Figure 1, earlier matrix 16 is placed in the quartz ampoule 14, matrix 16 feeds the preceding body gas of carbon source with the gap 15 of quartz ampoule 14.Present embodiment adopts the matrix of aluminium oxide material, propylene gas is the carbon source presoma, nitrogen is carrier gas and diluent, their mist is fed from inlet, and the holdup time of gas is 0.3s, adopts the microwave source that is positioned at the upper and lower part to add hot basal body, heating reaches the presoma pyrolysis temperature, temperature maintenance is at 1100 ℃, and the pyrolytic deposition through 1 hour can make carbon fiber as shown in Figure 4.
Embodiment three
As shown in Figure 1, earlier matrix 16 is placed in the quartz ampoule 14, matrix 16 feeds the preceding body gas of carbon source with the gap 15 of quartz ampoule 14.Present embodiment adopts the matrix of aluminium oxide material, acetylene gas is the carbon source presoma, nitrogen is carrier gas and diluent, their mist is fed from inlet, and the holdup time of gas is 0.1s, adopts the microwave source that is positioned at the upper and lower part to add hot basal body, heating reaches the presoma pyrolysis temperature, temperature maintenance is at 900 ℃, and the pyrolytic deposition through 1 hour can make carbon fiber as shown in Figure 4.
Embodiment four
As shown in Figure 1, earlier matrix 16 is placed in the quartz ampoule 14, matrix 16 feeds the preceding body gas of carbon source with the gap 15 of quartz ampoule 14.Present embodiment adopts the matrix of carbon/carbon compound material, methane gas is the carbon source presoma, nitrogen is carrier gas and diluent, and their mist is fed from inlet, and the holdup time of gas is 0.1s, the microwave source that employing is positioned at the upper and lower part adds hot basal body, heating reaches the presoma pyrolysis temperature, and temperature maintenance is at 1200 ℃, the pyrolytic deposition through 1 hour, can make the carbon fiber of vapor phase growth, as shown in Figure 5.
Embodiment five
As shown in Figure 1, earlier matrix 16 is placed in the quartz ampoule 14, matrix 16 feeds the preceding body gas of carbon source with the gap 15 of quartz ampoule 14.Present embodiment adopts silicon carbide substrate, methane gas is the carbon source presoma, nitrogen is carrier gas and diluent, and their mist is fed from inlet, and the holdup time of gas is 0.1s, the microwave source that employing is positioned at the upper and lower part adds hot basal body, heating reaches the presoma pyrolysis temperature, and temperature maintenance is at 1300 ℃, the pyrolytic deposition through 1 hour, can make the carbon fiber of vapor phase growth, as shown in Figure 6.
Embodiment six
As shown in Figure 1, earlier matrix 16 is placed in the quartz ampoule 14, matrix 16 feeds the preceding body gas of carbon source with the gap 15 of quartz ampoule 14.Present embodiment adopts the matrix of aluminium oxide material, methane gas is the carbon source presoma, and nitrogen is carrier gas and diluent, and their mist is fed from inlet, the holdup time of gas is 0.1s, the microwave source that employing is positioned at the upper and lower part adds hot basal body, and heating reaches the presoma pyrolysis temperature, and temperature maintenance is at 1100 ℃, pyrolytic deposition through 1 hour, can make the carbon fiber of vapor phase growth, this carbon fiber can obviously find out it is the CNT form, as shown in Figure 7.
In each embodiment described above, each matrix or carbon source presoma and process conditions can combined crosswise be used, and are not limited to the combination shown in the above embodiment.Said method adopts the method for heating using microwave, be subjected to microwave action by polar substances, non-thermal effect with the fast characteristics of spontaneous heating and firing rate and microwave is to the activation of substance reaction and the inductivity of process change, reduced activation energy, changed kinetics, thereby optionally promote reaction and improve the orientation reaction activity, be easy to the matrix surface gas-phase growth of carbon fibre.In addition, the method for this gas-phase growth of carbon fibre does not need extra catalyst as growth " seed ", but directly at the matrix surface grown carbon fiber.
The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1, a kind of method of gas-phase growth of carbon fibre may further comprise the steps:
Matrix is placed reaction cavity, and charge into carbon source precursor gas;
Adopt microwave that matrix is heated, make substrate temperature between 900 ℃ to 1300 ℃;
Carbon source precursor gas has the matrix surface pyrolysis of described temperature, and vapor phase growth goes out carbon fiber.
2, the method for gas-phase growth of carbon fibre as claimed in claim 1 is characterized in that: described fiber is grown by the non-catalytic mode at matrix surface.
3, the method for gas-phase growth of carbon fibre as claimed in claim 1 is characterized in that: described heating steps comprises by microwave matrix and precursor gas is heated.
4, the method for gas-phase growth of carbon fibre as claimed in claim 1 is characterized in that: described carbon source precursor gas comprises methane, acetylene or propylene.
5, the method for gas-phase growth of carbon fibre as claimed in claim 4 is characterized in that: described carbon source precursor gas also is mixed with nitrogen.
6, the method for gas-phase growth of carbon fibre as claimed in claim 1 is characterized in that: do not contain hydrogen in the described carbon source precursor gas.
7, the method for gas-phase growth of carbon fibre as claimed in claim 1 is characterized in that: the fiber of described vapor phase growth comprises CNT.
8, the method for gas-phase growth of carbon fibre as claimed in claim 1 is characterized in that: described carbon source precursor gas is 0.1-0.5 second in the holdup time of matrix surface.
9, the method for gas-phase growth of carbon fibre as claimed in claim 1 is characterized in that: the material of described matrix comprises aluminium oxide, carbon/carbon compound material or carborundum.
10, the method for gas-phase growth of carbon fibre as claimed in claim 1 is characterized in that: described reaction cavity is a quartz ampoule, forms the gap between described matrix and the quartz ampoule, is passed through by the gap to allow described carbon source precursor gas.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502578A (en) * | 2011-10-26 | 2012-06-20 | 上海交通大学 | Chemical vapor synthesis method for growing carbon nanotubes in mode of being attached to wall of pore channel of template |
| CN105349161A (en) * | 2015-11-06 | 2016-02-24 | 河北工业大学 | Method for producing hydrogen and carbon nanotubes through pyrolysis of waste tyres and biomass |
| CN105908491A (en) * | 2016-05-31 | 2016-08-31 | 哈尔滨工业大学 | Device and method for preparation of continuous carbon fiber with carbon nanotubes growing on surface |
| CN106587002A (en) * | 2016-11-23 | 2017-04-26 | 东莞劲胜精密组件股份有限公司 | Preparation method for carbon micro-tube |
| CN107338508A (en) * | 2017-06-15 | 2017-11-10 | 华南理工大学 | A kind of method of self-catalysis chemical vapor deposition synthesis overlength solid carbon fiber |
| CN109518306A (en) * | 2018-12-12 | 2019-03-26 | 深圳烯湾科技有限公司 | Modified carbon nano tube fiber and its preparation method and application |
| CN111019243A (en) * | 2019-12-12 | 2020-04-17 | 西北工业大学 | Modified carbon nanotube reinforced ethylene propylene diene monomer rubber heat-insulating material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1676664A (en) * | 2004-04-01 | 2005-10-05 | 中南大学 | Method for rapidly preparing carbon/carbon composite material under physics field by CVD |
| CN101270470B (en) * | 2008-05-07 | 2011-01-12 | 中南大学 | Method for synthesizing non-metal catalyst self-organizing growth carbon nano-tube with chemical vapor deposition |
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2009
- 2009-01-09 CN CN200910104869A patent/CN101476176B/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502578A (en) * | 2011-10-26 | 2012-06-20 | 上海交通大学 | Chemical vapor synthesis method for growing carbon nanotubes in mode of being attached to wall of pore channel of template |
| CN102502578B (en) * | 2011-10-26 | 2013-11-13 | 上海交通大学 | Chemical vapor synthesis method for growing carbon nanotubes in mode of being attached to wall of pore channel of template |
| CN105349161A (en) * | 2015-11-06 | 2016-02-24 | 河北工业大学 | Method for producing hydrogen and carbon nanotubes through pyrolysis of waste tyres and biomass |
| CN105908491A (en) * | 2016-05-31 | 2016-08-31 | 哈尔滨工业大学 | Device and method for preparation of continuous carbon fiber with carbon nanotubes growing on surface |
| CN105908491B (en) * | 2016-05-31 | 2018-04-10 | 哈尔滨工业大学 | Preparing superficial growth has the apparatus and method of continuous carbon fibre of CNT |
| CN106587002A (en) * | 2016-11-23 | 2017-04-26 | 东莞劲胜精密组件股份有限公司 | Preparation method for carbon micro-tube |
| CN107338508A (en) * | 2017-06-15 | 2017-11-10 | 华南理工大学 | A kind of method of self-catalysis chemical vapor deposition synthesis overlength solid carbon fiber |
| CN107338508B (en) * | 2017-06-15 | 2020-06-19 | 华南理工大学 | Method for synthesizing ultralong solid carbon fiber by autocatalysis chemical vapor deposition |
| CN109518306A (en) * | 2018-12-12 | 2019-03-26 | 深圳烯湾科技有限公司 | Modified carbon nano tube fiber and its preparation method and application |
| CN111019243A (en) * | 2019-12-12 | 2020-04-17 | 西北工业大学 | Modified carbon nanotube reinforced ethylene propylene diene monomer rubber heat-insulating material and preparation method thereof |
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| CN101476176B (en) | 2012-09-19 |
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