CN108625159A - Device and method for carbon cloth surface homoepitaxial carbon nanotube - Google Patents
Device and method for carbon cloth surface homoepitaxial carbon nanotube Download PDFInfo
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- CN108625159A CN108625159A CN201710181858.6A CN201710181858A CN108625159A CN 108625159 A CN108625159 A CN 108625159A CN 201710181858 A CN201710181858 A CN 201710181858A CN 108625159 A CN108625159 A CN 108625159A
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- reaction chamber
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- carbon nanotube
- carbon cloth
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 96
- 239000004744 fabric Substances 0.000 title claims abstract description 79
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 77
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 230000009467 reduction Effects 0.000 claims abstract description 34
- 239000011261 inert gas Substances 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 16
- 239000012298 atmosphere Substances 0.000 claims abstract description 15
- 238000010792 warming Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000009826 distribution Methods 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 5
- 238000009938 salting Methods 0.000 claims description 5
- 239000007770 graphite material Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000002787 reinforcement Effects 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- -1 Fig. 1 Chemical compound 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45561—Gas plumbing upstream of the reaction chamber
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45587—Mechanical means for changing the gas flow
- C23C16/45591—Fixed means, e.g. wings, baffles
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The invention discloses a kind of device and methods for carbon cloth surface homoepitaxial carbon nanotube, belong to the preparation field of carbon nanotube.The device in carbon cloth surface homoepitaxial carbon nanotube of the present invention, including vacuum reaction chamber and water power component；The method in carbon cloth surface homoepitaxial carbon nanotube of the present invention, includes the following steps：Step 1：The carbon cloth of destarch back loading Catalyst precursor solutions is wrapped on holder and is put into vacuum reaction chamber；Step 2：Vacuum reaction chamber is warming up to reduction temperature under atmosphere of inert gases；Step 3：The reduction that hydrogen carries out catalyst is passed through into the vacuum reaction chamber in step 2；Step 4：After reduction, vacuum reaction chamber is made to be warming up to growth temperature under atmosphere of inert gases；The present invention can realize the homoepitaxial of carbon nanotube on carbon cloth surface, reach the industrialization purpose of large-scale production.
Description
Technical field
The invention belongs to the preparation fields of carbon nanotube, and in particular to be used for carbon cloth surface homoepitaxial carbon nanotube
Device and method.
Background technology
Carbon cloth reinforced resin based composites are high with specific strength, specific modulus is high, density is low, thermal conductivity is good, heat is swollen
The excellent performances such as swollen coefficient is small, there is very wide application prospect.But due to carbon cloth surface is smooth and surface energy compared with
Low, weaker with the interface binding force of matrix resin, when composite material stress, carbon cloth is easy to happen unsticking with matrix resin,
This defect largely limits the raising of Mechanical Behavior of Carbon Fiber Reinforced Polymer.Carbon nanotube has outstanding
Mechanics, electric property, tensile strength are up to 30GPa, and it is multiple can to improve carbon cloth reinforced resin base as secondary reinforcement
The mechanical property and electrical and thermal conductivity performance of condensation material.
Commonly use the methods of chemical vapor deposition at present improves its smooth surface in carbon cloth surface load carbon nanotube,
The Interface adhesive strength of carbon cloth and resin is improved, but current research is confined to a small amount of carbon cloth sample, efficiency more
It is relatively low, it not yet realizes and grows carbon nanotube on large area carbon cloth surface, large-scale industrial production can not be carried out, simultaneously
The carbon nanotube that carbon cloth surface is grown is uneven, restricts the development of this experimental field.
Invention content
The technical problem to be solved in the present invention is to provide a kind of dresses for carbon cloth surface homoepitaxial carbon nanotube
It sets and method, overcomes the problems, such as that homoepitaxial carbon nanotube can not be carried out on large area carbon cloth surface in current technology, reach
To the industrialization purpose of large-scale production.
In order to solve the above technical problems, present invention offer technical solution is as follows：
A kind of device for carbon cloth surface homoepitaxial carbon nanotube, including vacuum reaction chamber and water power component；
The porous pump-line and vacuum elements that the top setting of the vacuum reaction chamber is connected with each other, the porous pumping
4 aspirating holes are uniformly provided on pipeline, the vacuum elements include vacuum pump；
Gas distribution plate is set at the upward 5cm in bottom end of the vacuum reaction chamber, 8-10 is provided in the gas distribution plate
A circular hole；
The bottom end of the vacuum reaction chamber is provided with gas supply assembly, and the gas supply assembly includes one and is connected with air inlet
Main pipeline；
The inner wall of the vacuum reaction chamber is provided with pressure sensor device and thermocouple；
The vacuum reaction chamber is internally provided with holder；
The water power component includes water circulation system, recirculated water cooling condenser and circuit control system.
Further, the vacuum reaction chamber is graphite material, and the porous pump-line and gas distribution plate are stainless
Steel material.
Further, the porous pump-line is circular ring shape pipeline, and the aspirating hole is the circular hole of diameter 1cm.
Further, the main pipeline includes three secondary ducts.
The present invention also provides a kind of methods for carbon cloth surface homoepitaxial carbon nanotube, include the following steps：
Step 1：The carbon cloth of destarch back loading Catalyst precursor solutions is wrapped on holder and is put into vacuum reaction
Room；
Step 2：Vacuum reaction chamber is warming up to reduction temperature under atmosphere of inert gases；
Step 3：The reduction that hydrogen carries out catalyst is passed through into the vacuum reaction chamber in step 2；
Step 4：After reduction, vacuum reaction chamber is made to be warming up to growth temperature under atmosphere of inert gases；
Step 5：The growth that carbon source mixed gas carries out carbon nanotube is passed through into the vacuum reaction chamber in step 4.
Further, the temperature of destarch is 400-500 DEG C in the step 1, the salt of catalyst precursor Co, Ni, Cu
One or more in solution, the pressure of vacuum reaction chamber is 0.01-0.03Mpa.
Further, the reduction temperature in the step 2 is 400-500 DEG C.Inert gas is nitrogen or argon gas.
Further, the hydrogen flowing quantity in the step 3 is 6-10L/min, and the time of reduction is 30min-60min.
Further, the growth temperature in the step 4 is 600-700 DEG C.Inert gas is nitrogen or argon gas.
Further, the carbon source mixed gas in the step 5 is hydrocarbon compound, hydrogen and nitrogen；The hydro carbons
The flow for closing object gas is 5-10L/min, the flow 5-10L/min of hydrogen, the flow 10-20L/min of nitrogen.
The invention has the advantages that：
It is of the invention can overcome the deficiencies in the prior art, provided for carbon cloth surface homoepitaxial carbon nanotube
Device is equipped with gas dispersion apparatus, and uniform point of carbon-source gas in furnace chamber is realized by flow distribution plate and porous pump-line
Cloth solves the problems, such as that growth carbon nanotube is non-uniform on large area carbon cloth；It is used for carbon cloth using the present invention
The method of surface homoepitaxial carbon nanotube can reach extensive in large area carbon cloth surface homoepitaxial carbon nanotube
The industrialization purpose of production.And process is easy to operate, improves the performance of carbon cloth/carbon nanotube multi-scale reinforcing body.
Description of the drawings
Fig. 1 is the structural schematic diagram of the device for carbon cloth surface homoepitaxial carbon nanotube of the present invention；
Fig. 2 is carbon cloth/carbon nanotube obtained after the homoepitaxial carbon nanotube of carbon cloth surface of the present invention
The scanning electron microscopic picture of multi-scale reinforcing body；
Fig. 3 is the flow diagram for carbon cloth surface homoepitaxial carbon nanotube of the present invention.
Specific implementation mode
The present invention provides a kind of device and methods for carbon cloth surface homoepitaxial carbon nanotube, to make this hair
Bright purpose, technical solution and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that herein
Described specific embodiment is only used to explain the present invention, is not intended to limit the present invention.
On the one hand, the present invention provides a kind of device for carbon cloth surface homoepitaxial carbon nanotube, such as Fig. 1, packet
Include vacuum reaction chamber 5 and water power component；
The porous pump-line 1 and vacuum elements that the top setting of vacuum reaction chamber 5 is connected with each other, porous pump-line 1
On be uniformly provided with 4 aspirating holes, vacuum elements include vacuum pump 2；
Gas distribution plate 6 is set at the upward 5cm in bottom end of vacuum reaction chamber 5,8-10 circle is provided in gas distribution plate 6
Hole；
The bottom end of vacuum reaction chamber 5 is provided with gas supply assembly, and gas supply assembly includes a main pipeline being connected with air inlet 7
11；
The inner wall of vacuum reaction chamber 5 is provided with pressure sensor device 4 and thermocouple；
Vacuum reaction chamber 5 is internally provided with holder 3；
Water power component includes water circulation system, recirculated water cooling condenser and circuit control system.
The device for carbon cloth surface homoepitaxial carbon nanotube of the present invention is equipped with gas dispersion apparatus, wherein
Gas is uniformly passed through vacuum reaction chamber 5 by the circular hole being arranged in gas distribution plate 6, and porous pump-line 1 is used for gas is uniform
Extraction solves to realize carbon-source gas being uniformly distributed in furnace chamber and grows carbon nanotube not on large area carbon cloth
Uniform problem.In addition other are arranged, as pressure sensor device 4 and thermocouple react indoor temperature and pressure for at-once monitor
Power；Water power component can preferably control the heating and cooling of vacuum reaction chamber 5 in experiment；These are all to prepare composite wood in next step
Material provides excellent basis.
As a further improvement on the present invention, vacuum reaction chamber 5 is graphite material, the porous pump-line 1 and gas
Flow distribution plate 6 is stainless steel.Graphite material heat-resisting quantity, thermal conductivity are good, and stainless steel is heat-resisting, high temperature resistant, and plastic
Property is good.
Further, porous pump-line 1 is circular ring shape pipeline, and the aspirating hole is the circular hole of diameter 1cm；Circular hole is set
It is equipped with conducive to gas is uniformly extracted out, to make gas be uniformly distributed in vacuum reaction room.
Preferably, main pipeline 11 includes three secondary ducts 8,9,10, and secondary duct connects with each gas bomb respectively, is respectively used to
Hydrogen, inert gas and carbon source mixed gas are conveyed into vacuum reaction room.
The practicality easy to operate of the device of the invention winds the carbon cloth of destarch back loading Catalyst precursor solutions
Vacuum reaction chamber 5 is put on holder 3, before the homoepitaxial carbon nanotube of carbon cloth surface, first turning on vacuum pump 2 will
Air pumps in vacuum reaction chamber 5, then opens secondary duct 9 and is passed through inert gas into vacuum reaction chamber 5, adjusts air flow rate
To OK range, make to be inert gas atmosphere, subsequent set temperature program, by adjusting different growth temperature in vacuum reaction room
Degree, growth time and gas flow carry out the experiment of different technical parameters.
On the other hand, the present invention also provides a kind of method for carbon cloth surface homoepitaxial carbon nanotube, with
Illustrate in lower embodiment.
Embodiment 1
A method of it being used for carbon cloth surface homoepitaxial carbon nanotube, is included the following steps：
Step 1：The carbon cloth of destarch back loading Catalyst precursor solutions is wrapped on holder and is put into vacuum reaction
Room；Wherein the temperature of destarch is 400 DEG C, and catalyst precursor is the salting liquid of Co, and the pressure of vacuum reaction chamber is 0.01Mpa.
Step 2：Vacuum reaction chamber is warming up to reduction temperature under atmosphere of inert gases；Wherein reduction temperature is 400 DEG C.
Inert gas is nitrogen.
Step 3：The reduction that hydrogen carries out catalyst is passed through into the vacuum reaction chamber in step 2；Wherein hydrogen flowing quantity is
The time of 6L/min, reduction are 30min.
Step 4：After reduction, vacuum reaction chamber is made to be warming up to growth temperature under atmosphere of inert gases；Wherein grow
Temperature is 600 DEG C.Inert gas is nitrogen.
Step 5：The growth that carbon source mixed gas carries out carbon nanotube is passed through into the vacuum reaction chamber in step 4；Wherein
Carbon source mixed gas is hydrocarbon compound, hydrogen and nitrogen；The flow of the hydrocarbon compound gas is 5L/min, the stream of hydrogen
Measure 5L/min, the flow 10L/min of nitrogen.
Vacuum reaction chamber carries out cooling down under nitrogen atmosphere after growth 10min, and it is more to obtain carbon cloth/carbon nanotube
Scale reinforcement.
Embodiment 2
A method of it being used for carbon cloth surface homoepitaxial carbon nanotube, is included the following steps：
Step 1：The carbon cloth of destarch back loading Catalyst precursor solutions is wrapped on holder and is put into vacuum reaction
Room；Wherein the temperature of destarch is 450 DEG C, and catalyst precursor is the salting liquid of Ni, and the pressure of vacuum reaction chamber is 0.02Mpa.
Step 2：Vacuum reaction chamber is warming up to reduction temperature under atmosphere of inert gases；Wherein reduction temperature is 400 DEG C.
Inert gas is argon gas.
Step 3：The reduction that hydrogen carries out catalyst is passed through into the vacuum reaction chamber in step 2；Wherein hydrogen flowing quantity is
The time of 8L/min, reduction are 60min.
Step 4：After reduction, vacuum reaction chamber is made to be warming up to growth temperature under atmosphere of inert gases；Wherein grow
Temperature is 600 DEG C.Inert gas is argon gas.
Step 5：The growth that carbon source mixed gas carries out carbon nanotube is passed through into the vacuum reaction chamber in step 4；Wherein
Carbon source mixed gas is hydrocarbon compound, hydrogen and nitrogen；The flow of the hydrocarbon compound gas is 8L/min, the stream of hydrogen
Measure 8L/min, the flow 15L/min of nitrogen.
Vacuum reaction chamber carries out cooling down under nitrogen atmosphere after growth 10min, and it is more to obtain carbon cloth/carbon nanotube
Scale reinforcement.
Embodiment 3
A method of it being used for carbon cloth surface homoepitaxial carbon nanotube, is included the following steps：
Step 1：The carbon cloth of destarch back loading Catalyst precursor solutions is wrapped on holder and is put into vacuum reaction
Room；Wherein the temperature of destarch is 500 DEG C, and catalyst precursor is the salting liquid of Cu, and the pressure of vacuum reaction chamber is 0.03Mpa.
Step 2：Vacuum reaction chamber is warming up to reduction temperature under atmosphere of inert gases；Wherein reduction temperature is 450 DEG C.
Inert gas is argon gas.
Step 3：The reduction that hydrogen carries out catalyst is passed through into the vacuum reaction chamber in step 2；Wherein hydrogen flowing quantity is
The time of 10L/min, reduction are 60min.
Step 4：After reduction, vacuum reaction chamber is made to be warming up to growth temperature under atmosphere of inert gases；Wherein grow
Temperature is 600 DEG C.Inert gas is argon gas.
Step 5：The growth that carbon source mixed gas carries out carbon nanotube is passed through into the vacuum reaction chamber in step 4；Wherein
Carbon source mixed gas is hydrocarbon compound, hydrogen and nitrogen；The flow of the hydrocarbon compound gas is 10L/min, hydrogen
Flow 10L/min, the flow 20L/min of nitrogen.
Vacuum reaction chamber carries out cooling down under nitrogen atmosphere after growth 5min, and it is more to obtain carbon cloth/carbon nanotube
Scale reinforcement.
Embodiment 4
A method of it being used for carbon cloth surface homoepitaxial carbon nanotube, is included the following steps：
Step 1：The carbon cloth of destarch back loading Catalyst precursor solutions is wrapped on holder and is put into vacuum reaction
Room；Wherein the temperature of destarch is 500 DEG C, and catalyst precursor is the salting liquid of Co, and the pressure of vacuum reaction chamber is 0.03Mpa.
Step 2：Vacuum reaction chamber is warming up to reduction temperature under atmosphere of inert gases；Wherein reduction temperature is 450 DEG C.
Inert gas is nitrogen.
Step 3：The reduction that hydrogen carries out catalyst is passed through into the vacuum reaction chamber in step 2；Wherein hydrogen flowing quantity is
The time of 10L/min, reduction are 60min.
Step 4：After reduction, vacuum reaction chamber is made to be warming up to growth temperature under atmosphere of inert gases；Wherein grow
Temperature is 700 DEG C.Inert gas is nitrogen.
Step 5：The growth that carbon source mixed gas carries out carbon nanotube is passed through into the vacuum reaction chamber in step 4；Wherein
Carbon source mixed gas is hydrocarbon compound, hydrogen and nitrogen；The flow of the hydrocarbon compound gas is 10L/min, hydrogen
Flow 10L/min, the flow 20L/min of nitrogen.
Vacuum reaction chamber carries out cooling down under nitrogen atmosphere after growth 10min, and it is more to obtain carbon cloth/carbon nanotube
Scale reinforcement.
From the point of view of the carbon cloth obtained from the combination of device and embodiment 1-4/carbon nanotube multi-scale reinforcing body, such as Fig. 2,
Carbon cloth surface grow be uniformly distributed, the carbon nanotube of marshalling, and the caliber of carbon nanotube is smaller, distribution compared with
It is narrow, concentrate on 20nm or so.Growth temperature control is at 600 DEG C, and growth time is controlled in 10min, when the reduction temperature of catalyst
When degree is 450 DEG C, under conditions of the recovery time is 30min, the catalyst precursor on carbon cloth surface be reduced into substantially for
Particle size is the catalyst granules of 20nm or so, further grows carbon nanotube in carbon cloth surface catalysis；Work as catalysis
When the recovery time of agent extends to 60min, the catalyst precursor on carbon cloth surface is reduced more abundant, fibre bundle table
It is surface catalysis agent even particle distribution, regular, and then the carbon nanotube pattern grown is more preferable, and be distributed more uniform.
Carbon fiber surface growth carbon nanotube needs certain temperature condition, because the cracking of carbon source is needed in certain temperature
Degree is lower to carry out, and when control growth time is 10min, when growth temperature is 600 DEG C, carbon cloth surface, which is grown, to be evenly distributed
Carbon nanotube, illustrate at this temperature, catalyst can obtain activity and play catalytic effect, and growth temperature increase
When to 700 DEG C, the quantity of carbon nanotube increased, this is because when temperature is higher, carbon source catalytic pyrolysis speed is accelerated, activity
The concentration of carbon atom increases, to grow the carbon nanotube of more even compact on carbon cloth surface.
The recovery time of catalyst is controlled in 60min, is 600 DEG C in growth temperature, growth time is the item of 5min
Under part, carbon cloth surface grows uniform carbon nanotube, and caliber is in 20nm or so, and length is in 400nm or so；When growth
Between when extending to 10min, the quantity of carbon nanotubes on carbon cloth surface is more, and length of carbon nanotube increases to 600-700nm,
This is because with the increase of growth time, carbon-source gas, which constantly cracks, becomes active atoms of carbon, and carbon cloth surface is urged
Catalyst particles are fully utilized, and are catalyzed out greater number of carbon nanotube, and the carbon nanotube top catalyst grown is still
So there is catalytic activity, continue catalytic deposition active atoms of carbon, therefore the length of carbon nanotube increases.
Provided by the present invention for the device and method of carbon cloth surface homoepitaxial carbon nanotube, can overcome existing
The constraint of technology, on carbon cloth surface, homoepitaxial goes out carbon nanotube, reaches the industrialization purpose of large-scale production, tested
Journey such as Fig. 3.Growth for carbon cloth surface carbon nanotube typically uses tube furnace progress, can only carry out every time at present
A small amount of experiment, it is less efficient, and exist and grow non-uniform problem, it cannot achieve large-scale industrial production.First, this hair
It is bright to use big volume chemical vapor deposition unit, carbon cloth is wrapped in particular stent, makes carbon-source gas in Pintsch process
The active atoms of carbon generated afterwards passes through carbon cloth and in surface deposition growing carbon nanotube, to realize in large area carbon fiber
Carbon nanotube is grown on cloth.Secondly, the present invention includes the gas positioned at vacuum reaction chamber bottom by the way that gas dispersion apparatus is arranged
Flow distribution plate and porous pump-line positioned at vacuum reaction chamber top, make gas be uniformly distributed in vacuum reaction room.Wherein
The gas that gas distribution plate is used to main pipeline air inlet being passed through is evenly dispersed, and is taken out there are four uniformly being opened on porous pump-line
Stomata, for uniformly extracting gas out, to realize the homoepitaxial of carbon cloth surface carbon nanotube, to prepare in next step
Composite material provides excellent basis.
Each technical characteristic of embodiment described above can be combined arbitrarily, to keep description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, it can also make several improvements and retouch, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of device for carbon cloth surface homoepitaxial carbon nanotube, which is characterized in that including vacuum reaction chamber and
Water power component；
The porous pump-line and vacuum elements that the top setting of the vacuum reaction chamber is connected with each other, the porous pump-line
On be uniformly provided with 4 aspirating holes, the vacuum elements include vacuum pump；
Gas distribution plate is set at the upward 5cm in bottom end of the vacuum reaction chamber, 8-10 circle is provided in the gas distribution plate
Hole；
The bottom end of the vacuum reaction chamber is provided with gas supply assembly, and the gas supply assembly includes a supervisor being connected with air inlet
Road；
The inner wall of the vacuum reaction chamber is provided with pressure sensor device and thermocouple；
The vacuum reaction chamber is internally provided with holder；
The water power component includes water circulation system, recirculated water cooling condenser and circuit control system.
2. the device according to claim 1 for carbon cloth surface homoepitaxial carbon nanotube, which is characterized in that institute
It is graphite material to state vacuum reaction chamber, and the porous pump-line and gas distribution plate are stainless steel.
3. the device according to claim 2 for carbon cloth surface homoepitaxial carbon nanotube, which is characterized in that institute
It is circular ring shape pipeline to state porous pump-line, and the aspirating hole is the circular hole of diameter 1cm.
4. the device according to claim 1 for carbon cloth surface homoepitaxial carbon nanotube, which is characterized in that institute
It includes three secondary ducts to state main pipeline.
5. any methods for carbon cloth surface homoepitaxial carbon nanotube of claim 1-4, which is characterized in that
Including：
Step 1：The carbon cloth of destarch back loading Catalyst precursor solutions is wrapped on holder and is put into vacuum reaction chamber；
Step 2：Vacuum reaction chamber is warming up to reduction temperature under atmosphere of inert gases；
Step 3：The reduction that hydrogen carries out catalyst is passed through into the vacuum reaction chamber in step 2；
Step 4：After reduction, vacuum reaction chamber is made to be warming up to growth temperature under atmosphere of inert gases；
Step 5：The growth that carbon source mixed gas carries out carbon nanotube is passed through into the vacuum reaction chamber in step 4.
6. the method according to claim 5 in carbon cloth surface homoepitaxial carbon nanotube, which is characterized in that
The temperature of destarch is 400-500 DEG C in the step 1, one kind or more in the salting liquid of catalyst precursor Co, Ni, Cu
Kind, the pressure of vacuum reaction chamber is 0.01-0.03MPa.
7. the method according to claim 5 in carbon cloth surface homoepitaxial carbon nanotube, which is characterized in that
Reduction temperature in the step 2 is 400-500 DEG C, and inert gas is nitrogen or argon gas.
8. the method according to claim 5 in carbon cloth surface homoepitaxial carbon nanotube, which is characterized in that
Hydrogen flowing quantity in the step 3 is 6-10L/min, and the time of reduction is 30min-60min.
9. the method according to claim 5 in carbon cloth surface homoepitaxial carbon nanotube, which is characterized in that
Growth temperature in the step 4 is 600-700 DEG C, and inert gas is nitrogen or argon gas.
10. the method according to claim 5 in carbon cloth surface homoepitaxial carbon nanotube, feature exists
In the carbon source mixed gas in the step 5 is hydrocarbon compound, hydrogen and nitrogen；The flow of the hydrocarbon compound gas
For 5-10L/min, the flow 5-10L/min of hydrogen, the flow 10-20L/min of nitrogen.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109750492A (en) * | 2018-12-20 | 2019-05-14 | 山东大学 | A kind of surface treatment method of carbon cloth surfaces homoepitaxial carbon nanotube early period |
| CN109763319A (en) * | 2018-12-20 | 2019-05-17 | 山东大学 | A kind of process growing carbon nanotube in PAN base carbon fibre surface catalysis based on sulfur doping modified catalyst |
| CN110777532A (en) * | 2019-11-29 | 2020-02-11 | 山东大学 | Control method for uniformly growing carbon nanotubes on surface of graphite fiber film cloth |
| CN111876999A (en) * | 2020-07-31 | 2020-11-03 | 山东大学 | Carbon nanotube-carbon fiber multi-scale reinforcement and preparation method and application thereof |
| CN115538147A (en) * | 2022-09-26 | 2022-12-30 | 贵州梅岭电源有限公司 | Preparation method of three-dimensional fluorinated carbon fiber flexible electrode |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165209A (en) * | 1996-11-05 | 1997-11-19 | 中国科学院物理研究所 | Order arranged carbon Nanometre tube and its preparing method and special device |
| US20050287064A1 (en) * | 2002-06-24 | 2005-12-29 | Martine Mayne | Method and device for depositing carbon nanotubes or nitrogen-doped carbon nanotubes by means of pyrolysis |
| US20070110659A1 (en) * | 2005-10-13 | 2007-05-17 | Hon Hai Precision Industry Co., Ltd. | Apparatus and method for producing carbon nanotubes |
| US20070148530A1 (en) * | 2005-12-22 | 2007-06-28 | Industrial Technology Research Institute | Apparatus and substrate structure for growing carbon nanotubes |
| US20100278717A1 (en) * | 2006-12-08 | 2010-11-04 | Denso Corporation | Method and apparatus for manufacturing carbon nanotube |
| JP2011016701A (en) * | 2009-07-10 | 2011-01-27 | Showa Denko Kk | Apparatus for producing carbon nanotube |
| CN103088648A (en) * | 2013-01-25 | 2013-05-08 | 中国科学院新疆生态与地理研究所 | Preparation method for carbon fiber material with composite nano structure |
| CN104310372A (en) * | 2014-09-30 | 2015-01-28 | 张映波 | Method for directly growing carbon nano tube array on fiber substrate |
| CN104532548A (en) * | 2015-01-29 | 2015-04-22 | 中国兵器工业集团第五三研究所 | In-situ growth method for carbon nano tubes (CNTs) on carbon fiber surface |
-
2017
- 2017-03-24 CN CN201710181858.6A patent/CN108625159A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165209A (en) * | 1996-11-05 | 1997-11-19 | 中国科学院物理研究所 | Order arranged carbon Nanometre tube and its preparing method and special device |
| US20050287064A1 (en) * | 2002-06-24 | 2005-12-29 | Martine Mayne | Method and device for depositing carbon nanotubes or nitrogen-doped carbon nanotubes by means of pyrolysis |
| US20070110659A1 (en) * | 2005-10-13 | 2007-05-17 | Hon Hai Precision Industry Co., Ltd. | Apparatus and method for producing carbon nanotubes |
| US20070148530A1 (en) * | 2005-12-22 | 2007-06-28 | Industrial Technology Research Institute | Apparatus and substrate structure for growing carbon nanotubes |
| US20100278717A1 (en) * | 2006-12-08 | 2010-11-04 | Denso Corporation | Method and apparatus for manufacturing carbon nanotube |
| JP2011016701A (en) * | 2009-07-10 | 2011-01-27 | Showa Denko Kk | Apparatus for producing carbon nanotube |
| CN103088648A (en) * | 2013-01-25 | 2013-05-08 | 中国科学院新疆生态与地理研究所 | Preparation method for carbon fiber material with composite nano structure |
| CN104310372A (en) * | 2014-09-30 | 2015-01-28 | 张映波 | Method for directly growing carbon nano tube array on fiber substrate |
| CN104532548A (en) * | 2015-01-29 | 2015-04-22 | 中国兵器工业集团第五三研究所 | In-situ growth method for carbon nano tubes (CNTs) on carbon fiber surface |
Non-Patent Citations (1)
| Title |
|---|
| 钱苗根等: "《材料表面技术及其应用手册》", 30 November 1998, 机械工业出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109750492A (en) * | 2018-12-20 | 2019-05-14 | 山东大学 | A kind of surface treatment method of carbon cloth surfaces homoepitaxial carbon nanotube early period |
| CN109763319A (en) * | 2018-12-20 | 2019-05-17 | 山东大学 | A kind of process growing carbon nanotube in PAN base carbon fibre surface catalysis based on sulfur doping modified catalyst |
| CN109763319B (en) * | 2018-12-20 | 2020-01-17 | 山东大学 | Process method for catalytically growing carbon nanotubes on surface of PAN-based carbon fiber based on sulfur-doped modified catalyst |
| CN110777532A (en) * | 2019-11-29 | 2020-02-11 | 山东大学 | Control method for uniformly growing carbon nanotubes on surface of graphite fiber film cloth |
| CN111876999A (en) * | 2020-07-31 | 2020-11-03 | 山东大学 | Carbon nanotube-carbon fiber multi-scale reinforcement and preparation method and application thereof |
| CN111876999B (en) * | 2020-07-31 | 2021-11-30 | 山东大学 | Carbon nanotube-carbon fiber multi-scale reinforcement and preparation method and application thereof |
| CN115538147A (en) * | 2022-09-26 | 2022-12-30 | 贵州梅岭电源有限公司 | Preparation method of three-dimensional fluorinated carbon fiber flexible electrode |
| CN115538147B (en) * | 2022-09-26 | 2023-10-17 | 贵州梅岭电源有限公司 | Preparation method of three-dimensional carbon fluoride fiber flexible electrode |
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