CN110745810B - Preparation method for rapidly growing carbon nano-tube on surface of carbon cloth at low temperature - Google Patents

Preparation method for rapidly growing carbon nano-tube on surface of carbon cloth at low temperature Download PDF

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CN110745810B
CN110745810B CN201911055232.6A CN201911055232A CN110745810B CN 110745810 B CN110745810 B CN 110745810B CN 201911055232 A CN201911055232 A CN 201911055232A CN 110745810 B CN110745810 B CN 110745810B
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carbon cloth
carbon
low temperature
furnace
cloth
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CN110745810A (en
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王延相
姚志强
王成国
魏化震
秦建杰
崔博文
马子明
岳阳
王永博
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Shandong University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/26—Mechanical properties

Abstract

The invention relates to a preparation method for rapidly growing carbon nanotubes on the surface of carbon cloth at low temperature. The preparation method comprises the following steps: step 1: desizing the carbon cloth; step 2: oxidizing the desized carbon cloth; and step 3: iron nitrate and cobalt nitrate are mixed according to a molar ratio of 1: 1 preparing a catalyst ethanol solution, wherein the total concentration of metal ions in the solution is 0.05 mol/L; and 4, step 4: putting the carbon cloth obtained in the step 2 into the catalyst solution prepared in the step 3, soaking for 10min, taking out and airing at room temperature; and 5: putting the carbon cloth obtained in the step 4 into a CVD furnace, opening a vacuum pump, pumping the pressure in the furnace to a vacuum state, introducing nitrogen, adjusting the air flow to maintain the air pressure in the furnace at 0.01MPa, heating to 380-430 ℃ at a heating rate of 10 ℃/min, and introducing C once2H2、H2And controlling N2、C2H2And H2The flow ratio of the three gases is 10: 5: 5L/min. The pressure in the furnace is kept at 0.01MPa all the time. C is turned off after 10min of growth2H2、H2In N at2Cooled to room temperature under protection, and the sample is taken out.

Description

Preparation method for rapidly growing carbon nano-tube on surface of carbon cloth at low temperature
Technical Field
The invention belongs to the field of preparation of carbon nanotubes, and particularly relates to a preparation method for rapidly growing carbon nanotubes on the surface of carbon cloth at low temperature.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Carbon Nanotubes (CNTs) have excellent mechanical, electrical and thermal properties, and their strength and modulus are nearly superior to all other known materials. Has become a hot research point in the field of materials in recent years. The interface between carbon fiber and resin can be obviously improved by introducing the carbon nano tube to the surface of the Carbon Fiber (CF), and the thermal property, the electrical property, the mechanical property, the wear resistance and the like of the composite material prepared from the CNTs-CF reinforcement and the epoxy resin are higher than those of a pure carbon fiber composite material. There are many methods available to introduce carbon nanotubes onto the surface of carbon fibers. The chemical vapor deposition method has the advantages of simple equipment, easy operation, large-scale production and the like, and is a method for growing carbon nanotubes on the surface of carbon fibers with the greatest prospect.
Zhang Asian et al (carbon fiber surface in-situ solid phase synergetic growth of carbon nanotubes [ J ]. The composite science, 2017,34 (2): 352-357) grow carbon nanotubes on the surface of carbon fibers by taking nickel nitrate with different concentrations as a catalyst, taking thiophene as a growth promotion promoter, taking nitrogen as a protective gas, and keeping the temperature at 850 ℃ for 2 hours, so that the tensile strength of the obtained CNTs-CF reinforcement monofilament is reduced to some extent.
Chinese patent document CN1868869A discloses a method for growing carbon nanotubes on a carbon cloth substrate. The carbon nano tube is synthesized on the surface of the carbon cloth by taking natural gas as a carbon source, Ni powder and sublimed S powder as catalysts and Ar as protective gas. The method needs high temperature of 1050-1300 ℃ for synthesis and has longer growth time.
Chinese patent CN109750492A is a surface treatment method for carbon cloth surface to grow carbon nanotubes uniformly in the early stage, comprising the following steps: step 1: and (3) putting the commercial carbon cloth into a CVD furnace, and removing the surface sizing agent at high temperature to obtain the desized carbon cloth. Step 2: soaking the desized carbon cloth in 20-45% of H2O2Putting the solution into an oven, heating to 70-90 ℃, and preserving heat for 1-2 h. And cleaning and drying to obtain the carbon cloth with the treated surface. And step 3: will be provided withThe carbon cloth obtained in the step 2 is paved on 0.05mol/L Co (NO)3)2Soaking in the ethanol solution for 10min, and oven drying. And 4, step 4: loading Co (NO) in the step 33)2The carbon cloth is put in a CVD furnace, the furnace is pressed and vacuumized, and then high-purity N is added2Heating the furnace to 500-600 ℃ under protection, and introducing C2H2、H2And N2Keeping the temperature of the mixed gas for 3-20min, and closing the gas C2H2And H2In N at2The sample was taken out after cooling to room temperature under the protection of (1).
In the prior art, when carbon nanotubes grow on the surface of carbon fibers, the growth temperature is controlled to be over 600 ℃ or even over 1000 ℃, and a catalyst loaded on the surface of the carbon fibers can diffuse to the surface of the carbon fibers at high temperature, so that the carbon fibers are etched, and the mechanical properties of the carbon fibers are influenced. The etching effect is enhanced along with the increase of the growth temperature and the growth time of the carbon nano tube, and the mechanical property of the carbon fiber is seriously reduced.
Disclosure of Invention
In order to overcome the above problems, the present invention provides a method capable of rapidly growing carbon nanotubes on the surface of a carbon cloth at a relatively low temperature. The method can solve the problems that the efficiency of the existing process is low, and the mechanical property of the fiber is reduced due to serious fiber etching.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a preparation method for rapidly growing carbon nanotubes on the surface of carbon cloth at low temperature comprises the following steps:
desizing carbon cloth, oxidizing the surface of the carbon cloth, and carrying out vapor deposition CVD in the presence of ferric nitrate and cobalt nitrate to form the carbon nano tube.
The composite catalyst is adopted, the damage of the catalyst to the fiber is reduced by utilizing the synergy of the composite catalyst, the carbon nano tube is quickly synthesized on the surface of the carbon cloth at low temperature, and the mechanical property of the carbon fiber is obviously improved.
In some embodiments, the carbon cloth desizing specifically comprises the steps of preserving heat for 1-2 hours at 400-480 ℃ under the protection of inert gas, removing resin and other viscous substances coated on the surface of the carbon cloth, improving the roughness of the carbon cloth, and facilitating subsequent oxidation treatment.
In some embodiments, hydrogen peroxide is used as an oxidant for surface oxidation, heat preservation is carried out for 1.5 hours at the temperature of 60-80 ℃, and the carbon cloth is taken out and dried, so that the number of oxygen-containing functional groups on the surface of the carbon cloth is increased, and the loading capacity and the bonding strength between the carbon cloth and CNTs are improved.
In order to obtain a better catalytic effect, the proportion of the iron nitrate and the cobalt nitrate is preferably selected, so that in some embodiments, the molar ratio of the iron nitrate to the cobalt nitrate is 1-1.5: 1-1.5, high catalytic efficiency, reduced CNTs generation temperature and improved mechanical properties of carbon fibers.
With the increase of the concentration of metal ions, the generation amount of CNTs is increased; however, when the concentration of the metal ions is increased to a certain extent, the production of CNTs is not increased much by increasing the concentration of the metal ions. Therefore, in some embodiments, the ferric nitrate and the cobalt nitrate are dissolved in the ethanol solution, and the total concentration of metal ions in the solution is 0.03-0.08 mol/L, so that the production amount of CNTs is increased, and the cost is reduced.
In some embodiments, the carbon cloth after surface oxidation is immersed in an ethanol solution of ferric nitrate and cobalt nitrate for 8-12 min, so that the ferric nitrate and the cobalt nitrate are effectively loaded on the carbon cloth, and the subsequent catalytic effect is ensured.
With the increase of the CVD temperature, the diameter of the CNTs is increased, and the graphitization degree is improved; however, if the temperature is too high, the structural defects of the carbon fibers are increased and the mechanical properties are reduced, so in some embodiments, the pressure is 0.01-0.03 MPa, the reaction temperature is 380-430 ℃ and the gas composition is N-2、C2H2And H2So as to improve the uniformity and specific surface area of the load of the CNTs, and the mechanical property of the carbon nano tube/carbon cloth reinforcement body is also enhanced.
In some embodiments, the N2、C2H2And H2The flow ratio of (A) to (B) is 8-12: 3-8: 3-8, and the loading quality, catalysis and electrochemical properties of the CNTs are improved.
The invention also provides a carbon nano tube/carbon cloth reinforcement prepared by any one of the methods.
The invention also provides the application of the carbon nano tube/carbon cloth reinforcement in the fields of aerospace and oil and gas industry.
The invention has the beneficial effects that:
(1) the application provides a method for quickly synthesizing carbon nanotubes on the surface of carbon cloth at low temperature, which is simple in operation, saves time, is high in efficiency, and can reduce the damage of a catalyst to fibers. The method can overcome the defects of the prior art and solve the problems of high preparation temperature, long time and serious fiber etching of the prior art. The product can obviously improve the mechanical property of the carbon fiber.
(2) The operation method is simple, low in cost, universal and easy for large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
Fig. 1 is a scanning electron microscope picture of the carbon cloth obtained in example 1 of the present invention. (A) Growing carbon cloth of the carbon nano tube; (B) and the carbon nano tubes are uniformly dispersed and grown on the surface of the carbon cloth.
Fig. 2 is a scanning electron microscope picture of the carbon cloth obtained in example 2 of the present invention. (A) Growing carbon cloth of the carbon nano tube; (B) and the carbon nano tubes are uniformly dispersed and grown on the surface of the carbon cloth.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background section, for SnO2The preparation technology of the supported noble metal is complex, the cost is high, and the large-scale production is not easy to realize. Therefore, the invention provides a method for rapidly growing carbon nanotubes on the surface of carbon cloth at a relatively low temperature. The method can solve the problems that the efficiency of the existing process is low, and the mechanical property of the fiber is reduced due to serious fiber etching.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method for rapidly growing the carbon nano tube on the surface of the carbon cloth at low temperature comprises the following steps:
step 1: putting the carbon cloth into a vertical CVD furnace, heating to 450 ℃ under the protection of nitrogen, preserving heat for 1.5h, desizing the carbon cloth, cooling to room temperature and taking out;
step 2: putting the desized carbon cloth into a hydrogen peroxide solution with the concentration of 30 wt% and keeping the temperature at 70 ℃ for 1.5h, taking out, cleaning and drying;
and step 3: iron nitrate and cobalt nitrate are mixed according to a molar ratio of 1: 1 preparing a catalyst ethanol solution, wherein the total concentration of metal ions in the solution is 0.05 mol/L.
And 4, step 4: putting the carbon cloth obtained in the step 2 into the catalyst solution prepared in the step 3, soaking for 10min, taking out and airing at room temperature;
and 5: putting the carbon cloth obtained in the step 4 into a CVD furnace, opening a vacuum pump, pumping the pressure in the furnace to a vacuum state, introducing nitrogen, adjusting the air flow to maintain the air pressure in the furnace at 0.01MPa, heating to 380-430 ℃ at a heating rate of 10 ℃/min, and introducing C once2H2、H2And controlling N2、C2H2And H2The flow ratio of the three gases is 10: 5: 5L/min. The pressure in the furnace is kept at 0.01MPa all the time. C is turned off after 10min of growth2H2、H2In N at2Cooling to room under protectionWarm, take out the sample.
Wherein, the temperature for heat preservation in the step 2 can be 60-80 ℃, and 70 ℃ is preferred.
Wherein, the total concentration of the metal ions in the step 3 can be 0.03mol/L, 0.04mol/L, 0.05mol/L and 0.06 mol/L.
Wherein the reaction temperature in the step 5 may be 380-430 ℃. Preferably 400 deg.c.
Wherein, the growth time in the step 5 can be 5-15min, preferably 10 min.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1
Step 1: putting the carbon cloth into a vertical CVD furnace, heating to 450 ℃ under the protection of nitrogen, preserving heat for 1.5h, desizing the carbon cloth, cooling to room temperature and taking out;
step 2: putting the desized carbon cloth into a hydrogen peroxide solution with the concentration of 30 wt% and keeping the temperature at 70 ℃ for 1.5h, taking out, cleaning and drying;
and step 3: iron nitrate and cobalt nitrate are mixed according to a molar ratio of 1: 1 preparing a catalyst ethanol solution, wherein the total concentration of metal ions in the solution is 0.05 mol/L.
And 4, step 4: putting the carbon cloth obtained in the step 2 into the catalyst solution prepared in the step 3, soaking for 10min, taking out and airing at room temperature;
and 5: putting the carbon cloth obtained in the step 4 into a CVD furnace, opening a vacuum pump, pumping the pressure in the furnace to a vacuum state, introducing nitrogen, adjusting the air flow to maintain the air pressure in the furnace at 0.01MPa, heating to 430 ℃ at the heating rate of 10 ℃/min, and introducing C once2H2、H2And controlling N2、C2H2And H2The flow ratio of the three gases is 10: 5: 5L/min. The pressure in the furnace is kept at 0.01MPa all the time. C is turned off after 10min of growth2H2、H2In N at2Cooled to room temperature under protection, and the sample is taken out. The obtained carbon cloth monofilament for growing the carbon nano tube has higher tensile strength than the carbon cloth without the slurryThe height is 12.8 percent.
Fig. one is a scanning electron microscope picture of the carbon cloth obtained in example 1 of the present invention. (A) Growing carbon cloth of the carbon nano tube; (B) and the carbon nano tubes are uniformly dispersed and grown on the surface of the carbon cloth.
Example 2
Step 1: putting the carbon cloth into a vertical CVD furnace, heating to 450 ℃ under the protection of nitrogen, preserving heat for 1.5h, desizing the carbon cloth, cooling to room temperature and taking out;
step 2: putting the desized carbon cloth into a hydrogen peroxide solution with the concentration of 30 wt% and keeping the temperature at 70 ℃ for 1.5h, taking out, cleaning and drying;
and step 3: iron nitrate and cobalt nitrate are mixed according to a molar ratio of 1: 1 preparing a catalyst ethanol solution, wherein the total concentration of metal ions in the solution is 0.05 mol/L.
And 4, step 4: putting the carbon cloth obtained in the step 2 into the catalyst solution prepared in the step 3, soaking for 10min, taking out and airing at room temperature;
and 5: putting the carbon cloth obtained in the step 4 into a CVD furnace, opening a vacuum pump, pumping the pressure in the furnace to a vacuum state, introducing nitrogen, adjusting the air flow to maintain the air pressure in the furnace at 0.01MPa, heating to 400 ℃ at the heating rate of 10 ℃/min, and introducing C once2H2、H2And controlling N2、C2H2And H2The flow ratio of the three gases is 10: 5: 5L/min. The pressure in the furnace is kept at 0.01MPa all the time. C is turned off after 10min of growth2H2、H2In N at2Cooled to room temperature under protection, and the sample is taken out.
Fig. 2 is a scanning electron microscope picture of the carbon cloth obtained in example 2 of the present invention. (A) Growing carbon cloth of the carbon nano tube; (B) and the carbon nano tubes are uniformly dispersed and grown on the surface of the carbon cloth.
Comparative example 1
Step 1: putting the carbon cloth into a vertical CVD furnace, heating to 450 ℃ under the protection of nitrogen, preserving heat for 1.5h, desizing the carbon cloth, cooling to room temperature and taking out;
step 2: putting the desized carbon cloth into a hydrogen peroxide solution with the concentration of 30 wt% and keeping the temperature at 70 ℃ for 1.5h, taking out, cleaning and drying;
and step 3: preparing 0.05mol/L catalyst ethanol solution by using ferric nitrate.
And 4, step 4: putting the carbon cloth obtained in the step 2 into the catalyst solution prepared in the step 3, soaking for 10min, taking out and airing at room temperature;
and 5: putting the carbon cloth obtained in the step 4 into a CVD furnace, opening a vacuum pump, pumping the pressure in the furnace to a vacuum state, introducing nitrogen, adjusting the air flow to maintain the air pressure in the furnace at 0.01MPa, heating to 400 ℃ at the heating rate of 10 ℃/min, and introducing C once2H2、H2And controlling N2、C2H2And H2The flow ratio of the three gases is 10: 5: 5L/min. The pressure in the furnace is kept at 0.01MPa all the time. C is turned off after 10min of growth2H2、H2In N at2Cooled to room temperature under protection, and the sample is taken out.
Comparative example 2
Step 1: putting the carbon cloth into a vertical CVD furnace, heating to 450 ℃ under the protection of nitrogen, preserving heat for 1.5h, desizing the carbon cloth, cooling to room temperature and taking out;
step 2: putting the desized carbon cloth into a hydrogen peroxide solution with the concentration of 30 wt% and keeping the temperature at 70 ℃ for 1.5h, taking out, cleaning and drying;
and step 3: cobalt nitrate is used for preparing 0.05mol/L catalyst ethanol solution.
And 4, step 4: putting the carbon cloth obtained in the step 2 into the catalyst solution prepared in the step 3, soaking for 10min, taking out and airing at room temperature;
and 5: putting the carbon cloth obtained in the step 4 into a CVD furnace, opening a vacuum pump, pumping the pressure in the furnace to a vacuum state, introducing nitrogen, adjusting the air flow to maintain the air pressure in the furnace at 0.01MPa, heating to 400 ℃ at the heating rate of 10 ℃/min, and introducing C once2H2、H2And controlling N2、C2H2And H2The flow ratio of the three gases is 10: 5: 5L/min. The pressure in the furnace is kept at 0.01MPa all the time. C is turned off after 10min of growth2H2、H2In N at2Cooled to room temperature under protection, and the sample is taken out.
TABLE 1 comparison of the Properties of the carbon nanotube/carbon cloth reinforcement of the present application
Number/performance index Tensile Strength of monofilament (GPa)
Example 1 4.1
Example 2 4.0
Comparative example 1 3.0
Comparative example 2 3.3
The research shows that: the morphology of the carbon nano tube grown by the invention is almost not different from that of the carbon nano tube in the attached drawing of the inventor's prior patent CN109750492A, which shows that the invention can reduce the growth temperature of the carbon nano tube by about 100 ℃ and improve the mechanical property of the fiber.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.

Claims (8)

1. A preparation method for rapidly growing carbon nanotubes on the surface of carbon cloth at low temperature is characterized by comprising the following steps:
desizing carbon cloth, oxidizing the surface of the carbon cloth, and carrying out vapor deposition CVD in the presence of ferric nitrate and cobalt nitrate to form a carbon nano tube;
the molar ratio of the ferric nitrate to the cobalt nitrate is 1-1.5: 1 to 1.5;
in the vapor deposition process, the pressure is 0.01-0.03 MPa, the reaction temperature is 380-430 ℃, and the gas composition is N2、C2H2And H2。
2. The method for preparing carbon nanotubes rapidly growing on the surface of carbon cloth at low temperature according to claim 1, wherein the step of desizing the carbon cloth is to preserve heat at 400-480 ℃ for 1-2h under the protection of inert gas.
3. The method for preparing the carbon nano tube rapidly growing on the surface of the carbon cloth at the low temperature as claimed in claim 1, wherein hydrogen peroxide is used as an oxidant for surface oxidation, the temperature is kept at 60-80 ℃ for 1.5h, and the carbon nano tube is taken out and dried.
4. The method for preparing the carbon nano tube rapidly growing on the surface of the carbon cloth at the low temperature as claimed in claim 1, wherein the ferric nitrate and the cobalt nitrate are dissolved in an ethanol solution, and the total concentration of metal ions in the solution is 0.03-0.08 mol/L.
5. The method for preparing carbon nanotubes rapidly grown on the surface of carbon cloth at low temperature according to claim 1, wherein the carbon cloth after surface oxidation is immersed in an ethanol solution of ferric nitrate and cobalt nitrate for 8-12 min.
6. The method for preparing carbon nanotubes rapidly grown on the surface of carbon cloth at low temperature according to claim 1, wherein the N is N2、C2H2And H2The flow ratio of (A) to (B) is 8-12: 3-8: 3 to 8.
7. A carbon nanotube/carbon cloth reinforcement prepared by the method of any one of claims 1 to 6.
8. Use of the carbon nanotube/carbon cloth reinforcement of claim 7 in the aerospace and oil and gas industry applications.
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CN102433732A (en) * 2011-08-02 2012-05-02 华东理工大学 Method for synthesizing carbon nanotube array on quartz fiber surface
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CN109610159A (en) * 2018-12-20 2019-04-12 山东大学 A kind of preparation method growing carbon nanotube in carbon fibre fabric surface catalysis using bimetallic catalyst
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

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1720346A (en) * 2003-01-13 2006-01-11 南泰若股份有限公司 Methods of making carbon nanotube films, layers, fabrics, ribbons, elements and articles
CN101665248A (en) * 2009-09-11 2010-03-10 清华大学 Method for preparing single-walled and double-walled carbon nanotubes based on layered dihydroxy metal hydroxide
CN102267693A (en) * 2011-07-06 2011-12-07 天津理工大学 Low-temperature preparation method of carbon nanotube
CN102433732A (en) * 2011-08-02 2012-05-02 华东理工大学 Method for synthesizing carbon nanotube array on quartz fiber surface
CN103496688A (en) * 2013-09-18 2014-01-08 西南交通大学 Method for preparing carbon-based ternary network composite material
CN109610159A (en) * 2018-12-20 2019-04-12 山东大学 A kind of preparation method growing carbon nanotube in carbon fibre fabric surface catalysis using bimetallic catalyst
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

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