CN110820322B - Method for growing carbon nanotubes on carbon fibers by using combined action of sodium lignin sulfonate and bimetallic catalyst - Google Patents

Method for growing carbon nanotubes on carbon fibers by using combined action of sodium lignin sulfonate and bimetallic catalyst Download PDF

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CN110820322B
CN110820322B CN201911203623.8A CN201911203623A CN110820322B CN 110820322 B CN110820322 B CN 110820322B CN 201911203623 A CN201911203623 A CN 201911203623A CN 110820322 B CN110820322 B CN 110820322B
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carbon fiber
bimetallic catalyst
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carbon nanotubes
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CN110820322A (en
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王延相
马子明
王成国
魏化震
崔博文
王永博
岳阳
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Shandong University
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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
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    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • 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 relates to a method for growing carbon nanotubes on carbon fibers by using the combined action of lignin and a bimetallic catalyst. The preparation method comprises the following steps: step 1: winding the carbon fiber into a vertical CVD furnace, introducing nitrogen, and keeping the temperature at 450 ℃ for 1.5h to remove a sizing agent; step 2: the carbon fiber is electrolyzed and desized and is led into an electrolytic bath, and the electrolyte is NH4H2PO4Electrolyzing the aqueous solution, washing with water and drying; and step 3: loading catalyst with solute including ferric nitrate, nickel nitrate and sodium lignosulfonate and solvent including absolute alcohol, and stoving. And 4, step 4: introducing carbon fiber into a tube furnace, introducing N2And H2The temperature in the furnace is 450 ℃ and the time is 5min, the aim is to reduce the catalyst, then the carbon fiber is led into another tube furnace to grow the carbon nano tube, and the gas which is led in is N2、H2And C2H2The long tube time is 5 min. The method can overcome the problem of poor connection between the carbon nanotube and the carbon fiber, thereby improving the mechanical property of the treated carbon fiber.

Description

Method for growing carbon nanotubes on carbon fibers by using combined action of sodium lignin sulfonate and bimetallic catalyst
Technical Field
The invention belongs to the preparation of a multi-scale combination of carbon fibers and carbon nanotubes, and particularly relates to a method for catalytically growing carbon nanotubes on the surface of carbon fibers with a bimetallic catalyst and improving the connectivity of the carbon fibers and the carbon nanotubes by using lignin. The method can improve the mechanical property of the carbon fiber.
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 fiber reinforced polymer composite materials (CFRPs) have the characteristics of excellent high specific strength, high specific modulus, light weight, fatigue resistance, corrosion resistance and the like, and are increasingly widely applied in the fields of aerospace, military and industry, sports goods such as racket and club and the like. Because the surface of the carbonized carbon fiber is inert and smooth and has low surface energy, when the carbonized carbon fiber is combined with a resin matrix to prepare CFRPs, the interface phase of the carbonized carbon fiber is poor in binding property and often becomes the primary position of stress concentration and damage when an external force is applied, and the development and application of the CFRPs are severely restricted.
The performance of the carbon fiber composite material is mainly determined by the interface between the fibers and the matrix, and the good interface connection provides structural integrity for the composite material, so that the effective transmission and release of load are ensured. The surface of the untreated carbon fiber is smooth, and the composite material is easy to be debonded from the matrix when being stressed, so that the further improvement of the mechanical property of the composite material is limited. In recent years, Carbon Nanotubes (CNTs) are chemically grafted to the surface of carbon fibers to improve the mechanical properties of composite materials, which is a major scientific focus. The CNTs are introduced into the interface of the multi-scale reinforcement composite material, so that the interface combination of carbon fibers and resin is increased, and a transitional buffer interface is formed at the same time, so that the stress transfer and transfer effects can be effectively realized when external force load is applied, and the mechanical property of the CFRPS is remarkably improved. In addition, the CNTs have excellent mechanical properties, electrical properties, thermal properties and the like, so that the CFRP has more characteristics and a wider application range.
And carbon nanotubes can be grown on the surface of the carbon fiber by practicing a known Chemical Vapor Deposition (CVD) method.
The principle of growing carbon nanotubes on the surface of carbon fibers is C2H2When the carbon source gas is catalyzed by the metal simple substance, carbon atoms are cracked, and the carbon atoms are diffused under the catalysis of the metal particles to grow the carbon nano tube in a top growth mode. The metal is obtained by firstly adding on the carbon fiberCarrying a metal compound, and then introducing hydrogen for reduction to obtain a metal simple substance.
Zhenglibao et al (research on carbon nanotubes grown on the surface of continuous carbon fibers and their structural properties [ D ] Shandong university, 2018.) deposited on the surface of carbon fibers at 650 ℃ for 10min by using cobalt nitrate as a catalyst, methane as a carbon source and argon as a protective gas, thereby growing the carbon nanotubes on the surface of the carbon fibers and improving the graphitization degree of the carbon fibers.
Chinese patent document CN102199872A discloses a method for in-situ growth of carbon nanotubes on the surface of a fiber. The carbon nanotube is synthesized by using ethanol or acetone as a carbon source, ferrocene as a catalyst, sulfur-containing substances such as sulfur and thiophene as a cocatalyst and hydrogen or a mixed gas of hydrogen and other inert gases as a carrier gas. The method needs to be synthesized at the high temperature of 600-1000 ℃, and a horizontal electric furnace is used as a reaction device, so that the samples cannot be produced on a large scale.
Disclosure of Invention
In order to overcome the problems, the invention provides a production method which is simple to operate, convenient to copy and implement, high in efficiency and low in cost. The method solves the problems that the damage of the fiber is high due to the fact that a single metal catalyst is used for growing the carbon nano tube at a high temperature in the past, the carbon nano tube is easy to agglomerate on the surface of the fiber, the dispersibility is poor, the exertion of the mechanical property of the composite material is seriously influenced, and the carbon nano tube on the produced carbon fiber is not tightly connected with the carbon fiber and is easy to fall off.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a method of growing carbon nanotubes on carbon fibers using sodium lignosulfonate in conjunction with a bimetallic catalyst, comprising:
desizing, electrolytic oxidation and dipping of carbon fiber in a mixed solution of sodium lignosulfonate and a bimetallic catalyst, drying and then growing a carbon nanotube on the treated carbon fiber by adopting a chemical vapor deposition method.
The application solves the problems of uneven growth and poor connection effect of the carbon nano tube in the past, the effect of the double-metal catalyst is obviously better and more stable than that of the single-metal catalyst, lignin is introduced, the relation between the carbon nano tube and the carbon fiber is further strengthened, the production process is stable and controllable, and the continuous and industrial production is convenient.
In some embodiments, the desizing temperature is 450-460 ℃ and the heat is preserved for 1.5-2 h, so that the resin material on the surface is removed, and the strength of the carbon fiber is improved.
In some embodiments, the electrolyte is 5-6 wt% ammonium dihydrogen phosphate solution, and the electrolysis is carried out for 80-90 s under the condition that the current intensity is 0.4-0.5A. The property of strong electrolyte of ammonium dihydrogen phosphate is utilized, the price is low, and the subsequent lignin modification effect can be effectively improved due to the mild modification degree of the ammonium dihydrogen phosphate during electrolysis. In addition, the electrolysis is better to operate, the current intensity is controllable and stable, and the method is more economical in industrial production.
The specific type of the bimetallic catalyst is not particularly limited in this application, and in some embodiments, the bimetallic catalyst is composed of ferric nitrate and nickel sulfate to improve the bonding interface strength of the carbon nanotubes and the carbon fibers and the mechanical properties of the carbon fibers.
In some embodiments, the molar ratio of iron nitrate, nickel sulfate, and sodium lignosulfonate is 1: 1: 1 to 1.5. The carbon tube grows more uniformly under the condition of double catalysts, and the bonding interface strength of the carbon nanotube and the carbon fiber is also improved by adding lignin.
The catalytic efficiency is improved along with the improvement of the concentration of the metal ions, but when the concentration of the metal ions reaches a certain value, the improvement of the catalytic efficiency is not large by continuously increasing the concentration of the metal ions. In some embodiments, the total concentration of metal ions in the mixed solution of sodium lignosulfonate and the bimetallic catalyst is 0.01-0.05 mol/L, so that the catalytic efficiency is improved.
In some embodiments, the dipping time is 5-6 min by a wire-moving method. The dipping time is effectively controlled by controlling the wire moving speed.
In some embodiments, the chemical vapor deposition method comprises the steps of: reducing the catalyst, growing carbon nanotubes again, and finally recovering the filament bundle by using a filament collecting machine; reducing and lengthening the tube for 5min by controlling the filament feeding speed, and finally recovering the filament bundle by using a filament collecting machine.
In some embodiments, at N2、H2In the mixed gas of (2) to reduce the catalyst, N2、H2Is 1: 1-1.2, and the reduction efficiency and the reduction effect are improved.
The invention also provides a carbon nano tube/carbon fiber reinforcement prepared by any one of the methods.
The invention also provides the application of the carbon nano tube/carbon fiber reinforcement in the fields of aerospace, military and industry and sports goods, wherein the sports goods comprise a racket and a ball rod.
The invention has the beneficial effects that:
(1) the invention provides a production method with simple operation, feasible process flow and low cost, the method has the advantages of less damage to the fiber due to the reduction of the growth temperature of the carbon nano tube, more uniform growth of the carbon tube under the condition of double catalysts, and the addition of lignin also improves the bonding interface strength of the carbon nano tube and the carbon fiber. 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 microscope image of a carbon fiber obtained in example 1 of the present invention. (A) Growing carbon fiber fabric of carbon nanotubes; (B) and the carbon nanotubes are dispersed and uniformly grown on the surface of the carbon fiber fabric.
FIG. 2 is a scanning microscope image of carbon fibers obtained in example 2 of the present invention. (A) Growing carbon fiber fabric of carbon nanotubes; (B) and the carbon nanotubes are dispersed and uniformly grown on the surface of the carbon fiber fabric.
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 art, the method aims at the problems that the damage of the carbon nano tube grown by the existing single metal catalyst at a higher temperature to the fiber is high, the carbon nano tube is easy to agglomerate on the surface of the fiber, the dispersibility is poor, the exertion of the mechanical property of the composite material is seriously influenced, and the connection between the carbon nano tube and the carbon fiber on the produced carbon fiber is not very tight and is easy to fall off. Therefore, the invention provides a method for growing carbon nanotubes on carbon fibers by using the combined action of sodium lignin sulfonate and a bimetallic catalyst, which comprises the following steps:
step 1: putting the carbon fiber into a vertical CVD furnace, heating to 450 ℃ at a heating rate of 20 ℃/min in the atmosphere of nitrogen, preserving heat for 1.5h, removing a sizing agent on the surface of the fiber, cooling to room temperature, and taking out;
step 2: the carbon fiber fabric obtained in the step 1 is electrolyzed for 80s in an electrolytic bath filled with ammonium dihydrogen phosphate solution with the concentration of 5 percent by weight under the condition of 0.4A of current intensity, and then is dried in an oven after being washed to remove surface electrolyte;
and step 3: preparing a solution by using ferric nitrate, nickel sulfate and sodium lignin sulfonate with the same molar ratio as solutes and absolute ethyl alcohol as a solvent, wherein the total concentration of metal ions used as a catalyst is 0.05mol/L, and the concentration of lignin salts is also 0.05mol, introducing the carbon fiber subjected to electrolytic etching and treated in the step 2 into the catalyst solution for 10min, and loading a catalyst precursor on the surface of the carbon fiber;
and 4, step 4: the carbon fiber treated in the step 3 is firstly reduced with catalyst H through a tube furnace at 450 DEG C2And N2The flow rates of the carbon nanotubes are all 0.5L/min, the carbon nanotubes are reduced and then introduced into another tube furnace with the temperature of 450 ℃ for growing the carbon nanotubes, and the gas introduced into the furnace is N2、H2And C2H2The flow rates of the gases are 0.3L/min, 0.3L/min and 0.6L/min in sequence, the reduction and long pipe time are 5min by controlling the wire feeding speed, and finally the wire bundles are recovered by a wire collecting machine.
Wherein, the current intensity in the step 2 can be 0.1A-0.4A, preferably 0.4A, and the electrolysis time can be 60s-100s, preferably 80 s.
Wherein, the total concentration of the metal ions in the step 3 can be 0.01mol/L, 0.02mol/L, 0.03mol/L, 0.04mol/L and 0.05 mol/L.
Wherein, the growth temperature of the carbon nano tube in the step 4 can be 400 ℃, 450 ℃, 500 ℃ and 550 ℃. Preferably 450 deg.c.
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 fiber fabric into a vertical CVD furnace, heating to 450 ℃ at a heating rate of 15 ℃/min in the atmosphere of nitrogen, preserving heat for 1.5h, removing a sizing agent on the surface of the fiber, cooling to room temperature, and taking out;
step 2: the resulting carbon fiber fabric was prepared by filling with a 5% strength by weight solution of ammonium dihydrogen phosphate. Electrolyzing for 80s in an electrolytic cell under the condition that the current intensity is 0.4A, and drying in a drying oven after removing the surface electrolyte through water washing;
and step 3: preparing a solution by using ferric nitrate, nickel sulfate and sodium lignin sulfonate with the same molar ratio as solutes and absolute ethyl alcohol as a solvent, wherein the concentrations of metal ions serving as a catalyst are all 0.05mol/L and the concentrations of lignin salts are also 0.05mol/L, introducing the carbon fiber subjected to electrolytic etching and treated in the step 2 into the catalyst solution for 10min, and loading a catalyst precursor on the surface of the carbon fiber;
and 4, step 4: the carbon fiber treated in the step 3 is firstly reduced with catalyst H through a tube furnace at 450 DEG C2And N2The flow rates of the two are all 0.5L/min, the carbon nano tubes are reduced and then introduced into another tube furnace with the temperature of 450 ℃ to grow carbon nano tubes, and the gas introduced into the furnace is N2、H2And C2H2The flow rates of the gases are 0.3L/min, 0.3L/min and 0.6L/min in sequence, the reduction and long pipe time are 5min by controlling the wire feeding speed, and finally the wire bundles are recovered by a wire collecting machine.
FIG. 1 is a scanning microscope image of a carbon fiber obtained in example 1 of the present invention. (A) Growing carbon fiber fabric of carbon nanotubes; (B) and the carbon nanotubes are dispersed and uniformly grown on the surface of the carbon fiber fabric.
Example 2
Step 1: putting the carbon fiber into a vertical CVD furnace, heating to 450 ℃ at a heating rate of 15 ℃/min under the atmosphere of nitrogen, preserving heat for 1.5h, removing a sizing agent on the surface of the fiber, cooling to room temperature, and taking out;
step 2: electrolyzing the obtained carbon fiber for 100s in an electrolytic bath filled with 5 wt% ammonium dihydrogen phosphate solution under the condition of 0.2A of current intensity, and then drying in an oven after removing surface electrolyte by washing;
and step 3: preparing a solution by using ferric nitrate, nickel sulfate and sodium lignin sulfonate with the same molar ratio as solutes and absolute ethyl alcohol as a solvent, wherein the concentrations of metal ions serving as a catalyst are all 0.03mol/L and the concentrations of lignin salts are also 0.03mol/L, introducing the carbon fiber subjected to electrolytic etching and treated in the step 2 into the catalyst solution for 10min, and loading a catalyst precursor on the surface of the carbon fiber;
and 4, step 4: the carbon fiber treated in the step 3 is firstly reduced with catalyst H through a tube furnace at 450 DEG C2And N2The flow rates of the two are all 0.5L/min, the carbon nano tubes are reduced and then introduced into another tube furnace with the temperature of 400 ℃ to grow carbon nano tubes, and the gas introduced into the furnace is N2、H2And C2H2The flow rates of the gases are 0.3L/min, 0.3L/min and 0.6L/min in sequence, the reduction time is 5 minutes and the long pipe time is 10 minutes by controlling the wire feeding speed, and finally the wire bundles are recovered by a wire collecting machine.
FIG. 2 is a scanning microscope image of carbon fibers obtained in example 2 of the present invention. (A) Growing carbon fiber fabric of carbon nanotubes; (B) carbon nanotubes which are uniformly dispersed and grow on the surface of the carbon fiber fabric;
example 3
Step 1: putting the carbon fiber fabric into a vertical CVD furnace, heating to 450 ℃ at a heating rate of 15 ℃/min in the atmosphere of nitrogen, preserving heat for 1.5h, removing a sizing agent on the surface of the fiber, cooling to room temperature, and taking out;
step 2: electrolyzing the obtained carbon fiber for 60s in an electrolytic bath filled with 5 wt% ammonium dihydrogen phosphate solution under the condition of 0.2A of current intensity, and then drying in an oven after removing surface electrolyte through water washing;
and step 3: preparing a solution by using ferric nitrate, nickel sulfate and sodium lignin sulfonate with the same molar ratio as solutes and absolute ethyl alcohol as a solvent, wherein the concentrations of metal ions serving as a catalyst are all 0.03mol/L and the concentrations of lignin salts are also 0.03mol/L, introducing the carbon fiber subjected to electrolytic etching and treated in the step 2 into the catalyst solution for 10min, and loading a catalyst precursor on the surface of the carbon fiber;
and 4, step 4: the carbon fiber treated in the step 3 is firstly reduced with catalyst H through a tube furnace at 450 DEG C2And N2The flow rates of the two are all 0.5L/min, the carbon nano tubes are reduced and then introduced into another tubular furnace with the temperature of 500 ℃ to grow carbon nano tubes, and the gas introduced into the furnace is N2、H2And C2H2The flow rates of the gases are 0.3L/min, 0.3L/min and 0.6L/min in sequence, the reduction and long pipe time are 5min by controlling the wire feeding speed, and finally the wire bundles are recovered by a wire collecting machine.
Example 4
Step 1: putting the carbon fiber fabric into a vertical CVD furnace, heating to 450 ℃ at a heating rate of 15 ℃/min in the atmosphere of nitrogen, preserving heat for 1.5h, removing a sizing agent on the surface of the fiber, cooling to room temperature, and taking out;
step 2: electrolyzing the obtained carbon fiber for 60s in an electrolytic bath filled with 5 wt% ammonium dihydrogen phosphate solution under the condition of 0.4A of current intensity, and then drying in an oven after removing surface electrolyte through water washing;
and step 3: preparing a solution by using ferric nitrate, nickel sulfate and sodium lignin sulfonate with the same molar ratio as solutes and absolute ethyl alcohol as a solvent, wherein the concentrations of metal ions serving as a catalyst are all 0.03mol/L and the concentrations of lignin salts are also 0.03mol/L, introducing the carbon fiber subjected to electrolytic etching and treated in the step 2 into the catalyst solution for 10min, and loading a catalyst precursor on the surface of the carbon fiber;
and 4, step 4: the carbon fiber treated in the step 3 is firstly reduced with catalyst H through a tube furnace at 450 DEG C2And N2The flow rates of the two are all 0.5L/min, the carbon nano tubes are reduced and then introduced into another tubular furnace with the temperature of 500 ℃ to grow carbon nano tubes, and the gas introduced into the furnace is N2、H2And C2H2The flow rates of the gases are 0.3L/min, 0.3L/min and 0.6L/min in sequence, the reduction is carried out for 5min by controlling the wire feeding speed, the long pipe time is 10min, and finally the wire bundles are recovered by a wire collecting machine.
Example 5
Step 1: putting the carbon fiber fabric into a vertical CVD furnace, heating to 450 ℃ at a heating rate of 15 ℃/min in the atmosphere of nitrogen, preserving heat for 1.5h, removing a sizing agent on the surface of the fiber, cooling to room temperature, and taking out;
step 2: electrolyzing the obtained carbon fiber for 80s in an electrolytic bath filled with 5 wt% ammonium dihydrogen phosphate solution under the condition of 0.3A of current intensity, and then drying in an oven after removing surface electrolyte through water washing;
and step 3: preparing a solution by using ferric nitrate, nickel sulfate and sodium lignin sulfonate with the same molar ratio as solutes and absolute ethyl alcohol as a solvent, wherein the concentrations of metal ions serving as a catalyst are all 0.03mol/L and the concentrations of lignin salts are also 0.05mol/L, introducing the carbon fiber subjected to electrolytic etching and treated in the step 2 into the catalyst solution for 10min, and loading a catalyst precursor on the surface of the carbon fiber;
and 4, step 4: the carbon fiber treated in the step 3 is firstly reduced with catalyst H through a tube furnace at 450 DEG C2And N2The flow rates of the two are all 0.5L/min, the carbon nano tubes are reduced and then introduced into another tube furnace with the temperature of 550 ℃ to grow the carbon nano tubes, and the gas introduced into the furnace is N2、H2And C2H2The flow rates of the gases are 0.3L/min, 0.3L/min and 0.6L/min in sequence, the reduction is carried out for 5min by controlling the wire feeding speed, the long pipe time is 10min, and finally the wire bundles are recovered by a wire collecting machine.
Comparative example 1
The difference from example 1 is that: no sodium lignosulfonate was added to the solute in step 3.
Comparative example 2
The difference from example 1 is that, in step 2: the obtained carbon fiber fabric is put into a hydrogen peroxide solution with the concentration of 30 wt% and is kept warm for 1.5h at 70 ℃, and then is taken out, cleaned and dried.
TABLE 1 comparison of the Properties of carbon nanotube/carbon fiber textile reinforcements prepared in the present application
Figure GDA0002640136290000081
The scanned graph shows that the carbon nanotubes grown by the method are obviously and uniformly distributed, and are coated and distributed on the carbon fibers, and the numerical value in the monofilament tensile test also shows that the strength is improved because the carbon nanotubes are uniform and have good connection degree with the carbon fibers.
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 (11)

1. A method for growing carbon nanotubes on carbon fibers by using the combined action of sodium lignin sulfonate and a bimetallic catalyst is characterized by comprising the following steps of: desizing, electrolytic oxidation and dipping of carbon fibers in a mixed solution of sodium lignosulfonate and a bimetallic catalyst, drying, and then growing carbon nanotubes on the treated carbon fibers by adopting a chemical vapor deposition method.
2. The method for growing carbon nanotubes on carbon fibers by using the combined action of sodium lignosulfonate and a bimetallic catalyst as in claim 1, wherein the desizing temperature is 450-460 ℃ and the temperature is kept for 1.5-2 h.
3. The method for growing carbon nanotubes on carbon fibers by using the joint action of sodium lignosulfonate and a bimetallic catalyst as in claim 1, wherein the electrolyte is 5-6 wt% ammonium dihydrogen phosphate solution, and the electrolysis is carried out for 80-90 s under the condition that the current intensity is 0.4-0.5A.
4. The method of growing carbon nanotubes on carbon fibers using sodium lignosulfonate in combination with a bimetallic catalyst in claim 1, wherein the bimetallic catalyst is comprised of ferric nitrate, nickel sulfate.
5. The method of growing carbon nanotubes on carbon fibers using sodium lignosulfonate in combination with a bimetallic catalyst according to claim 4, wherein the molar ratio of the ferric nitrate, the nickel sulfate and the sodium lignosulfonate is 1: 1: 1 to 1.5.
6. The method for growing carbon nanotubes on carbon fibers by using the combined action of sodium lignosulfonate and a bimetallic catalyst as in claim 1, wherein the total concentration of metal ions in the mixed solution of the sodium lignosulfonate and the bimetallic catalyst is 0.01-0.05 mol/L.
7. The method for growing carbon nanotubes on carbon fibers by using the combined action of sodium lignin sulfonate and a bimetallic catalyst according to claim 1, wherein the dipping time is 5-6 min by a wire-moving method.
8. The method of growing carbon nanotubes on carbon fibers using sodium lignosulfonate in combination with a bimetallic catalyst in accordance with claim 1, wherein the chemical vapor deposition process comprises the steps of: reducing the catalyst, growing carbon nanotube and recovering the filament bundle with a filament recovering machine.
9. The method of growing carbon nanotubes on carbon fibers using sodium lignosulfonate in combination with a bimetallic catalyst in accordance with claim 8, wherein N is N2、H2In the mixed gas of (2) to reduce the catalyst, N2、H2Is 1: 1 to 1.2.
10. Carbon nanotube/carbon fiber reinforcement prepared by the method of any one of claims 1-9.
11. Use of the carbon nanotube/carbon fiber reinforcement of claim 10 in the fields of aerospace, military and industrial, and sporting goods including rackets, clubs.
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