CN112080710B - Surface coating method of carbon fiber and prepared coated carbon fiber - Google Patents

Surface coating method of carbon fiber and prepared coated carbon fiber Download PDF

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CN112080710B
CN112080710B CN202010973757.4A CN202010973757A CN112080710B CN 112080710 B CN112080710 B CN 112080710B CN 202010973757 A CN202010973757 A CN 202010973757A CN 112080710 B CN112080710 B CN 112080710B
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carbon fiber
titanium
heat treatment
coating
nickel
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CN112080710A (en
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苟国庆
高唯
陈佳
于金朋
郭糠
单美乐
朱忠尹
张曦
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Southwest Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/02—Pretreatment of the fibres or filaments
    • C22C47/04—Pretreatment of the fibres or filaments by coating, e.g. with a protective or activated covering
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/027—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal matrix material comprising a mixture of at least two metals or metal phases or metal matrix composites, e.g. metal matrix with embedded inorganic hard particles, CERMET, MMC.
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/20—Electroplating using ultrasonics, vibrations
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/22—Electroplating combined with mechanical treatment during the deposition
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0607—Wires

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Abstract

A surface coating method of carbon fiber and the prepared coated carbon fiber thereof, the method comprises carbon fiber pretreatment and carbon fiber coating, wherein the carbon fiber pretreatment comprises degumming, coarsening, neutralizing and drying treatment of the carbon fiber in sequence, and the carbon fiber pretreatment also comprises heat treatment of the carbon fiber after the drying treatment; the heat treatment is carried out in a closed environment filled with inert gas, the temperature of the heat treatment is 700-800 ℃, and the time of the heat treatment is 1.5-5 h; the carbon fiber coating comprises the steps of preparing a titanium nano coating on the surface of the pretreated carbon fiber to obtain titanium-plated carbon fiber, and preparing nickel-titanium alloy and Fe on the surface of the titanium-plated carbon fiber3O4A nanoparticle composite coating; wherein nickel-titanium alloy and Fe are prepared on the surface of the titanium-plated carbon fiber3O4The nano-particle composite coating adopts a double-frequency ultrasonic mode. The coated carbon fiber prepared by the coating method has good wettability with a metal material matrix, has electromagnetic shielding performance of medium-high frequency range and low frequency range, and can be used for preparing a magnetic shielding composite material with excellent performance.

Description

Surface coating method of carbon fiber and prepared coated carbon fiber
Technical Field
The invention relates to a surface coating method of carbon fibers and coated carbon fibers prepared by the same, and belongs to the technical field of composite materials.
Background
The carbon fiber has a series of excellent performances such as high specific strength, high specific modulus, high temperature resistance, ablation resistance, abrasion resistance and the like, is a main reinforcing fiber for lightening and improving the performance of civil airliners and helicopters, and is also applied to magnetic suspension trains.
The carbon fiber can be used as a reinforcing fiber of a metal material on a vehicle body, but due to the non-metal property of the carbon fiber, the combination of the carbon fiber and the metal material becomes a bottleneck of the development of the composite material. Because the mechanical and physical bonding interface strength is low, the carbon fibers are often pulled out, peeled or shed when bearing load, and the performance of the composite material is limited, so that the key point for preparing the composite material with excellent physical performance and mechanical performance is to improve the wettability between the metal matrix and the carbon fibers.
In addition, the power of the magnetic suspension train is converted from electric energy to magnetic energy, and in the process of huge electromagnetic energy conversion, radiation emitted by the electromagnetic energy can seriously affect various control systems of the train. Therefore, an important problem to be solved by magnetic levitation trains is the problem of electromagnetic shielding. The existing maglev train body structure mainly uses aluminum alloy as a main material and has a certain electromagnetic shielding effect, but common alloy cannot meet the electromagnetic shielding requirement for key positions with high electromagnetic shielding requirements. Electromagnetic shielding is also a concern when preparing carbon fiber reinforced composites.
In order to facilitate the use of carbon fibers for magnetic levitation vehicles, the prior art has used various methods for surface treatment of carbon fibers, with surface metallization being the most common treatment. In the prior art, metals such as nickel or copper are generally coated on the surface of carbon fiber, but the technical requirements of the carbon fiber as a reinforced fiber and electromagnetic shielding cannot be met at the same time. Therefore, a need exists for a method for treating the surface of carbon fibers that can not only better bond the carbon fibers to the matrix, but also enhance the electromagnetic shielding effect of the matrix.
Disclosure of Invention
The invention aims to provide a surface coating method of carbon fiber and the prepared coated carbon fiber, and the coated carbon fiber prepared by the coating method has good wettability with a metal material matrix and can enhance the electromagnetic shielding performance of the matrix.
The invention adopts the technical scheme that the invention achieves the aim that: a surface coating method of carbon fiber comprises carbon fiber pretreatment and carbon fiber coating, wherein the carbon fiber pretreatment comprises degumming, coarsening, neutralizing and drying treatment of the carbon fiber in sequence;
the carbon fiber pretreatment also comprises the step of carrying out heat treatment on the dried carbon fiber; the heat treatment is carried out in a closed environment filled with inert gas, the heat treatment temperature is 700-800 ℃, the heat treatment time is 1.5-5 h, and the product is cooled to room temperature under the protection of inert gas after heat treatment;
the carbon fiber coating comprises the steps of preparing a titanium nano coating on the surface of the pretreated carbon fiber to obtain titanium-plated carbon fiber, and preparing nickel-titanium alloy and Fe on the surface of the titanium-plated carbon fiber3O4A nanoparticle composite coating;
the nickel-titanium alloy and the Fe are prepared on the surface of the titanium-plated carbon fiber by a composite electroplating method3O4The specific operation of the nano-particle composite coating is as follows:
s21, preparing a plating solution according to the following components:
NiSO nickel sulfate hexahydrate4·6H2O50-60 g/L, titanyl sulfate TiO (SO)4)3.5-10.5g/L, boric acid H3BO330-40g/L sodium dodecyl benzene sulfonate C12H25OSO31.8-2.5g/L, trisodium citrate Na3C6H5O750-60g/L of butanedioic acid imine C4H5NO2 8-10g/L、Fe3O420-50g/L of nano particles;
s22, placing the electroplating solution prepared in the step S21 in a double-frequency ultrasonic field electrolytic tank under the combined action of bath type ultrasonic waves and probe type ultrasonic waves, placing a mechanical stirring device in the electrolytic tank, turning on power supplies of a bath type ultrasonic generator, a probe type ultrasonic generator and the mechanical stirring device, and carrying out pre-plating homogenization treatment on the electroplating solution;
s23, connecting a nickel plate serving as an anode with the anode of an alternating current power supply, connecting carbon fibers serving as a cathode with the cathode of the alternating current power supply, immersing the cathode and the anode into the electroplating solution subjected to homogenization treatment before plating while keeping the bath type ultrasonic generator, the probe type ultrasonic generator and the mechanical stirring device working, and electroplating the cathode by adopting a double-frequency ultrasonic and mechanical stirring mode to obtain the nickel-titanium alloy and Fe alloy with the surfaces being nickel-titanium alloy and Fe3O4Carbon fibers of the nanoparticle composite coating;
the plating parameters were as follows: pH 3-5, electroplating temperature 30-40 deg.C, and cathode current density 2-4A/dm2Electroplating time of 10-20min
The power range of the bath type ultrasonic generator is 100-400W, and the frequency range is 50-120 kHz;
the power range of the probe type ultrasonic generator is 300-800W, and the frequency range is 20-60 kHz;
the stirring speed of the mechanical stirring device is 300-1500 rpm.
Compared with the prior art, the beneficial effect of the above technical scheme is:
firstly, the roughness of the surface of the carbon fiber can be increased through degumming, coarsening and neutralization treatment, so that strong mechanical engaging force is generated between the carbon fiber and a coating, and metal ions are rapidly and efficiently deposited on the surface of the carbon fiber in the subsequent coating process.
And secondly, placing the dried carbon fiber in a closed environment filled with inert gas, and carrying out heat treatment at 700-800 ℃ for 1.5-5 h to remove impurities on the surface of the carbon fiber, so that the carbonization degree of the carbon fiber is improved, the coating quality of the surface of the carbon fiber is improved, the activity of the surface charge of the carbon fiber is improved, and the electromagnetic shielding effect of the carbon fiber after coating is improved.
The applicant determines, through research, that Ti is adopted as an intermediate coating, and the electronic structure arrangement outside the Ti nucleus is as follows: 1s22s22p63s23p63d24s2Four layers of electrons, the outermost layer being 3d24s2And thus the valencies are +2, +3 and + 4. The carbon atom in the carbon fiber has six electrons outside the core: 1s22s22p22s of outer electrons22p2Can proceed sp and sp respectively2And sp3Hybridization to form 2, 3 or 4 covalent bonds. The transition layer is formed by titanium atoms prior to carbon bonding, facilitating further bonding of the target metal to titanium with metallic bonds. Experience and test prove that the Ti coating greatly improves the combination effect between metal and nonmetal. Besides titanium, chromium also has a certain effect of promoting the combination of metal and nonmetal, but chromium plating has great pollution, and the titanium plating process is simple, environment-friendly, low in cost and convenient to popularize and apply.
Plating a nickel-titanium alloy on the surface of the titanium-plated carbon fiber, wherein the same metal has the best compatibility, and the nickel-titanium alloy has good combination with titanium on the surface of the carbon fiber due to the existence of metal titanium, so that a plating layer is more stable; moreover, tests prove that the hardness, the wear resistance and the corrosion resistance of the obtained nickel-titanium alloy layer are all superior to those of a pure nickel layer, and the nickel-titanium alloy plating layer containing 10-30% of titanium has the corrosion resistance which is improved by 40-60% compared with the corrosion resistance of a 100% nickel plating layer with the same thickness, and the toughness of the nickel-titanium alloy layer is doubled.
Fifthly, the applicant obtains the nickel-titanium alloy and Fe prepared in the technical scheme through a large number of tests3O4The electroplating solution of the nano-particle composite coating is non-toxic and pollution-free, stable, not turbid and strong in impurity resistance; wherein, nickel sulfate hexahydrate and titanyl sulfate are used as main salts to provide nickel ions and titanium ions, and boric acid is used as a buffering agent to stabilize pH; sodium dodecyl benzene sulfonate is adopted as an anionic surface activator, when the activator is dissolved in a solution, the surface of the nano-particles can adsorb a high-molecular polyelectrolyte and a surfactant which are used as dispersing agents, so that the surface energy is reduced, the agglomeration is reduced, and a relatively good dispersion state is maintainedThe nano particles can smoothly enter the coating; by adopting trisodium citrate as a main coordination agent and succinic acid imine as an auxiliary coordination agent, compact, uniform and continuous nickel-titanium alloy and Fe can be formed on the surface of the titanium-plated carbon fiber3O4And (4) coating the nano-particle composite coating.
Sixthly, the main factors influencing the electroplating comprise the pH value, the current density, the electroplating time and the temperature of the electroplating solution, the optimal electroplating process is obtained through a large number of experimental comparison analyses, and the nickel-titanium alloy and the Fe obtained under the electroplating process3O4The nano-particle composite coating is continuous and compact, complete and stable in combination.
Seven, Fe3O4Has good magnetic property, conductive property and excellent wave-absorbing property, and has wide application in the field of electromagnetic shielding and wave-absorbing materials. The technical proposal adds Fe into the titanium-nickel alloy plating solution3O4The nano particles can simultaneously obtain a metal and nano particle composite coating on the surface of the carbon fiber, so that the carbon fiber is more easily and stably compounded with a metal matrix as a reinforcing fiber, and the carbon fiber has electromagnetic shielding performance of medium and high frequency bands and low frequency bands simultaneously, and can be used for preparing a magnetic shielding composite material with excellent performance.
Though the aggregation of the nanoparticles is reduced to a certain extent by the simple stirring method, the effects of inhibiting the aggregation of the nanoparticles and dispersing the nanoparticle aggregates are not very ideal, and the nanoparticle aggregates formed in the plating solution are difficult to disperse. The technical proposal is used for preparing nickel-titanium alloy and Fe3O4Before the nano-particle composite coating is coated, a method of double-frequency ultrasound and mechanical stirring is adopted, the double-frequency ultrasound can generate a uniform sound field, and the mechanical effect, the thermal effect, the acoustic flow effect and the cavitation effect of the double-frequency ultrasound and the stirring of a mechanical stirring device on the electroplating solution and other factors are utilized to disperse Fe in the electroplating solution3O4The nano particles reduce the agglomeration probability of the nano particles and have good dispersion effect. In the electroplating process, a method of double-frequency ultrasound and mechanical stirring is also adopted to ensure Fe in the electroplating process3O4The nanoparticles are in the electroplating solutionUniformly distributed, so that the nano particles and the matrix metal are co-deposited, and the obtained nano composite coating has fine and uniform matrix metal grains and compact structure.
Further, the specific operation of removing the photoresist in the carbon fiber pretreatment of the invention is as follows: firstly, oxidizing carbon fibers at 400 ℃ in an air atmosphere for 30min, and then soaking the carbon fibers with oxidized surfaces in acetone at room temperature for 3 h.
Further, the specific operation of coarsening in the carbon fiber pretreatment of the invention is as follows: and placing the carbon fiber in concentrated nitric acid, heating to 90 ℃ for coarsening, wherein the coarsening time is 20min respectively.
Further, the specific operation of neutralization in the carbon fiber pretreatment of the invention is as follows: and (3) carrying out alkali washing on the roughened carbon fiber on the surface of the carbon fiber by adopting a sodium hydroxide solution, and then washing and filtering by using distilled water.
Further, the specific operation of preparing the titanium nano coating on the surface of the pretreated carbon fiber is as follows:
s11, mixing hydrochloric acid (concentrated 35% hydrochloric acid) with acetone (CH)3COCH3) Mixing to obtain a mixed solution; wherein the ratio of the hydrochloric acid to the acetone is 1mL to (5-10) mL;
s12, mixing titanium powder into ethanol, grinding uniformly, and then adding the mixture into the mixed solution prepared in the step S11 for sufficient ultrasonic dispersion to obtain a titanium powder suspension, wherein the particle size of the titanium powder is 300-400 meshes; titanium powder: ethanol: the mixture ratio of the mixed solution is 1 g: (3-6) mL: (10-20) ml;
s13, adding the pretreated carbon fibers into the titanium powder suspension prepared in the step S12, ultrasonically dispersing for 20-30min, filtering and drying in vacuum to obtain a mixture of titanium powder and carbon fibers; wherein the mass ratio of the carbon fiber to the titanium powder is 1: 3-4;
s14, placing the mixture of the titanium powder and the carbon fiber into a tube furnace, carrying out heat treatment in an inert gas atmosphere, wherein the heat treatment temperature is 700-800 ℃, the heat treatment time is 0.5-2.5 h, and cooling to room temperature under the protection of inert gas after heat treatment to obtain the titanium-plated carbon fiber.
The preparation process is simple, the cost is low, a layer of titanium film which is uniformly distributed and consists of nano titanium particles can be prepared on the surface of the carbon fiber, and the subsequent combination of the carbon fiber and the metal coating is facilitated.
Further, the nickel-titanium alloy and the Fe are prepared on the surface of the titanium-plated carbon fiber by a composite electroplating method3O4Fe for nano-particle composite coating3O4The particle size of the nano-particles is 20nm-50 nm.
Experiments prove that the nano particles with the particle sizes can be better and uniformly co-deposited with the nickel-titanium metal coating to form the residual titanium-plated carbon fiber surface.
Further, the nickel-titanium alloy and the Fe are prepared on the surface of the titanium-plated carbon fiber by a composite electroplating method3O4In step S22 of the nanoparticle composite plating, the parameters of the homogenization treatment before plating are as follows:
the power range of the bath type ultrasonic generator is 100-400W, and the frequency range is 50-120 kHz;
the power range of the probe type ultrasonic generator is 300-800W, and the frequency range is 20-60 kHz;
the stirring speed of the mechanical stirring device is 300-1500 rpm;
the homogenization treatment time before plating is 2-3 h.
The homogenized dual-frequency ultrasonic waves can generate a high-speed spraying effect towards the surface of the nano aggregate when cavitation nuclei generated in the cavitation process are broken, and the impact waves generated by the broken cavitation bubbles can impact, peel and erode the surface of the aggregate so as to gradually break the aggregate and uniformly disperse the aggregate into the plating solution, so that the dispersion of the nano aggregate is realized.
The invention also provides the coated carbon fiber which is prepared by the coating method.
Detailed Description
Example one
A surface coating method of carbon fiber and the prepared coated carbon fiber thereof, the method comprises carbon fiber pretreatment and carbon fiber coating, wherein the carbon fiber pretreatment comprises degumming, coarsening, neutralizing and drying treatment of the carbon fiber in sequence;
the specific operation of removing the photoresist is as follows: firstly, oxidizing carbon fibers at 400 ℃ in an air atmosphere for 30min, and then soaking the carbon fibers with oxidized surfaces in acetone at room temperature for 3 h.
The specific operation of the coarsening is as follows: and placing the carbon fiber in concentrated nitric acid, heating to 90 ℃ for coarsening, wherein the coarsening time is 20min respectively.
The specific operation of the neutralization is as follows: and (3) carrying out alkali washing on the roughened carbon fiber on the surface of the carbon fiber by adopting a sodium hydroxide solution, and then washing and filtering by using distilled water.
The carbon fiber pretreatment also comprises the step of carrying out heat treatment on the dried carbon fiber; carrying out heat treatment in a closed environment filled with inert gas, wherein the temperature of the heat treatment is 750 ℃, the time of the heat treatment is 3h, and cooling to room temperature under the protection of the inert gas after the heat treatment;
the carbon fiber coating comprises the steps of preparing a titanium nano coating on the surface of the pretreated carbon fiber to obtain titanium-plated carbon fiber, and preparing nickel-titanium alloy and Fe on the surface of the titanium-plated carbon fiber3O4A nanoparticle composite coating;
the specific operation of preparing the titanium nano coating on the surface of the pretreated carbon fiber is as follows:
s11, mixing hydrochloric acid and acetone to obtain a mixed solution; wherein the ratio of the hydrochloric acid to the acetone is 1mL to 8 mL;
s12, mixing titanium powder into ethanol, grinding uniformly, and then adding the mixture into the mixed solution prepared in the step S11 for sufficient ultrasonic dispersion to obtain a titanium powder suspension, wherein the particle size of the titanium powder is 300-400 meshes; titanium powder: ethanol: the mixture ratio of the mixed solution is 1 g: 5mL of: 15 ml;
s13, adding the pretreated carbon fibers into the titanium powder suspension prepared in the step S12, ultrasonically dispersing for 25min, filtering and drying in vacuum to obtain a mixture of titanium powder and carbon fibers; wherein the mass ratio of the carbon fiber to the titanium powder is 1: 3;
s14, placing the mixture of the titanium powder and the carbon fiber into a tube furnace, carrying out heat treatment in an inert gas atmosphere, wherein the heat treatment temperature is 750 ℃, the heat treatment time is 2 hours, and cooling to room temperature under the protection of inert gas after heat treatment to obtain the titanium-plated carbon fiber.
Preparing nickel-titanium alloy and Fe on the surface of titanium-plated carbon fiber by composite electroplating method3O4The specific operation of the nano-particle composite coating is as follows:
s21, preparing a plating solution according to the following components:
NiSO4·6H2O 55g/L、TiO(SO4)7g/L、H3BO3 35g/L，C12H25OSO3 2g/L、Na3C6H5O7 55g/L、C4H5NO29g/L、Fe3O430g/L of nanoparticles; wherein, Fe3O4The particle size of the nano particles is 20nm-50 nm;
s22, placing the electroplating solution prepared in the step S21 in a double-frequency ultrasonic field electrolytic tank under the combined action of bath type ultrasonic waves and probe type ultrasonic waves, placing a mechanical stirring device in the electrolytic tank, turning on power supplies of a bath type ultrasonic wave generator, a probe type ultrasonic wave generator and the mechanical stirring device, and carrying out pre-plating homogenization treatment on the electroplating solution, wherein the parameters of the pre-plating homogenization treatment are as follows:
the power of the bath type ultrasonic generator is 300W, and the frequency is 80 kHz;
the power of the probe type ultrasonic generator is 600W, and the frequency is 50 kHz;
the stirring speed of the mechanical stirring device is 1000 rpm;
the homogenization treatment time before plating is 3 h.
S23, connecting a nickel plate serving as an anode with the anode of an alternating current power supply, connecting carbon fibers serving as a cathode with the cathode of the alternating current power supply, immersing the cathode and the anode into the electroplating solution subjected to homogenization treatment before plating while keeping the bath type ultrasonic generator, the probe type ultrasonic generator and the mechanical stirring device working, and electroplating the cathode by adopting a double-frequency ultrasonic and mechanical stirring mode to obtain the nickel-titanium alloy and Fe alloy with the surfaces being nickel-titanium alloy and Fe3O4Carbon fibers of the nanoparticle composite coating;
the plating parameters were as follows: pH 4, electroplating temperature 35 deg.C, and cathode current density 3A/dm2Electroplating time 15min
The power of the bath type ultrasonic generator is 300W, and the frequency is 80 kHz;
the power of the probe type ultrasonic generator is 600W, and the frequency is 50 kHz;
the stirring speed of the mechanical stirring apparatus was 1000 rpm.
The magnetic performance of the coated carbon fiber prepared in the mutexample was analyzed by an FD-MT-A magnetic balance, and the saturated magnetization of the coated carbon fiber prepared in this mutexample was up to 45emu/g, as measured at room temperature with an applied magnetic field of 2T. Therefore, the coated carbon fiber prepared by the method has high magnetic conductivity and good electromagnetic shielding performance.
Example two
A surface coating method of carbon fiber and the prepared coated carbon fiber thereof, the method comprises carbon fiber pretreatment and carbon fiber coating, wherein the carbon fiber pretreatment comprises degumming, coarsening, neutralizing and drying treatment of the carbon fiber in sequence;
the specific operation of removing the photoresist is as follows: firstly, oxidizing carbon fibers at 400 ℃ in an air atmosphere for 30min, and then soaking the carbon fibers with oxidized surfaces in acetone at room temperature for 3 h.
The specific operation of the coarsening is as follows: and placing the carbon fiber in concentrated nitric acid, heating to 90 ℃ for coarsening, wherein the coarsening time is 20min respectively.
The specific operation of the neutralization is as follows: and (3) carrying out alkali washing on the roughened carbon fiber on the surface of the carbon fiber by adopting a sodium hydroxide solution, and then washing and filtering by using distilled water.
The carbon fiber pretreatment also comprises the step of carrying out heat treatment on the dried carbon fiber; carrying out heat treatment in a closed environment filled with inert gas, wherein the temperature of the heat treatment is 700 ℃, the time of the heat treatment is 5h, and cooling to room temperature under the protection of the inert gas after the heat treatment;
the carbon fiber coating comprises the steps of preparing a titanium nano coating on the surface of the pretreated carbon fiber to obtain titanium-plated carbon fiber, and preparing nickel-titanium alloy and Fe on the surface of the titanium-plated carbon fiber3O4A nanoparticle composite coating;
the specific operation of preparing the titanium nano coating on the surface of the pretreated carbon fiber is as follows:
s11, mixing hydrochloric acid and acetone to obtain a mixed solution; wherein the ratio of the hydrochloric acid to the acetone is 1mL to 5 mL;
s12, mixing titanium powder into ethanol, grinding uniformly, and then adding the mixture into the mixed solution prepared in the step S11 for sufficient ultrasonic dispersion to obtain a titanium powder suspension, wherein the particle size of the titanium powder is 300-400 meshes; titanium powder: ethanol: the mixture ratio of the mixed solution is 1 g: 3mL of: 10 ml;
s13, adding the pretreated carbon fibers into the titanium powder suspension prepared in the step S12, ultrasonically dispersing for 20min, filtering and drying in vacuum to obtain a mixture of titanium powder and carbon fibers; wherein the mass ratio of the carbon fiber to the titanium powder is 1: 4;
s14, placing the mixture of the titanium powder and the carbon fiber into a tube furnace, carrying out heat treatment in an inert gas atmosphere, wherein the heat treatment temperature is 700 ℃, the heat treatment time is 2.5h, and cooling to room temperature under the protection of inert gas after heat treatment to obtain the titanium-plated carbon fiber.
Preparing nickel-titanium alloy and Fe on the surface of titanium-plated carbon fiber by composite electroplating method3O4The specific operation of the nano-particle composite coating is as follows:
s21, preparing a plating solution according to the following components:
NiSO4·6H2O 50g/L、TiO(SO4)3.5g/L、H3BO3 30g/L，C12H25OSO3 1.8g/L、Na3C6H5O750g/L、C4H5NO28g/L、Fe3O420g/L of nanoparticles; wherein, Fe3O4The particle size of the nano particles is 20nm-50 nm;
s22, placing the electroplating solution prepared in the step S21 in a double-frequency ultrasonic field electrolytic tank under the combined action of bath type ultrasonic waves and probe type ultrasonic waves, placing a mechanical stirring device in the electrolytic tank, turning on power supplies of a bath type ultrasonic wave generator, a probe type ultrasonic wave generator and the mechanical stirring device, and carrying out pre-plating homogenization treatment on the electroplating solution, wherein the parameters of the pre-plating homogenization treatment are as follows:
the power of the bath type ultrasonic generator is 400W, and the frequency is 50 kHz;
the power of the probe type ultrasonic generator is 800W, and the frequency is 20 kHz;
the stirring speed of the mechanical stirring device is 300 rpm;
the homogenization treatment time before plating is 2 h.
S23, connecting a nickel plate serving as an anode with the anode of an alternating current power supply, connecting carbon fibers serving as a cathode with the cathode of the alternating current power supply, immersing the cathode and the anode into the electroplating solution subjected to homogenization treatment before plating while keeping the bath type ultrasonic generator, the probe type ultrasonic generator and the mechanical stirring device working, and electroplating the cathode by adopting a double-frequency ultrasonic and mechanical stirring mode to obtain the nickel-titanium alloy and Fe alloy with the surfaces being nickel-titanium alloy and Fe3O4Carbon fibers of the nanoparticle composite coating;
the plating parameters were as follows: pH 3, electroplating temperature 30 deg.C, and cathode current density 4A/dm2Electroplating time 10min
The power of the bath type ultrasonic generator is 400W, and the frequency is 50 kHz;
the power of the probe type ultrasonic generator is 800W, and the frequency is 20 kHz;
the stirring speed of the mechanical stirring device was 300 rpm.
EXAMPLE III
A surface coating method of carbon fiber and the prepared coated carbon fiber thereof, the method comprises carbon fiber pretreatment and carbon fiber coating, wherein the carbon fiber pretreatment comprises degumming, coarsening, neutralizing and drying treatment of the carbon fiber in sequence;
the specific operation of removing the photoresist is as follows: firstly, oxidizing carbon fibers at 400 ℃ in an air atmosphere for 30min, and then soaking the carbon fibers with oxidized surfaces in acetone at room temperature for 3 h.
The specific operation of the coarsening is as follows: and placing the carbon fiber in concentrated nitric acid, heating to 90 ℃ for coarsening, wherein the coarsening time is 20min respectively.
The specific operation of the neutralization is as follows: and (3) carrying out alkali washing on the roughened carbon fiber on the surface of the carbon fiber by adopting a sodium hydroxide solution, and then washing and filtering by using distilled water.
The carbon fiber pretreatment also comprises the step of carrying out heat treatment on the dried carbon fiber; carrying out heat treatment in a closed environment filled with inert gas, wherein the temperature of the heat treatment is 800 ℃, the time of the heat treatment is 1.5h, and cooling to room temperature under the protection of the inert gas after the heat treatment;
the carbon fiber coating comprises the steps of preparing a titanium nano coating on the surface of the pretreated carbon fiber to obtain titanium-plated carbon fiber, and preparing nickel-titanium alloy and Fe on the surface of the titanium-plated carbon fiber3O4A nanoparticle composite coating;
the specific operation of preparing the titanium nano coating on the surface of the pretreated carbon fiber is as follows:
s11, mixing hydrochloric acid and acetone to obtain a mixed solution; wherein the ratio of the hydrochloric acid to the acetone is 1mL to 10 mL;
s12, mixing titanium powder into ethanol, grinding uniformly, and then adding the mixture into the mixed solution prepared in the step S11 for sufficient ultrasonic dispersion to obtain a titanium powder suspension, wherein the particle size of the titanium powder is 300-400 meshes; titanium powder: ethanol: the mixture ratio of the mixed solution is 1 g: 6mL of: 20ml of the solution;
s13, adding the pretreated carbon fibers into the titanium powder suspension prepared in the step S12, ultrasonically dispersing for 30min, filtering and drying in vacuum to obtain a mixture of titanium powder and carbon fibers; wherein the mass ratio of the carbon fiber to the titanium powder is 1: 3;
s14, placing the mixture of the titanium powder and the carbon fiber into a tube furnace, carrying out heat treatment in an inert gas atmosphere, wherein the heat treatment temperature is 750 ℃, the heat treatment time is 2 hours, and cooling to room temperature under the protection of inert gas after heat treatment to obtain the titanium-plated carbon fiber.
Preparing nickel-titanium alloy and Fe on the surface of titanium-plated carbon fiber by composite electroplating method3O4The specific operation of the nano-particle composite coating is as follows:
s21, preparing a plating solution according to the following components:
NiSO4·6H2O 60g/L、TiO(SO4)10.5g/L、H3BO3 40g/L，C12H25OSO3 2.5g/L、Na3C6H5O760g/L、C4H5NO210g/L、Fe3O450g/L of nanoparticles; wherein, Fe3O4The particle size of the nano particles is 20nm-50 nm;
s22, placing the electroplating solution prepared in the step S21 in a double-frequency ultrasonic field electrolytic tank under the combined action of bath type ultrasonic waves and probe type ultrasonic waves, placing a mechanical stirring device in the electrolytic tank, turning on power supplies of a bath type ultrasonic wave generator, a probe type ultrasonic wave generator and the mechanical stirring device, and carrying out pre-plating homogenization treatment on the electroplating solution, wherein the parameters of the pre-plating homogenization treatment are as follows:
the power of the bath type ultrasonic generator is 100W, and the frequency is 120 kHz;
the power of the probe type ultrasonic generator is 300W, and the frequency is 60 kHz;
the stirring speed of the mechanical stirring device is 1500 rpm;
the homogenization treatment time before plating is 3 h.
S23, connecting a nickel plate serving as an anode with the anode of an alternating current power supply, connecting carbon fibers serving as a cathode with the cathode of the alternating current power supply, immersing the cathode and the anode into the electroplating solution subjected to homogenization treatment before plating while keeping the bath type ultrasonic generator, the probe type ultrasonic generator and the mechanical stirring device working, and electroplating the cathode by adopting a double-frequency ultrasonic and mechanical stirring mode to obtain the nickel-titanium alloy and Fe alloy with the surfaces being nickel-titanium alloy and Fe3O4Carbon fibers of the nanoparticle composite coating;
the plating parameters were as follows: pH 5, electroplating temperature 40 deg.C, and cathode current density 2A/dm2Electroplating time 20min
The power of the bath type ultrasonic generator is 100W, and the frequency is 120 kHz;
the power of the probe type ultrasonic generator is 300W, and the frequency is 60 kHz;
the stirring speed of the mechanical stirring device was 1500 rpm.

Claims (8)

1. The surface coating method of the carbon fiber comprises carbon fiber pretreatment and carbon fiber coating, wherein the carbon fiber pretreatment comprises degumming, coarsening, neutralizing and drying treatment of the carbon fiber in sequence, and is characterized in that:
the carbon fiber pretreatment also comprises the step of carrying out heat treatment on the dried carbon fiber; the heat treatment is carried out in a closed environment filled with inert gas, the temperature of the heat treatment is 700-800 ℃, the time of the heat treatment is 1.5-5 h, and the heat treatment is carried out and then is cooled to the room temperature under the protection of the inert gas;
the carbon fiber coating comprises the steps of preparing a titanium nano coating on the surface of the pretreated carbon fiber to obtain titanium-plated carbon fiber, and preparing nickel-titanium alloy and Fe on the surface of the titanium-plated carbon fiber3O4A nanoparticle composite coating;
the nickel-titanium alloy and the Fe are prepared on the surface of the titanium-plated carbon fiber by a composite electroplating method3O4The specific operation of the nano-particle composite coating is as follows:
s21, preparing a plating solution according to the following components:
NiSO4·6H2O 50-60g/L、TiO(SO4) 3.5-10.5g/L、H3BO3 30-40g/L，C12H25OSO3 1.8-2.5g/L、Na3C6H5O7 50-60g/L、C4H5NO2 8-10g/L、Fe3O420-50g/L of nano particles;
s22, placing the electroplating solution prepared in the step S21 in a double-frequency ultrasonic field electrolytic tank under the combined action of bath type ultrasonic waves and probe type ultrasonic waves, placing a mechanical stirring device in the electrolytic tank, turning on power supplies of a bath type ultrasonic generator, a probe type ultrasonic generator and the mechanical stirring device, and carrying out pre-plating homogenization treatment on the electroplating solution;
s23, connecting a nickel plate serving as an anode with the anode of an alternating current power supply, connecting carbon fibers serving as a cathode with the cathode of the alternating current power supply, immersing the cathode and the anode into the electroplating solution subjected to homogenization treatment before plating while keeping the bath type ultrasonic generator, the probe type ultrasonic generator and the mechanical stirring device working, and electroplating the cathode by adopting a double-frequency ultrasonic and mechanical stirring mode to obtain the nickel-titanium alloy and Fe alloy with the surfaces being nickel-titanium alloy and Fe3O4Nanoparticle composite platingCarbon fibers of the layer;
the plating parameters were as follows: pH 3-5, electroplating temperature 30-40 deg.C, and cathode current density 2-4A/dm2Electroplating time of 10-20min
The power range of the bath type ultrasonic generator is 100-400W, and the frequency range is 50-120 kHz;
the power range of the probe type ultrasonic generator is 300-800W, and the frequency range is 20-60 kHz;
the stirring speed of the mechanical stirring device is 300-1500 rpm.
2. The surface coating method of carbon fiber according to claim 1, characterized in that: the specific operation of removing the photoresist in the carbon fiber pretreatment is as follows: firstly, oxidizing carbon fibers at 400 ℃ in an air atmosphere for 30min, and then soaking the carbon fibers with oxidized surfaces in acetone at room temperature for 3 h.
3. The surface coating method of carbon fiber according to claim 1, characterized in that: the specific operation of coarsening in the carbon fiber pretreatment is as follows: and placing the carbon fiber in concentrated nitric acid, heating to 90 ℃ for coarsening, wherein the coarsening time is 20min respectively.
4. The surface coating method of carbon fiber according to claim 1, characterized in that: the specific operation of neutralization in the carbon fiber pretreatment is as follows: and (3) carrying out alkali washing on the roughened carbon fiber on the surface of the carbon fiber by adopting a sodium hydroxide solution, and then washing and filtering by using distilled water.
5. The surface coating method for carbon fiber according to any one of claims 1 to 4, characterized in that: the specific operation of preparing the titanium nano coating on the surface of the pretreated carbon fiber is as follows:
s11, mixing hydrochloric acid and acetone to obtain a mixed solution; wherein the ratio of the hydrochloric acid to the acetone is 1mL to (5-10) mL;
s12, mixing titanium powder into ethanol, grinding uniformly, and then adding the mixture into the mixed solution prepared in the step S11 for sufficient ultrasonic dispersion to obtain a titanium powder suspension, wherein the particle size of the titanium powder is 300-400 meshes; titanium powder: ethanol: the mixture ratio of the mixed solution is 1 g: (3-6) mL: (10-20) ml;
s13, adding the pretreated carbon fibers into the titanium powder suspension prepared in the step S12, ultrasonically dispersing for 20-30min, filtering and drying in vacuum to obtain a mixture of titanium powder and carbon fibers; wherein the mass ratio of the carbon fiber to the titanium powder is 1: 3-4;
s14, placing the mixture of the titanium powder and the carbon fiber into a tube furnace, carrying out heat treatment in an inert gas atmosphere, wherein the heat treatment temperature is 700-800 ℃, the heat treatment time is 0.5-2.5 h, and cooling to room temperature under the protection of inert gas after heat treatment to obtain the titanium-plated carbon fiber.
6. The surface coating method of carbon fiber according to claim 1, characterized in that: the nickel-titanium alloy and the Fe are prepared on the surface of the titanium-plated carbon fiber by a composite electroplating method3O4Fe for nano-particle composite coating3O4The particle size of the nano-particles is 20nm-50 nm.
7. The surface coating method of carbon fiber according to claim 1, characterized in that: the nickel-titanium alloy and the Fe are prepared on the surface of the titanium-plated carbon fiber by a composite electroplating method3O4In step S22 of the nanoparticle composite plating, the parameters of the homogenization treatment before plating are as follows:
the power range of the bath type ultrasonic generator is 100-400W, and the frequency range is 50-120 kHz;
the power range of the probe type ultrasonic generator is 300-800W, and the frequency range is 20-60 kHz;
the stirring speed of the mechanical stirring device is 300-1500 rpm;
the homogenization treatment time before plating is 2-3 h.
8. A coated carbon fiber is characterized in that: the coated carbon fiber is prepared by the coating method of any one of claims 1 to 7.
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