CN113024995A - High-strength high-modulus electromagnetic shielding functional structure integrated light material and preparation method thereof - Google Patents

High-strength high-modulus electromagnetic shielding functional structure integrated light material and preparation method thereof Download PDF

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CN113024995A
CN113024995A CN202110154857.9A CN202110154857A CN113024995A CN 113024995 A CN113024995 A CN 113024995A CN 202110154857 A CN202110154857 A CN 202110154857A CN 113024995 A CN113024995 A CN 113024995A
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fabric
nickel
carbon fiber
pda
modulus
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CN113024995B (en
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朱姝
周剑锋
瞿明城
史如静
张礼颖
范如意
王天成
琚铭楷
郭青钊
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Donghua University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives

Abstract

The invention relates to a high-strength high-modulus electromagnetic shielding function structure integrated light material and a preparation method thereof, wherein the high-strength high-modulus electromagnetic shielding function structure integrated light material is a CF-Ni-PDA/CNT/epoxy composite material which is composed of nickel-plated carbon fibers (carbon fibers with nickel oxide on the surface), a polydopamine layer, carboxylated CNT and epoxy resin; the polydopamine layer is positioned between the nickel-plated carbon fiber and the epoxy resin, the polydopamine layer is connected with the nickel-plated carbon fiber through Ni-N bonds and hydrogen bonds, and the polydopamine layer is connected with the epoxy resin through N-C bonds; the preparation method comprises the following steps: firstly, carrying out surface oxidation on carbon fibers after chemical nickel plating, then depositing and accumulating a dopamine layer to obtain CF-Ni-PDA, and then preparing the CF-Ni-PDA/CNT/epoxy composite material by using the CF-Ni-PDA, carboxylated CNT and epoxy resin as main raw materials and adopting a vacuum auxiliary resin infusion molding method. Compared with the light material with the electromagnetic shielding function prepared by the prior art, the material with higher tensile strength and modulus can be prepared, and the preparation method is controllable.

Description

High-strength high-modulus electromagnetic shielding functional structure integrated light material and preparation method thereof
Technical Field
The invention belongs to the technical field of composite materials, and relates to a high-strength high-modulus electromagnetic shielding function structure integrated light material and a preparation method thereof.
Background
With the development of 5G technology, the demand of aerospace, electronics and other industries for materials with electromagnetic shielding Effectiveness (EMI) is more and more extensive. For example, the widespread use of electronic products is prone to electromagnetic interference, which is a new type of pollution that disturbs the normal operation of electronic devices, and therefore it is necessary to provide some kind of blocking mechanism to isolate the interior of the device from the surrounding electromagnetic environment and to shield the electromagnetic radiation from the external environment. Electromagnetic shielding is to control the transmission of electromagnetic waves by isolating the area to be protected with a shielding body, i.e. to attenuate the electromagnetic waves by the reflection or absorption of conductive or magnetic conductive materials, so as to prevent the protected object from being subjected to electromagnetic interference.
Materials with electromagnetic shielding functionality typically require EMI in excess of 20 dB. Conventional shielding materials include metal sheets, wire meshes, foamed metals, and volume conductive coatings with metal powders, but the disadvantages of high density, high weight, high cost, and corrosion susceptibility of metal materials such as copper, aluminum, iron, and steel limit their practical applications. In recent years, there has been a search forThe novel electromagnetic shielding material replaces the traditional metal material, and the lightweight is needed to be realized at the same time in some application occasions, namely the density is lower than 1.7g/cm3. The conductive polymer-based composite material is popular in the field of electromagnetic shielding due to the advantages of light weight, corrosion resistance, good flexibility, good processability, low cost and the like, can be used for antenna systems, protected aircraft composite boards, replaceable unit shells of avionic circuits, connector gaskets, static and space charge dissipation materials, electronic pressure-sensitive switches or sensors of different types and the like, and can be used as a potential material of electrical equipment, airplanes, automobile parts and the like through multifunctional design to be applied to the fields of navy and aerospace. A great deal of research has been conducted on polymer-based conductive composite materials in which a polymer matrix is not conductive and electromagnetic shielding effectiveness depends on a conductive filler, and various carbon materials, such as graphene, carbon aerogel, amorphous carbon, carbon black, and Carbon Nanotubes (CNTs), have been widely used for electromagnetic shielding research due to unique properties of the carbon materials and the composite materials thereof, such as high conductivity, light weight, high specific surface area, environmental friendliness, excellent flexibility, low density, chemical stability, and excellent mechanical properties.
In the prior art, such materials that can simultaneously meet the performance requirements are usually resin-based composite materials filled with nano materials such as graphene, carbon nanotubes, nano silver wires and the like. However, these materials cannot be used as structural materials because of their strength and modulus, and it is difficult for them to exceed 450MPa in tensile strength and 55GPa in modulus. Therefore, the prior art generally applies these nanocomposites as coatings to the surface of the structural materials. The biggest problem of this method is that the durability of the paint is poor, and once a small area is peeled off, the electromagnetic shielding effectiveness is greatly reduced. The method of plating metal on the carbon fiber and preparing the resin-based composite material is also adopted, but the bonding property of the plated carbon fiber and the resin is poor, so that the composite material has lower properties such as tensile strength, modulus, interlaminar shear strength and the like.
Therefore, the research on the material with high tensile strength, modulus and interlaminar shear strength and electromagnetic shielding function number is of great significance.
Disclosure of Invention
The invention provides a high-strength high-modulus electromagnetic shielding function structure integrated light material and a preparation method thereof, aiming at solving the technical problems of insufficient tensile strength, modulus and interlaminar shear strength and insufficient electromagnetic shielding function in the prior art. After the surface of the carbon fiber is plated with nickel, the nickel-plated carbon fiber is subjected to superficial oxidation, so that the surface can generate strong interaction with the polydopamine sizing agent, and the composite material can reach the performance indexes of high strength and high modulus; meanwhile, because the oxidation degree is not deep, the electromagnetic shielding effectiveness of the composite material can not be influenced, and the EMI value still exceeds 20 dB.
In order to achieve the purpose, the invention adopts the following scheme:
the high-strength high-modulus electromagnetic shielding functional structure integrated light material is a CF-Ni-PDA/CNT/epoxy composite material which is composed of nickel-plated carbon fibers, a Polydopamine (PDA) layer, carboxylated CNT and epoxy resin;
the nickel-plated carbon fiber is a carbon fiber with nickel oxide on the surface;
the polydopamine layer is positioned between the nickel-plated carbon fiber and the epoxy resin, the polydopamine layer is connected with the nickel-plated carbon fiber through Ni-N bonds and hydrogen bonds, and the polydopamine layer is connected with the epoxy resin through N-C bonds.
As a preferred technical scheme:
according to the high-strength high-modulus electromagnetic shielding functional structure integrated light material, the nickel oxide can be continuous or discontinuous, a continuous layer structure is better, the nickel oxide is preferably a continuous layer structure, and the thickness of the nickel oxide is 10-100 nm.
The high-strength high-modulus electromagnetic shielding functional structure integrated light material comprises a nickel-plated carbon fiber surface, wherein the thickness of the nickel layer is about 1 mu m, and the nickel layer is connected with the carbon fiber through Van der Waals force, mechanical riveting and Ni-OH-C bonding; the nickel oxide is positioned on the surface of the nickel layer; the main function of the nickel layer is to provide higher conductivity, and the function of the outermost nickel oxide layer is to provide activity that can generate hydrogen bonds with the sizing agent.
In the high-strength high-modulus electromagnetic shielding functional structure integrated light material, in the CF-Ni-PDA/CNT/epoxy composite material, the nickel-plated carbon fiber is in the form of fabric, and the fabric is in the form of unidirectional fabric, plain fabric, satin fabric, twill fabric or non-buckling fabric (NCF);
the CF-Ni-PDA/CNT/epoxy composite material has an ILSS (interlaminar shear strength) of 40-70 MPa, a tensile strength of 450-600 MPa, a tensile modulus of 55-65 GPa, and an electromagnetic shielding effectiveness of 29-40 dB.
In the high-strength high-modulus electromagnetic shielding functional structure integrated lightweight material, the epoxy resin is glycidyl ether, glycidyl ester, glycidylamine, linear aliphatic or alicyclic epoxy resin.
The high-strength high-modulus electromagnetic shielding functional structure integrated light material has the advantages that the thickness of a Polydopamine (PDA) layer is 100 nm-1 mu m; in the CF-Ni-PDA/CNT/epoxy composite material, the content of the carboxylated CNT is 0.3-2 wt% of the mass of the epoxy resin, and the volume content of the nickel-plated carbon fiber accounts for 48-52 vt% of the total volume of the composite material.
The invention also provides a method for preparing the high-strength high-modulus electromagnetic shielding function structure integrated light material, which comprises the steps of firstly carrying out surface oxidation on carbon fibers after chemical nickel plating, then depositing and accumulating a dopamine (PDA) layer to obtain CF-Ni-PDA, and then preparing the CF-Ni-PDA/CNT/epoxy composite material by using the CF-Ni-PDA, the carboxylated CNT and the epoxy resin as main raw materials and adopting a vacuum auxiliary resin infusion molding method.
As a preferred technical scheme:
according to the preparation method of the high-strength high-modulus electromagnetic shielding functional structure integrated light material, the surface oxidation is superficial oxidation; the specific process of carrying out superficial oxidation on the carbon fiber after chemical nickel plating comprises the following steps: soaking the carbon fiber after chemical nickel plating in an excessive hydrogen peroxide water solution with the concentration of 28-32 wt%, wherein the mass of hydrogen peroxide is preferably more than 1% of that of the copper mesh, the water bath temperature is set to be 70-90 ℃, and the soaking time is 10-20 min; washing with deionized water and absolute ethyl alcohol in sequence (washing CF-Ni with deionized water, and removing residual water with absolute ethyl alcohol) to obtain superficially oxidized CF-Ni;
principle of superficial oxidation: and oxidizing the shallow surface of the nickel layer on the carbon fiber after the chemical nickel plating by using hydrogen peroxide. If the hydrogen peroxide concentration is too low or the water bath temperature is too low, the oxidation efficiency is too low; if the concentration of the hydrogen peroxide is too high or the temperature of the water bath is too high, the oxidation reaction is violent and the controllability is low. The subsequent step is to remove the hydrogen peroxide solution remaining on the surface of the carbon fiber after electroless nickel plating.
The specific process for depositing the dopamine (PDA) layer to obtain the CF-Ni-PDA comprises the following steps: placing the CF-Ni subjected to superficial oxidation into a dopamine solution, carrying out constant-temperature oscillation reaction for 20-30 h at 20-40 ℃, washing with deionized water after the reaction is finished, and placing into a 60-100 ℃ drying oven for drying for later use to obtain CF-Ni-PDA;
the concentration of the dopamine solution is 0.05-0.5 wt.%, and the pH value is 8.2-8.7 (ultrasonic mixing is performed at room temperature for 10-20 min and uniform mixing is performed).
Principle of deposition of dopamine (PDA) layer: due to the friendly adhesion of dopamine to various substrates, polymerization reaction can occur on the surface of CF-Ni under alkaline conditions, and a dopamine (PDA) layer is deposited on the surface of the CF-Ni. PDA can form two interactions of Ni-N chemical bond and hydrogen bond with the superficial oxidized CF-Ni surface.
According to the preparation method of the high-strength high-modulus electromagnetic shielding functional structure integrated light material, the preparation process of the carbon fiber after chemical nickel plating comprises the following steps:
(1) and (3) desizing: refluxing the CF two-dimensional fabric with acetone at 40-80 ℃ for 2-4 h to obtain a desized CF fabric;
the purpose of desizing is as follows: the original sizing agent on the surface of the commercial CF fabric is removed, because the main component of the part is epoxy resin, and if the sizing agent is not removed, the subsequent nickel plating effect is influenced. When the temperature is lower than 40 ℃ or less than 2h, the pulp is removed insufficiently and the pulp remains; higher than 80 ℃ or more than 4 hours, has potential safety hazard and wastes energy.
(2) Coarsening: immersing the desized CF fabric into a roughening solution prepared from ammonium persulfate and sulfuric acid, carrying out intermittent ultrasonic treatment at room temperature (ultrasonic treatment for 2-3 min every 15 min) for 0.5-2 h, taking out, washing with deionized water, and drying for later use;
in the coarsening liquid, the concentration of ammonium persulfate is 180-220 g/L; the concentration of the sulfuric acid is 90-110 mL/L;
the purpose of coarsening is as follows: the CF surface is roughened to make the CF surface rough, thereby increasing the contact area between the coating and the CF and obtaining a dense metal coating with good bonding force.
(3) Sensitization: immersing the coarsened CF into a sensitizing solution prepared from stannous chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 10-20 min, taking out, washing with deionized water, and drying for later use;
in the sensitizing solution, the concentration of stannous chloride is 18-25 g/L, and the concentration of hydrochloric acid is 35-50 mL/L;
the purpose of sensitization is as follows: sn (OH) Cl and Sn (OH)2Combined to form floccule Sn2(OH)3Cl, as a layer of reducing substance, adhered to the CF surface.
(4) And (3) activation: immersing the sensitized CF into an activation solution prepared from palladium chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 10-20 min, taking out, washing with deionized water, and drying for later use;
in the activating solution, the concentration of palladium chloride is 0.2-0.3 g/L, and the concentration of hydrochloric acid is 2-3 mL/L;
the purpose of activation is as follows: when the CF is immersed in the noble metal solution for activation treatment, the reducing substances on the surface of the carbon fiber lead the noble metal Pb in the solution2+Reducing into catalytic crystal nucleus and adsorbing on the surface of CF to be used as a catalyst in the chemical plating process. Sensitization and activation are key steps in the chemical plating pretreatment process, and a layer of Pb-Sn colloid is adsorbed on the surface of CF after activation treatment.
(5) Reduction: placing the activated CF in a reducing solution, and carrying out ultrasonic treatment at room temperature for 3-7 min;
the preparation method of the reducing solution comprises the following steps: weighing 18-22 g of NaH2PO2·H2Diluting the O to 1.5-2.5L, stirring at room temperature for 3-7 min to prepare a uniform reducing solution,
the purpose of reduction is as follows: reduction of Pd remaining on the surface of carbon fibers2+。
(6) And (3) gel releasing: placing the reduced CF in a hydrochloric acid solution, carrying out ultrasonic treatment at 40-45 ℃ for 3-7 min, taking out, washing with deionized water for three times, and drying for later use; the concentration of the hydrochloric acid solution was 10 wt.%;
the purpose of dispergation is as follows: debonding, i.e. removing Sn adsorbed on the CF surface2(OH)3And (4) Cl. Sn around palladium particles can be selectively removed in the dispergation process2+So that the palladium core is exposed to serve as a catalyst for chemical reaction during chemical plating.
(7) Chemical nickel plating: and (3) placing the dispergated CF into a plating solution prepared in advance, reacting for 0.8-1.5 h at the temperature of 50-70 ℃, taking out after the reaction is finished, washing with deionized water, and drying in a drying oven at the temperature of 60-100 ℃ to obtain the chemical nickel-plated carbon fiber.
Purpose of nickel plating: chemical nickel plating, wherein the surface of CF has palladium core with catalytic activity, and metal ions in the plating solution generate oxidation-reduction reaction on the surface of CF to deposit a uniform and compact metal nickel layer.
The preparation method of the high-strength high-modulus electromagnetic shielding functional structure integrated light material comprises the following specific processes of: firstly, mixing epoxy resin and a curing agent in a ratio of 4.2: 1-3.8: 1, doping the mixture with carboxylated modified CNT, uniformly stirring, and defoaming in a vacuum oven at 50-70 ℃ for 20-50 minutes to obtain a resin mixture; and then carrying out vacuum assisted resin infusion molding on the defoamed resin mixture and CF-Ni-PDA, and curing for 3-6 h at 100-150 ℃ to obtain the CF-Ni-PDA/CNT/epoxy composite material.
Purpose and principle: by doping the carboxylated CNT, the conductivity of the composite material is enhanced by utilizing the synergistic effect of the CF and the CNT, so that the electromagnetic shielding effect of the composite material is improved. After the CNT is carboxylated, the adhesive capacity of the CNT and an epoxy resin matrix can be improved due to the existence of carboxyl, and the mechanical property of the composite material is enhanced.
The mechanism of the invention is as follows:
the invention adopts the epoxy resin as a matrix and the continuous carbon fiber as a reinforcement, so that the material can realize the characteristics of light weight, high strength and high modulus, namely the material has the density far lower than that of a metal electromagnetic shielding material and the tensile strength and the modulus far higher than those of a resin electromagnetic shielding material filled with nano particles. However, the electrical conductivity of the carbon fiber is lower than that of metal, and if the carbon fiber is directly used, the electromagnetic shielding efficiency is lower, so that the common requirement (more than 20dB) cannot be met. Therefore, the invention plates a metal nickel layer on the surface of the carbon fiber, so that the conductivity of the carbon fiber is improved by one order of magnitude, thereby improving the electromagnetic shielding efficiency of the composite material. The bonding property of the nickel-plated carbon fiber and the epoxy resin matrix is poor, and the invention provides a method for enhancing the interaction interface between the nickel-plated carbon fiber and the epoxy resin matrix by adopting a superficial oxidation and dopamine deposition combination method. The superficial oxidation is to oxidize only a superficial layer (10-100 nm) in a nickel layer through weak oxidation, wherein a part of nickel oxide and poly-dopamine which is subsequently deposited on the nickel layer and polymerized in situ form Ni-N bonds, a part of nickel oxide and amido bonds in the poly-dopamine can generate a large amount of hydrogen bonds, and meanwhile, amino groups on the poly-dopamine can react with epoxy groups in epoxy resin monomers to form N-C chemical bonds, so that the poly-dopamine is used as a bridge, and the interface strength between the nickel-plated carbon fibers subjected to superficial oxidation and the epoxy resin matrix is enhanced. Because the fiber and the matrix have stronger interface bonding strength, when the composite material is stressed, the stress can be fully transmitted to the fiber through the interface, so that the advantages of high strength and high modulus of the fiber are exerted, and the composite material integrally has high tensile strength, tensile modulus and ILSS. The most prominent of these is ILSS, since this performance index intuitively reflects the interfacial bonding ability of the fiber to the resin. The epoxy resin matrix is also doped with carboxylated CNT, and the adhesive capacity of the CNT and the epoxy resin matrix can be improved due to the existence of carboxyl, so that the mechanical property of the epoxy resin matrix in the composite material can be improved, and the mechanical property of the composite material is further enhanced.
Because the thickness of the nickel oxide layer is small, the nickel-plated carbon fiber can keep higher conductivity, and the composite material can also keep higher electromagnetic shielding efficiency. On the other hand, by doping the carboxylated CNT, the conductivity of the composite material is enhanced by utilizing the synergistic effect of the CF-Ni and the CNT, so that the electromagnetic shielding effectiveness of the composite material is improved. When the electromagnetic wave reaches the surface of the material, most incident electromagnetic wave is reflected, the shielding mechanism of the composite material is reflection, the other part of the electromagnetic wave penetrates through the first layer of carbon fiber, but the energy is exhausted through multiple internal reflections, and the internal absorption of the composite material to the electromagnetic wave is improved. The poly-dopamine on the surface of the fiber has little influence on the electromagnetic shielding effectiveness of the composite material, and the electromagnetic shielding value of the composite material is not obviously changed after surface treatment of different dopamine concentrations.
Advantageous effects
(1) Compared with other similar materials, the high-strength high-modulus electromagnetic shielding functional structure integrated light material has higher tensile strength and modulus and higher EMI value;
(2) according to the preparation method of the high-strength high-modulus electromagnetic shielding functional structure integrated light material, the material with higher tensile strength and modulus than the light material with the electromagnetic shielding function prepared in the prior art can be prepared, and the preparation method is controllable; after the surface of the carbon fiber is plated with nickel, performing superficial oxidation on the nickel-plated carbon fiber to enable the surface to generate strong interaction with the polydopamine sizing agent, so that the composite material achieves the performance indexes of high strength and high modulus; meanwhile, because the oxidation degree is not deep, the electromagnetic shielding effectiveness of the composite material is not influenced, and the EMI value is still high.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the teachings of the present invention, and such equivalents also fall within the scope of the appended claims.
(1) Testing the interlaminar shear strength: the interlaminar shear strength of the composite material plate is represented by a three-point bending short beam shear test, the test standard is ASTM D2344, the standard size of a sample is 4mm in thickness, 24mm in length, 8mm in width, the span-thickness ratio is 4:1, the test speed is 1.0mm/min, and 6 samples are tested in parallel to obtain the interlaminar shear strength of the composite material; interlaminar shear strength calculation formula:
Figure RE-GDA0003048849330000061
wherein tau is interlaminar shear strength and unit MPa; p is the maximum load when the sample is damaged, and the unit is N; b is the width of the pattern in mm; h is the thickness of the sample in mm.
(2) And (3) testing tensile property: and testing the tensile property of the composite material by adopting an Instron microcomputer controlled electronic universal testing machine. The size of a tensile sample strip is 120 multiplied by 15 multiplied by 1mm, a strain gauge is stuck to the middle position of the sample strip in the pulling direction, aluminum reinforcing sheets are polished and stuck to the two sides of the sample strip, the tensile rate is 2mm/min, and 6 samples are tested in parallel to obtain the tensile strength and the modulus of the composite material.
(3) Electromagnetic shielding effectiveness analysis: electromagnetic shielding effectiveness (EMI SE) of WR90 waveband (8.2GHz-12.4GHz) composite material is tested by using ZNB20 vector network analyzer of Luode and Schwarz (China) science and technology company, microwave S parameters of the composite material are obtained by using a waveguide method test, and the size of a sample is 22.86 multiplied by 10.16 multiplied by 1.0mm3。
Example 1
A preparation method of a high-strength high-modulus electromagnetic shielding functional structure integrated light material comprises the following specific steps:
(1) preparing the carbon fiber after chemical nickel plating:
(1.1) desizing: refluxing the unidirectional CF two-dimensional fabric with acetone at 40 ℃ for 4h to obtain a desized CF fabric;
(1.2) coarsening: immersing the desized CF fabric into a roughening solution prepared from ammonium persulfate and sulfuric acid, carrying out intermittent ultrasonic treatment at room temperature for 0.5h, taking out, washing with deionized water, and drying for later use; wherein, in the coarsening liquid, the concentration of ammonium persulfate is 180 g/L; the concentration of the sulfuric acid is 90 mL/L;
(1.3) sensitization: immersing the coarsened CF fabric into sensitizing solution prepared from stannous chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 10min, washing with deionized water after taking out, and drying for later use; wherein, in the sensitizing solution, the concentration of stannous chloride is 18g/L, and the concentration of hydrochloric acid is 35 mL/L;
(1.4) activation: immersing the sensitized CF fabric into an activation solution prepared from palladium chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 10min, taking out, washing with deionized water, and drying for later use; wherein, in the activating solution, the concentration of palladium chloride is 0.2g/L, and the concentration of hydrochloric acid is 2 mL/L;
(1.5) reduction: weighing 18g NaH2PO2·H2Diluting O to 1.5L, stirring at room temperature for 3min to prepare a uniform reducing solution; placing the activated CF fabric in a reducing solution, and carrying out ultrasonic treatment at room temperature for 3 min;
(1.6) dispergation: placing the reduced CF fabric in a hydrochloric acid solution with the concentration of 10 wt.% to perform ultrasonic treatment at 40 ℃ for 3min, taking out the CF fabric, washing the CF fabric with deionized water for three times, and drying the CF fabric for later use;
(1.7) electroless nickel plating: placing the dispergated CF fabric in a plating solution prepared in advance, reacting for 1.5h at the temperature of 50 ℃, taking out the fabric after the reaction is finished, and washing the fabric by using deionized water to obtain the fabric formed by the carbon fiber after chemical nickel plating, wherein the surface layer of the carbon fiber is a nickel layer, and the bonding force between the nickel layer and the carbon fiber is Van der Waals force, mechanical riveting and Ni-OH-C bonding;
(2) soaking the fabric formed by the carbon fiber after chemical nickel plating in excessive hydrogen peroxide water solution with the concentration of 28 wt%, setting the water bath temperature at 70 ℃ and the soaking time at 10 min; washing with deionized water and absolute ethyl alcohol in sequence to obtain a superficially oxidized CF-Ni fabric;
the surface of the nickel-plated carbon fiber in the shallow oxidized CF-Ni fabric contains a nickel layer with the thickness of 0.8 mu m and carbon fiber of nickel oxide with the thickness of 10nm, and the nickel oxide is positioned on the surface of the nickel layer;
(3) placing the CF-Ni fabric subjected to superficial oxidation into a dopamine solution, and carrying out constant-temperature oscillation reaction for 30h at the temperature of 20 ℃ to obtain a CF-Ni-PDA fabric; wherein the concentration of the dopamine solution is 0.05 wt.%, and the pH value is 8.2;
(4) firstly, mixing glycidyl ether epoxy resin E51 and diethyltoluenediamine in a ratio of 4.2:1, doping with carboxylated CNT, uniformly stirring, and defoaming in a vacuum oven at 50 ℃ for 50 minutes to obtain a resin mixture; and then carrying out vacuum assisted resin infusion molding on the defoamed resin mixture and the CF-Ni-PDA fabric, and curing for 6 hours at 100 ℃ to obtain the CF-Ni-PDA/CNT/epoxy composite material.
The prepared CF-Ni-PDA/CNT/epoxy composite material is composed of nickel-plated carbon fibers, a polydopamine layer, carboxylated CNTs and glycidyl ether epoxy resin E51, wherein in the CF-Ni-PDA/CNT/epoxy composite material, the content of the carboxylated CNTs is 0.3 wt% of the mass of the glycidyl ether epoxy resin E51, and the volume content of the nickel-plated carbon fibers accounts for 48 vt% of the total volume of the composite material; the nickel-plated carbon fiber is in a fabric form, the polydopamine layer is positioned between the nickel-plated carbon fiber and the glycidyl ether epoxy resin E51, the thickness of the polydopamine layer is 0.1 mu m, the polydopamine layer is connected with the nickel-plated carbon fiber through Ni-N bonds and hydrogen bonds, and the polydopamine layer is connected with the glycidyl ether epoxy resin E51 through N-C bonds; the carboxylated CNTs were uniformly dispersed in the glycidyl ether epoxy resin E51;
the CF-Ni-PDA/CNT/epoxy composite material has the interlaminar shear strength of 40MPa, the tensile strength of 450MPa, the tensile modulus of 55GPa and the electromagnetic shielding effectiveness of 29 dB.
Example 2
A preparation method of a high-strength high-modulus electromagnetic shielding functional structure integrated light material comprises the following specific steps:
(1) preparing the carbon fiber after chemical nickel plating:
(1.1) desizing: refluxing the plain CF two-dimensional fabric for 3.5 hours by acetone at 50 ℃ to obtain a desized CF fabric;
(1.2) coarsening: immersing the desized CF fabric into a roughening solution prepared from ammonium persulfate and sulfuric acid, carrying out intermittent ultrasonic treatment at room temperature for 1h, taking out, washing with deionized water, and drying for later use; wherein, in the coarsening liquid, the concentration of ammonium persulfate is 190 g/L; the concentration of the sulfuric acid is 95 mL/L;
(1.3) sensitization: immersing the coarsened CF fabric into sensitizing solution prepared from stannous chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 20min, washing with deionized water after taking out, and drying for later use; wherein, in the sensitizing solution, the concentration of stannous chloride is 19g/L, and the concentration of hydrochloric acid is 45 mL/L;
(1.4) activation: immersing the sensitized CF fabric into an activation solution prepared from palladium chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 13min, taking out, washing with deionized water, and drying for later use; wherein, in the activating solution, the concentration of palladium chloride is 0.2g/L, and the concentration of hydrochloric acid is 2 mL/L;
(1.5) reduction: weighing 20g NaH2PO2·H2Diluting O to 1.7L, stirring at room temperature for 5min to prepare a uniform reducing solution; placing the activated CF fabric in a reducing solution, and carrying out ultrasonic treatment at room temperature for 5 min;
(1.6) dispergation: placing the reduced CF fabric in a hydrochloric acid solution with the concentration of 10 wt.% to perform ultrasonic treatment at 41 ℃ for 4min, taking out the CF fabric, washing the CF fabric with deionized water for three times, and drying the CF fabric for later use;
(1.7) electroless nickel plating: placing the dispergated CF fabric in a plating solution prepared in advance, reacting for 1.2h at the temperature of 57 ℃, taking out the fabric after the reaction is finished, and washing the fabric by using deionized water to obtain the fabric formed by the carbon fiber after chemical nickel plating, wherein the surface layer of the carbon fiber is a nickel layer, and the binding force between the nickel layer and the carbon fiber is Van der Waals force, mechanical riveting and Ni-OH-C bonding;
(2) soaking the fabric formed by the carbon fiber after chemical nickel plating in excessive hydrogen peroxide water solution with the concentration of 30 wt%, setting the water bath temperature at 72 ℃ and the soaking time at 11 min; washing with deionized water and absolute ethyl alcohol in sequence to obtain a superficially oxidized CF-Ni fabric;
the surface of the nickel-plated carbon fiber in the shallow oxidized CF-Ni fabric contains a nickel layer with the thickness of 1.3 mu m and carbon fiber of nickel oxide with the thickness of 21nm, and the nickel oxide is positioned on the surface of the nickel layer;
(3) placing the CF-Ni fabric subjected to superficial oxidation into a dopamine solution, and carrying out constant-temperature oscillation reaction for 25 hours at 28 ℃ to obtain CF-Ni-PDA; wherein the concentration of the dopamine solution is 0.3 wt.%, and the pH value is 8.3;
(4) firstly, mixing glycidyl ether epoxy resin E51 and diethyltoluenediamine in a ratio of 4.1:1, doping with carboxylated CNT, uniformly stirring, and defoaming in a vacuum oven at 54 ℃ for 45 minutes to obtain a resin mixture; and then pouring and molding the defoamed resin mixture and the CF-Ni-PDA fabric by using vacuum-assisted resin, and curing for 5.5 hours at 110 ℃ to obtain the CF-Ni-PDA/CNT/epoxy composite material.
The prepared CF-Ni-PDA/CNT/epoxy composite material is composed of nickel-plated carbon fibers, a polydopamine layer, carboxylated CNTs and glycidyl ether epoxy resin E51, wherein in the CF-Ni-PDA/CNT/epoxy composite material, the content of the carboxylated CNTs is 1.8 wt% of the mass of the glycidyl ether epoxy resin E51, and the volume content of the nickel-plated carbon fibers accounts for 52 vt% of the total volume of the composite material; the nickel-plated carbon fiber is in a fabric shape, the polydopamine layer is positioned between the nickel-plated carbon fiber and the glycidyl ether epoxy resin E51, the thickness of the polydopamine layer is 0.7 mu m, the polydopamine layer is connected with the nickel-plated carbon fiber through Ni-N bonds and hydrogen bonds, and the polydopamine layer is connected with the glycidyl ether epoxy resin E51 through N-C bonds; the carboxylated CNTs were uniformly dispersed in the glycidyl ether epoxy resin E51;
the CF-Ni-PDA/CNT/epoxy composite material has the interlaminar shear strength of 47MPa, the tensile strength of 515MPa, the tensile modulus of 61GPa and the electromagnetic shielding effectiveness of 38 dB.
Example 3
A preparation method of a high-strength high-modulus electromagnetic shielding functional structure integrated light material comprises the following specific steps:
(1) preparing the carbon fiber after chemical nickel plating:
(1.1) desizing: refluxing the satin CF two-dimensional fabric for 2.5 hours by using acetone at 70 ℃ to obtain a desized CF fabric;
(1.2) coarsening: immersing the desized CF fabric into a roughening solution prepared from ammonium persulfate and sulfuric acid, carrying out intermittent ultrasonic treatment at room temperature for 2h, taking out, washing with deionized water, and drying for later use; wherein, in the coarsening liquid, the concentration of ammonium persulfate is 210 g/L; the concentration of the sulfuric acid is 106 mL/L;
(1.3) sensitization: immersing the coarsened CF fabric into sensitizing solution prepared from stannous chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 15min, washing with deionized water after taking out, and drying for later use; wherein, in the sensitizing solution, the concentration of stannous chloride is 21g/L, and the concentration of hydrochloric acid is 38 mL/L;
(1.4) activation: immersing the sensitized CF fabric into an activation solution prepared from palladium chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 17min, taking out, washing with deionized water, and drying for later use; wherein, in the activating solution, the concentration of palladium chloride is 0.2g/L, and the concentration of hydrochloric acid is 2 mL/L;
(1.5) reduction: 19g of NaH are weighed out2PO2·H2Diluting O to 1.6L, stirring at room temperature for 4min to prepare a uniform reducing solution; placing the activated CF fabric in a reducing solution, and carrying out ultrasonic treatment at room temperature for 4 min;
(1.6) dispergation: placing the reduced CF fabric in a hydrochloric acid solution with the concentration of 10 wt.% to perform ultrasonic treatment at 43 ℃ for 6min, taking out the CF fabric, washing the CF fabric with deionized water for three times, and drying the CF fabric for later use;
(1.7) electroless nickel plating: placing the dispergated CF fabric in a plating solution prepared in advance, reacting for 1.4h at the temperature of 52 ℃, taking out the fabric after the reaction is finished, and washing the fabric by using deionized water to obtain the fabric formed by the carbon fiber after chemical nickel plating, wherein the surface layer of the carbon fiber is a nickel layer, and the bonding force between the nickel layer and the carbon fiber is Van der Waals force, mechanical riveting and Ni-OH-C bonding;
(2) soaking the fabric formed by the carbon fiber after chemical nickel plating in an excessive hydrogen peroxide water solution with the concentration of 29 wt%, setting the water bath temperature at 75 ℃ and the soaking time at 13 min; washing with deionized water and absolute ethyl alcohol in sequence to obtain a superficially oxidized CF-Ni fabric;
the surface of the nickel-plated carbon fiber in the shallow oxidized CF-Ni fabric contains a nickel layer with the thickness of 1 mu m and a carbon fiber of nickel oxide with the thickness of 37nm, and the nickel oxide is positioned on the surface of the nickel layer;
(3) placing the CF-Ni fabric subjected to superficial oxidation into a dopamine solution, and carrying out constant-temperature oscillation reaction for 28h at 24 ℃ to obtain a CF-Ni-PDA fabric; wherein the concentration of the dopamine solution is 0.1 wt.%, and the pH value is 8.4;
(4) firstly, mixing glycidyl ether epoxy resin E51 and diethyltoluenediamine in a ratio of 4:1, doping with carboxylated CNT, uniformly stirring, and defoaming in a vacuum oven at 58 ℃ for 40 minutes to obtain a resin mixture; and then pouring and molding the defoamed resin mixture and the CF-Ni-PDA fabric by using vacuum-assisted resin, and curing for 5 hours at 120 ℃ to obtain the CF-Ni-PDA/CNT/epoxy composite material.
The prepared CF-Ni-PDA/CNT/epoxy composite material is composed of nickel-plated carbon fibers, a polydopamine layer, carboxylated CNTs and glycidyl ether epoxy resin E51, wherein in the CF-Ni-PDA/CNT/epoxy composite material, the content of the carboxylated CNTs is 0.9 wt% of the mass of the glycidyl ether epoxy resin E51, and the volume content of the nickel-plated carbon fibers accounts for 50 vt% of the total volume of the composite material; the nickel-plated carbon fiber is in a fabric shape, the polydopamine layer is positioned between the nickel-plated carbon fiber and the glycidyl ether epoxy resin E51, the thickness of the polydopamine layer is 0.2 mu m, the polydopamine layer is connected with the nickel-plated carbon fiber through Ni-N bonds and hydrogen bonds, and the polydopamine layer is connected with the glycidyl ether epoxy resin E51 through N-C bonds; the carboxylated CNTs were uniformly dispersed in the glycidyl ether epoxy resin E51;
the CF-Ni-PDA/CNT/epoxy composite material has the interlaminar shear strength of 43MPa, the tensile strength of 471MPa, the tensile modulus of 57GPa and the electromagnetic shielding effectiveness of 33 dB.
Example 4
A preparation method of a high-strength high-modulus electromagnetic shielding functional structure integrated light material comprises the following specific steps:
(1) preparing the carbon fiber after chemical nickel plating:
(1.1) desizing: refluxing the twill CF two-dimensional fabric with acetone at 60 ℃ for 3h to obtain a desized CF fabric;
(1.2) coarsening: immersing the desized CF fabric into a roughening solution prepared from ammonium persulfate and sulfuric acid, carrying out intermittent ultrasonic treatment at room temperature for 1.5h, taking out, washing with deionized water, and drying for later use; wherein, in the coarsening liquid, the concentration of ammonium persulfate is 200 g/L; the concentration of the sulfuric acid is 100 mL/L;
(1.3) sensitization: immersing the coarsened CF fabric into sensitizing solution prepared from stannous chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 13min, washing with deionized water after taking out, and drying for later use; wherein, in the sensitizing solution, the concentration of stannous chloride is 20g/L, and the concentration of hydrochloric acid is 42 mL/L;
(1.4) activation: immersing the sensitized CF fabric into an activation solution prepared from palladium chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 15min, taking out, washing with deionized water, and drying for later use; wherein, in the activating solution, the concentration of palladium chloride is 0.3g/L, and the concentration of hydrochloric acid is 3 mL/L;
(1.5) reduction: 21g of NaH was weighed2PO2·H2Diluting O to 1.8L, stirring at room temperature for 6min to prepare a uniform reducing solution; placing the activated CF fabric in a reducing solution, and carrying out ultrasonic treatment at room temperature for 6 min;
(1.6) dispergation: placing the reduced CF fabric in a hydrochloric acid solution with the concentration of 10 wt.% to perform ultrasonic treatment at 42 ℃ for 5min, taking out the CF fabric, washing the CF fabric with deionized water for three times, and drying the CF fabric for later use;
(1.7) electroless nickel plating: placing the dispergated CF fabric in a plating solution prepared in advance, reacting for 1h at the temperature of 66 ℃, taking out the CF fabric after the reaction is finished, and washing the CF fabric with deionized water to obtain a fabric formed by the carbon fiber after chemical nickel plating, wherein the surface layer of the carbon fiber is a nickel layer, and the bonding force between the nickel layer and the carbon fiber is Van der Waals force, mechanical riveting and Ni-OH-C bonding;
(2) soaking the fabric formed by the carbon fiber after chemical nickel plating in excessive hydrogen peroxide water solution with the concentration of 31 wt%, setting the water bath temperature at 78 ℃ and the soaking time at 15 min; washing with deionized water and absolute ethyl alcohol in sequence to obtain a superficially oxidized CF-Ni fabric;
the surface of the nickel-plated carbon fiber in the shallow oxidized CF-Ni fabric contains a nickel layer with the thickness of 1.2 mu m and carbon fiber of nickel oxide with the thickness of 52nm, and the nickel oxide is positioned on the surface of the nickel layer;
(3) placing the CF-Ni fabric subjected to superficial oxidation into a dopamine solution, and carrying out constant-temperature oscillation reaction for 23 hours at the temperature of 32 ℃ to obtain a CF-Ni-PDA fabric; wherein the concentration of the dopamine solution is 0.2 wt.%, and the pH value is 8.5;
(4) firstly, mixing glycidyl ether epoxy resin E51 and diethyltoluenediamine in a ratio of 3.9:1, doping with carboxylated CNT, uniformly stirring, and defoaming in a vacuum oven at 62 ℃ for 37 minutes to obtain a resin mixture; and then pouring and molding the defoamed resin mixture and the CF-Ni-PDA fabric by using vacuum-assisted resin, and curing for 4.5 hours at the temperature of 130 ℃ to obtain the CF-Ni-PDA/CNT/epoxy composite material.
The prepared CF-Ni-PDA/CNT/epoxy composite material is composed of nickel-plated carbon fibers, a polydopamine layer, carboxylated CNTs and glycidyl ether epoxy resin E51, wherein in the CF-Ni-PDA/CNT/epoxy composite material, the content of the carboxylated CNTs is 1.2 wt% of the mass of the glycidyl ether epoxy resin E51, and the volume content of the nickel-plated carbon fibers accounts for 49 vt% of the total volume of the composite material; the nickel-plated carbon fiber is in a fabric shape, the polydopamine layer is positioned between the nickel-plated carbon fiber and the glycidyl ether epoxy resin E51, the thickness of the polydopamine layer is 0.5 mu m, the polydopamine layer is connected with the nickel-plated carbon fiber through Ni-N bonds and hydrogen bonds, and the polydopamine layer is connected with the glycidyl ether epoxy resin E51 through N-C bonds; the carboxylated CNTs were uniformly dispersed in the glycidyl ether epoxy resin E51;
the CF-Ni-PDA/CNT/epoxy composite material has the interlaminar shear strength of 51MPa, the tensile strength of 496MPa, the tensile modulus of 58GPa and the electromagnetic shielding effectiveness of 34 dB.
Example 5
A preparation method of a high-strength high-modulus electromagnetic shielding functional structure integrated light material comprises the following specific steps:
(1) preparing the carbon fiber after chemical nickel plating:
(1.1) desizing: refluxing the non-bent CF two-dimensional fabric for 3 hours by using acetone at 65 ℃ to obtain a desized CF fabric;
(1.2) coarsening: immersing the desized CF fabric into a roughening solution prepared from ammonium persulfate and sulfuric acid, carrying out intermittent ultrasonic treatment at room temperature for 1h, taking out, washing with deionized water, and drying for later use; wherein, in the coarsening liquid, the concentration of ammonium persulfate is 205 g/L; the concentration of the sulfuric acid is 103 mL/L;
(1.3) sensitization: immersing the coarsened CF fabric into sensitizing solution prepared from stannous chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 17min, washing with deionized water after taking out, and drying for later use; wherein, in the sensitizing solution, the concentration of stannous chloride is 24g/L, and the concentration of hydrochloric acid is 44 mL/L;
(1.4) activation: immersing the sensitized CF fabric into an activation solution prepared from palladium chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 19min, taking out, washing with deionized water, and drying for later use; wherein, in the activating solution, the concentration of palladium chloride is 0.3g/L, and the concentration of hydrochloric acid is 3 mL/L;
(1.5) reduction: 21g of NaH was weighed2PO2·H2Diluting O to 2L, stirring at room temperature for 6min to prepare a uniform reducing solution; placing the activated CF fabric in a reducing solution, and carrying out ultrasonic treatment at room temperature for 6 min;
(1.6) dispergation: placing the reduced CF fabric in a hydrochloric acid solution with the concentration of 10 wt.% to perform ultrasonic treatment at 44 ℃ for 6min, taking out the CF fabric, washing the CF fabric with deionized water for three times, and drying the CF fabric for later use;
(1.7) electroless nickel plating: placing the dispergated CF fabric in a plating solution prepared in advance, reacting for 1.1h at the temperature of 62 ℃, taking out the fabric after the reaction is finished, and washing the fabric by using deionized water to obtain the fabric formed by the carbon fiber after chemical nickel plating, wherein the surface layer of the carbon fiber is a nickel layer, and the bonding force between the nickel layer and the carbon fiber is Van der Waals force, mechanical riveting and Ni-OH-C bonding;
(2) soaking the fabric formed by the carbon fiber after chemical nickel plating in excessive hydrogen peroxide water solution with the concentration of 32 wt%, setting the water bath temperature to be 83 ℃, and the soaking time to be 17 min; washing with deionized water and absolute ethyl alcohol in sequence to obtain a superficially oxidized CF-Ni fabric;
the surface of the nickel-plated carbon fiber in the shallow oxidized CF-Ni fabric contains a nickel layer with the thickness of 1.5 mu m and carbon fiber of nickel oxide with the thickness of 63nm, and the nickel oxide is positioned on the surface of the nickel layer;
(3) placing the CF-Ni fabric subjected to superficial oxidation into a dopamine solution, and carrying out constant-temperature oscillation reaction for 26 hours at 26 ℃ to obtain a CF-Ni-PDA fabric; wherein the concentration of the dopamine solution is 0.4 wt.%, and the pH value is 8.6;
(4) firstly, mixing glycidyl ether epoxy resin E51 and diethyltoluenediamine in a ratio of 3.9:1, doping with carboxylated CNT, uniformly stirring, and defoaming in a vacuum oven at 66 ℃ for 33 minutes to obtain a resin mixture; and then pouring and molding the defoamed resin mixture and the CF-Ni-PDA fabric by using vacuum-assisted resin, and curing for 4 hours at 135 ℃ to obtain the CF-Ni-PDA/CNT/epoxy composite material.
The prepared CF-Ni-PDA/CNT/epoxy composite material is composed of nickel-plated carbon fibers, a polydopamine layer, carboxylated CNTs and glycidyl ether epoxy resin E51, wherein in the CF-Ni-PDA/CNT/epoxy composite material, the content of the carboxylated CNTs accounts for 2 wt% of the mass of the glycidyl ether epoxy resin E51, and the volume content of the nickel-plated carbon fibers accounts for 51 vt% of the total volume of the composite material; the nickel-plated carbon fiber is in a fabric form, the polydopamine layer is positioned between the nickel-plated carbon fiber and the glycidyl ether epoxy resin E51, the thickness of the polydopamine layer is 0.6 mu m, the polydopamine layer is connected with the nickel-plated carbon fiber through Ni-N bonds and hydrogen bonds, and the polydopamine layer is connected with the glycidyl ether epoxy resin E51 through N-C bonds; the carboxylated CNTs were uniformly dispersed in the glycidyl ether epoxy resin E51;
the CF-Ni-PDA/CNT/epoxy composite material has the interlaminar shear strength of 58MPa, the tensile strength of 557MPa, the tensile modulus of 59GPa and the electromagnetic shielding effectiveness of 40 dB.
Example 6
A preparation method of a high-strength high-modulus electromagnetic shielding functional structure integrated light material comprises the following specific steps:
(1) preparing the carbon fiber after chemical nickel plating:
(1.1) desizing: refluxing the unidirectional CF two-dimensional fabric with acetone at 75 ℃ for 2h to obtain a desized CF fabric;
(1.2) coarsening: immersing the desized CF fabric into a roughening solution prepared from ammonium persulfate and sulfuric acid, carrying out intermittent ultrasonic treatment at room temperature for 0.5h, taking out, washing with deionized water, and drying for later use; wherein, in the coarsening liquid, the concentration of ammonium persulfate is 215 g/L; the concentration of the sulfuric acid is 108 mL/L;
(1.3) sensitization: immersing the coarsened CF fabric into sensitizing solution prepared from stannous chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 18min, washing with deionized water after taking out, and drying for later use; wherein, in the sensitizing solution, the concentration of stannous chloride is 23g/L, and the concentration of hydrochloric acid is 48 mL/L;
(1.4) activation: immersing the sensitized CF fabric into an activation solution prepared from palladium chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 17min, taking out, washing with deionized water, and drying for later use; wherein, in the activating solution, the concentration of palladium chloride is 0.3g/L, and the concentration of hydrochloric acid is 3 mL/L;
(1.5) reduction: weighing 22g NaH2PO2·H2Diluting O to 2.2L, stirring at room temperature for 7min to obtain uniform reductionLiquid; placing the activated CF fabric in a reducing solution, and carrying out ultrasonic treatment at room temperature for 7 min;
(1.6) dispergation: placing the reduced CF fabric in a hydrochloric acid solution with the concentration of 10 wt.% to perform ultrasonic treatment for 7min at 45 ℃, taking out the CF fabric, washing the CF fabric with deionized water for three times, and drying the CF fabric for later use;
(1.7) electroless nickel plating: placing the dispergated CF fabric in a plating solution prepared in advance, reacting for 1.3h at the temperature of 54 ℃, taking out the fabric after the reaction is finished, and washing the fabric by using deionized water to obtain the fabric formed by the carbon fiber after chemical nickel plating, wherein the surface layer of the carbon fiber is a nickel layer, and the bonding force between the nickel layer and the carbon fiber is Van der Waals force, mechanical riveting and Ni-OH-C bonding;
(2) soaking the fabric formed by the carbon fiber after chemical nickel plating in excessive hydrogen peroxide water solution with the concentration of 30 wt%, setting the water bath temperature to be 86 ℃, and the soaking time to be 19 min; washing with deionized water and absolute ethyl alcohol in sequence to obtain a superficially oxidized CF-Ni fabric;
the surface of the nickel-plated carbon fiber in the shallow oxidized CF-Ni fabric contains a nickel layer with the thickness of 1.1 mu m and a carbon fiber of nickel oxide with the thickness of 86nm, and the nickel oxide is positioned on the surface of the nickel layer;
(3) placing the CF-Ni fabric subjected to superficial oxidation into a dopamine solution, and carrying out constant-temperature oscillation reaction for 22 hours at 35 ℃ to obtain a CF-Ni-PDA fabric; wherein the concentration of the dopamine solution is 0.5 wt.%, and the pH value is 8.7;
(4) firstly, mixing glycidyl ether epoxy resin E51 and diethyltoluenediamine in a ratio of 3.8:1, doping with carboxylated CNT, uniformly stirring, and defoaming in a vacuum oven at 68 ℃ for 27 minutes to obtain a resin mixture; and then pouring and molding the defoamed resin mixture and the CF-Ni-PDA fabric by using vacuum-assisted resin, and curing for 3.5 hours at 140 ℃ to obtain the CF-Ni-PDA/CNT/epoxy composite material.
The prepared CF-Ni-PDA/CNT/epoxy composite material is composed of nickel-plated carbon fibers, a polydopamine layer, carboxylated CNTs and glycidyl ether epoxy resin E51, wherein in the CF-Ni-PDA/CNT/epoxy composite material, the content of the carboxylated CNTs is 1.5 wt% of the mass of the glycidyl ether epoxy resin E51, and the volume content of the nickel-plated carbon fibers accounts for 52 vt% of the total volume of the composite material; the nickel-plated carbon fiber is in a fabric shape, the polydopamine layer is positioned between the nickel-plated carbon fiber and the glycidyl ether epoxy resin E51, the thickness of the polydopamine layer is 0.9 mu m, the polydopamine layer is connected with the nickel-plated carbon fiber through Ni-N bonds and hydrogen bonds, and the polydopamine layer is connected with the glycidyl ether epoxy resin E51 through N-C bonds; the carboxylated CNTs were uniformly dispersed in the glycidyl ether epoxy resin E51;
the CF-Ni-PDA/CNT/epoxy composite material has the interlaminar shear strength of 66MPa, the tensile strength of 588MPa, the tensile modulus of 65GPa and the electromagnetic shielding effectiveness of 35 dB.
Example 7
A preparation method of a high-strength high-modulus electromagnetic shielding functional structure integrated light material comprises the following specific steps:
(1) preparing the carbon fiber after chemical nickel plating:
(1.1) desizing: refluxing the plain CF two-dimensional fabric with acetone at 80 ℃ for 2h to obtain a desized CF fabric;
(1.2) coarsening: immersing the desized CF fabric into a roughening solution prepared from ammonium persulfate and sulfuric acid, carrying out intermittent ultrasonic treatment at room temperature for 2h, taking out, washing with deionized water, and drying for later use; wherein, in the coarsening liquid, the concentration of ammonium persulfate is 220 g/L; the concentration of the sulfuric acid is 110 mL/L;
(1.3) sensitization: immersing the coarsened CF fabric into sensitizing solution prepared from stannous chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 14min, washing with deionized water after taking out, and drying for later use; wherein, in the sensitizing solution, the concentration of stannous chloride is 25g/L, and the concentration of hydrochloric acid is 50 mL/L;
(1.4) activation: immersing the sensitized CF fabric into an activation solution prepared from palladium chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 20min, taking out, washing with deionized water, and drying for later use; wherein, in the activating solution, the concentration of palladium chloride is 0.3g/L, and the concentration of hydrochloric acid is 3 mL/L;
(1.5) reduction: weighing 22g NaH2PO2·H2Diluting O to 2.5L, stirring at room temperature for 7min to prepare a uniform reducing solution; placing the activated CF fabric in a reducing solution, and carrying out ultrasonic treatment at room temperature for 7 min;
(1.6) dispergation: placing the reduced CF fabric in a hydrochloric acid solution with the concentration of 10 wt.% to perform ultrasonic treatment for 7min at 45 ℃, taking out the CF fabric, washing the CF fabric with deionized water for three times, and drying the CF fabric for later use;
(1.7) electroless nickel plating: placing the dispergated CF fabric in a plating solution prepared in advance, reacting for 0.8h at the temperature of 70 ℃, taking out the fabric after the reaction is finished, and washing the fabric by using deionized water to obtain the fabric formed by the carbon fiber after chemical nickel plating, wherein the surface layer of the carbon fiber is a nickel layer, and the bonding force between the nickel layer and the carbon fiber is Van der Waals force, mechanical riveting and Ni-OH-C bonding;
(2) soaking the fabric formed by the carbon fiber after chemical nickel plating in an excessive hydrogen peroxide water solution with the concentration of 29 wt%, setting the water bath temperature at 90 ℃ and the soaking time at 20 min; washing with deionized water and absolute ethyl alcohol in sequence to obtain a superficially oxidized CF-Ni fabric;
the surface of the nickel-plated carbon fiber in the fabric contains a nickel layer with the thickness of 0.9 mu m and carbon fiber of nickel oxide with the thickness of 100nm, and the nickel oxide is positioned on the surface of the nickel layer;
(3) placing the CF-Ni fabric subjected to superficial oxidation into a dopamine solution, and carrying out constant-temperature oscillation reaction for 20 hours at 40 ℃ to obtain a CF-Ni-PDA fabric; wherein the concentration of the dopamine solution is 0.5 wt.%, and the pH value is 8.7;
(4) firstly, mixing glycidyl ether epoxy resin E51 and diethyltoluenediamine in a ratio of 3.8:1, doping with carboxylated CNT, uniformly stirring, and defoaming in a vacuum oven at 70 ℃ for 20 minutes to obtain a resin mixture; and then pouring and molding the defoamed resin mixture and the CF-Ni-PDA fabric by using vacuum-assisted resin, and curing for 3 hours at 150 ℃ to obtain the CF-Ni-PDA/CNT/epoxy composite material.
The prepared CF-Ni-PDA/CNT/epoxy composite material is composed of nickel-plated carbon fibers, a polydopamine layer, carboxylated CNTs and glycidyl ether epoxy resin E51, wherein in the CF-Ni-PDA/CNT/epoxy composite material, the content of the carboxylated CNTs is 0.6 wt% of the mass of the glycidyl ether epoxy resin E51, and the volume content of the nickel-plated carbon fibers accounts for 50 vt% of the total volume of the composite material; the nickel-plated carbon fiber is in a fabric shape, the polydopamine layer is positioned between the nickel-plated carbon fiber and the glycidyl ether epoxy resin E51, the thickness of the polydopamine layer is 1 mu m, the polydopamine layer is connected with the nickel-plated carbon fiber through Ni-N bonds and hydrogen bonds, and the polydopamine layer is connected with the glycidyl ether epoxy resin E51 through N-C bonds; the carboxylated CNTs were uniformly dispersed in the glycidyl ether epoxy resin E51;
the CF-Ni-PDA/CNT/epoxy composite material has the interlaminar shear strength of 70MPa, the tensile strength of 600MPa, the tensile modulus of 63GPa and the electromagnetic shielding effectiveness of 32 dB.

Claims (9)

1. The high-strength high-modulus electromagnetic shielding functional structure integrated light material is characterized in that the material is a CF-Ni-PDA/CNT/epoxy composite material consisting of nickel-plated carbon fibers, a polydopamine layer, carboxylated CNT and epoxy resin;
the nickel-plated carbon fiber is a carbon fiber with nickel oxide on the surface;
the polydopamine layer is positioned between the nickel-plated carbon fiber and the epoxy resin, the polydopamine layer is connected with the nickel-plated carbon fiber through Ni-N bonds and hydrogen bonds, and the polydopamine layer is connected with the epoxy resin through N-C bonds.
2. The high-strength high-modulus electromagnetic shielding functional structure integrated light material as claimed in claim 1, wherein the thickness of the nickel oxide is 10-100 nm.
3. The high-strength high-modulus electromagnetic shielding function structure integrated light material as claimed in claim 1, wherein the surface of the nickel-plated carbon fiber further comprises a nickel layer, and the nickel layer is connected with the carbon fiber by van der waals force, mechanical riveting and Ni-OH-C bonding; the nickel oxide is positioned on the surface of the nickel layer.
4. The high-strength high-modulus electromagnetic shielding functional structure integrated light material as claimed in claim 1, wherein in the CF-Ni-PDA/CNT/epoxy composite material, the nickel-plated carbon fiber is in the form of fabric, and the fabric has a structure of unidirectional fabric, plain fabric, satin fabric, twill fabric or non-buckling fabric;
the CF-Ni-PDA/CNT/epoxy composite material has an interlaminar shear strength of 40-70 MPa, a tensile strength of 450-600 MPa, a tensile modulus of 55-65 GPa, and an electromagnetic shielding effectiveness of 29-40 dB.
5. The high-strength high-modulus electromagnetic shielding functional structure integrated light material as claimed in claim 1, wherein the thickness of the polydopamine layer is 100 nm-1 μm; in the CF-Ni-PDA/CNT/epoxy composite material, the content of the carboxylated CNT is 0.3-2 wt% of the mass of the epoxy resin, and the volume content of the nickel-plated carbon fiber accounts for 48-52 vt% of the total volume of the composite material.
6. The method for preparing the high-strength high-modulus electromagnetic shielding function structure integrated light material as claimed in claim 1, is characterized in that: firstly, carrying out surface oxidation on carbon fibers after chemical nickel plating, then depositing and accumulating a dopamine layer to obtain CF-Ni-PDA, and then preparing the CF-Ni-PDA/CNT/epoxy composite material by using the CF-Ni-PDA, carboxylated CNT and epoxy resin as main raw materials and adopting a vacuum auxiliary resin infusion molding method.
7. The preparation method of the high-strength high-modulus electromagnetic shielding functional structure integrated lightweight material as claimed in claim 6, wherein the surface oxidation is superficial oxidation; the specific process of carrying out superficial oxidation on the carbon fiber after chemical nickel plating comprises the following steps: soaking the carbon fiber after chemical nickel plating in a hydrogen peroxide water solution with the concentration of 28-32 wt.%, setting the water bath temperature to be 70-90 ℃ and the soaking time to be 10-20 min; washing with deionized water and absolute ethyl alcohol in sequence to obtain superficially oxidized CF-Ni;
the specific process for depositing the polydopamine layer to obtain the CF-Ni-PDA comprises the following steps: placing the CF-Ni subjected to superficial oxidation into a dopamine solution, and carrying out constant-temperature oscillation reaction for 20-30 h at the temperature of 20-40 ℃ to obtain CF-Ni-PDA;
the concentration of the dopamine solution is 0.05-0.5 wt.%, and the pH value is 8.2-8.7.
8. The preparation method of the high-strength high-modulus electromagnetic shielding functional structure integrated light material as claimed in claim 6, wherein the preparation process of the carbon fiber after chemical nickel plating is as follows:
(1) and (3) desizing: refluxing the CF two-dimensional fabric with acetone at 40-80 ℃ for 2-4 h to obtain a desized CF fabric;
(2) coarsening: immersing the desized CF fabric into a roughening solution prepared from ammonium persulfate and sulfuric acid, carrying out intermittent ultrasonic treatment at room temperature for 0.5-2 h, taking out, washing with deionized water, and drying for later use;
in the coarsening liquid, the concentration of ammonium persulfate is 180-220 g/L; the concentration of the sulfuric acid is 90-110 mL/L;
(3) sensitization: immersing the coarsened CF fabric into a sensitizing solution prepared from stannous chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 10-20 min, taking out, washing with deionized water, and drying for later use;
in the sensitizing solution, the concentration of stannous chloride is 18-25 g/L, and the concentration of hydrochloric acid is 35-50 mL/L;
(4) and (3) activation: immersing the sensitized CF fabric into an activation solution prepared from palladium chloride and hydrochloric acid, carrying out ultrasonic treatment at room temperature for 10-20 min, taking out, washing with deionized water, and drying for later use;
in the activating solution, the concentration of palladium chloride is 0.2-0.3 g/L, and the concentration of hydrochloric acid is 2-3 mL/L;
(5) reduction: placing the activated CF fabric in a reducing solution, and carrying out ultrasonic treatment at room temperature for 3-7 min;
the preparation method of the reducing solution comprises the following steps: weighing 18-22 g of NaH2PO2·H2Diluting the O to 1.5-2.5L, stirring at room temperature for 3-7 min to prepare a uniform reducing solution,
(6) and (3) gel releasing: placing the reduced CF fabric in a hydrochloric acid solution, carrying out ultrasonic treatment at 40-45 ℃ for 3-7 min, taking out, washing with deionized water for three times, and drying for later use; the concentration of the hydrochloric acid solution was 10 wt.%;
(7) chemical nickel plating: and (3) placing the dispergated CF fabric into a plating solution prepared in advance, reacting for 0.8-1.5 h at the temperature of 50-70 ℃, taking out after the reaction is finished, and washing with deionized water to obtain the chemical nickel-plated carbon fiber.
9. The preparation method of the high-strength high-modulus electromagnetic shielding functional structure integrated light material as claimed in claim 6, wherein the vacuum assisted resin infusion molding method comprises the following specific processes: mixing epoxy resin and a curing agent in a ratio of 4.2: 1-3.8: 1, doping with carboxylated CNT, uniformly stirring, and defoaming in a vacuum oven at 50-70 ℃ for 20-50 minutes to obtain a resin mixture; and then carrying out vacuum assisted resin infusion molding on the defoamed resin mixture and CF-Ni-PDA, and curing for 3-6 h at 100-150 ℃ to obtain the CF-Ni-PDA/CNT/epoxy composite material.
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CN116355501A (en) * 2023-02-28 2023-06-30 中国船舶集团有限公司第十二研究所 Preparation method of carbon nano tube-chopped carbon fiber composite modified epoxy coating

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