CN113999495A - Carbon fiber/epoxy composite material with integrated structure and function and preparation method thereof - Google Patents

Carbon fiber/epoxy composite material with integrated structure and function and preparation method thereof Download PDF

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CN113999495A
CN113999495A CN202111369562.XA CN202111369562A CN113999495A CN 113999495 A CN113999495 A CN 113999495A CN 202111369562 A CN202111369562 A CN 202111369562A CN 113999495 A CN113999495 A CN 113999495A
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carbon fiber
transition metal
composite material
epoxy
epoxy resin
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CN113999495B (en
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沈小军
范梦漩
朱松青
管纪鹏
党蕊琼
郭少聪
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Jiaxing University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
    • 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
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    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
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    • 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
    • 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
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K9/02—Ingredients treated with inorganic substances

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Abstract

The invention relates to a carbon fiber/epoxy composite material with integrated structure and function and a preparation method thereof, wherein the composite material comprises a carbon fiber fabric reinforcing material, an epoxy resin matrix material and a nano-scale transition metal sulfide which is decorated on the surface of carbon fiber and has functionality; transition metal sulfide refers to petaloid tungsten sulfide synthesized by a hydrothermal method. According to the invention, the dense nanoflower microstructure is introduced on the surface of the carbon fiber by the compounded surfactant and a hydrothermal method, so that the contact area of the fiber and an epoxy resin matrix is increased, the interface of the matrix resin and the carbon fiber is combined more tightly, and the composite material shows excellent interlayer shearing performance. And due to the introduction of the tungsten sulfide nanoflower, the composite material is endowed with a certain electromagnetic absorption function.

Description

Carbon fiber/epoxy composite material with integrated structure and function and preparation method thereof
Technical Field
The invention belongs to the field of preparation of polymer-based composite materials, and particularly relates to a structure-function integrated carbon fiber/epoxy composite material and a preparation method thereof.
Background
Carbon Fiber/Epoxy Resin Composites (CFRERC) are advanced Composites that use Epoxy Resin as a matrix and Carbon fibers as a reinforcement material. The composite material has the main properties of advanced composite materials, namely high specific strength and specific modulus, and also has a series of excellent properties such as high fatigue strength, small thermal expansion coefficient, corrosion resistance, stable structure size, designable material properties and the like. As a new advanced composite material, EP/CF composite materials can be used as structural materials for load bearing, and can meet the field where strict requirements are placed on weight, strength, rigidity, fatigue characteristics, and the like, and in addition, EP/CF composite materials can also function as functional materials due to their high temperature and chemical stability. The method is widely applied to various high and new technical fields and civil fields such as cultural and sports equipment, medical machinery, automobiles, traffic, energy, buildings, machinery, chemical engineering and the like.
The carbon fiber/epoxy composite material has a history of more than sixty years, but research and application will be deeper along with the development of high-tech science and technology, the appearance and performance of new materials are promoted by designability of the structure and performance of the carbon fiber/epoxy composite material, and the application field of the carbon fiber/epoxy composite material will become more and more extensive. The structural integrated functional material is the main development direction of the high-performance carbon fiber/epoxy resin composite material, and the material has the characteristics of light weight, high strength, high toughness, high temperature resistance, corrosion resistance, wear resistance, low cost and structural function integration, and can adapt to special environmental requirements. Wangsheng of Shandong university departs from a conventional interlayer structure, and utilizes carbon fiber, aramid fiber, multi-walled carbon nanotubes (MWCNTs) and carbon nitride (C)3N4) The fillers are designed into a series of mixed knotsThe structure not only improves the mechanical properties of the carbon fiber/epoxy composite material, such as interlaminar shear strength (ILSS), tensile modulus, flexural modulus and the like, but also greatly improves the damping performance of the material. According to the extra waves of Wuhan theory university, carbonyl iron powder is added into carbon fiber cloth to improve the density of fiber yarn bundles, and meanwhile, the absorption loss of a CF/EP composite material is improved, so that the material has a more stable sandwich structure and has a shielding performance controllable in the interlayer direction.
In the prior art, CNTs are deposited on the surface of carbon fibers to improve interlayer performance and electromagnetic shielding performance, but the carbon fibers have the disadvantages of poor dispersibility, complex preparation, high price and the like. The transition metal sulfide with controllable morphology can more conveniently regulate and control the electromagnetic shielding performance of the whole material.
However, a considerable number of products in carbon fiber composites are laminate structures, which are typically "three-phase" structures on a microscopic scale, including carbon fiber reinforcement phases, resin matrix phases, and interphase phases, where interphase phases are ligaments and bridges that transfer loads from the resin to the carbon fibers. The structure, composition, property, combination mode and interface bonding strength of the interface phase play an important role in the mechanical property of the carbon fiber resin matrix composite material. The carbon fiber has smooth surface, small specific surface area, few active groups and poor wettability with a resin matrix, so that the carbon fiber layers are completely bonded by the resin, the interface phase becomes the weakest link of the composite material, and the cracking and peeling phenomena among the layers of the material are easily caused in the using process. Therefore, how to improve the interfacial bonding between the carbon fiber and the epoxy matrix is the key to improve the interlaminar shear performance of the composite material.
In recent years, researchers have focused on modifying carbon fibers themselves primarily to improve their surface roughness and polarity. The surface roughness of the carbon fiber is improved, so that a strong mechanical locking effect can be formed between the fiber and the resin matrix, and when the material is loaded, concave and convex points on the surface of the fiber can more powerfully catch the resin matrix, so that the aim that the fiber is not easy to pull out from the resin matrix is fulfilled.
Disclosure of Invention
In order to overcome the defect that the carbon fiber/epoxy resin composite material in the prior art is poor in interface phase affinity and is a weak link of the composite material, the invention introduces the nanometer microstructure of petal-shaped transition metal sulfide on the surface of the carbon fiber, and has three purposes: 1, improving the roughness of an interface, being beneficial to epoxy infiltration and increasing the contact area of two phases of the interface; 2, providing a mechanical interlocking effect, so that the material is more difficult to break and peel between layers when being loaded, and shows excellent interlaminar shear performance; and 3, introducing tungsten disulfide nanosheets with high specific surface area and high dielectric loss to be compounded with carbon fibers, increasing the electromagnetic wave attenuation capability of the material, improving the electromagnetic shielding performance and endowing the composite material with a certain electromagnetic absorption function. The research of introducing the electromagnetic absorption function while improving the interlaminar shear performance of the carbon fiber/epoxy composite material by growing the petaloid tungsten sulfide on the surface of the carbon fiber is not reported in a public way.
In order to solve the technical problems, the invention provides the following technical scheme:
a structure function integrated carbon fiber/epoxy composite material comprises the following raw materials: carbon fiber cloth with nano transition metal sulfide modified on the surface, epoxy resin and curing agent.
The mass ratio of the carbon fiber cloth to the epoxy resin to the curing agent is 1: 2-5: 0.2-0.3.
The gram weight of the carbon fiber cloth is 200-300.
The epoxy resin is bisphenol type epoxy resin, such as bisphenol A epoxy resin, bisphenol S epoxy resin and bisphenol F epoxy resin, and the epoxy value is 0.30-0.51. Specifically, for example, the bisphenol A epoxy resin is at least one selected from the group consisting of E-51, E-44, E-42 and E-35.
The curing agent is selected from at least one of 593 and 591.
The transition metal sulfide is at least one selected from tungsten sulfide, molybdenum sulfide, chromium sulfide and nickel sulfide.
The transition metal sulfide is in a nanometer flower shape and is formed by stacking two-dimensional sheet structures with the diameters of about 3-5 mu m.
The transition metal sulfide is obtained by in-situ growth on the surface of the carbon fiber cloth reinforced material through hydrothermal reaction, and specifically, the carbon fiber material with the surface cleaned and a transition metal sulfide precursor solution are reacted for 12 to 36 hours at the temperature of between 150 and 200 ℃.
The transition metal sulfide precursor solution is obtained by uniformly mixing a transition metal source, a sulfur source, a reducing agent and a surfactant.
Further, the transition metal source is a salt of at least one of tungsten, molybdenum, chromium and nickel, such as sodium, potassium/ammonium salt (A) of transition metal oxyacid2MO4A is Na, K or NH4M is W, Mo, Ni or Cr), a halide of a transition Metal (MX)nM is W, Mo, Ni or Cr, X is a halogen atom, and n is an integer of 2 to 6).
The sulphur source is selected from thiourea and/or thioacetamide, providing sulphur ions; the reducing agent is selected from at least one of hydroxylamine hydrochloride and oxalic acid.
The surfactant is a compound of quaternary ammonium salt cationic surfactant and fatty alcohol hydroxyethyl sodium sulfonate according to the mass ratio of 3-5:1, and the general formula of the quaternary ammonium salt cationic surfactant can be expressed as [ AB3N]+X-Wherein A is a long-chain alkyl group of 12 to 20 carbon atoms, B is a methyl or ethyl group, and X is a halogen atom such as chlorine or bromine; preferably, the quaternary ammonium salt cationic surfactant is selected from at least one of cetyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium bromide.
The inventor has unexpectedly discovered that by adopting the combination of the long-chain alkyl quaternary ammonium salt surfactant and the fatty alcohol hydroxyethyl sodium sulfonate as the surfactant, although the two surfactants have head groups with different charges, precipitation can be generated due to electrostatic action or liquid crystal greatly limits the application of the surfactants, and a stable microemulsion system can be obtained when the combination ratio is proper. And because of strong electrostatic attraction of the anions and the cations, the electric property in the adsorption layer is partially neutralized, the electrostatic repulsion between the charge ions in the surface adsorption layer is weakened, the surface interface property is greatly changed, the surface energy is reduced, and the anion and cation surfactant compound system can be usedCompared with single component, the surface interfacial tension is lower, the efficiency of reducing the surface tension is improved, the usage amount of the surfactant is reduced, and meanwhile, the comprehensive synergy and the stability are higher. In addition, the anion and cation surfactant compound system can form abundant microstructures in aqueous solution, such as spherical and rod-shaped micelles, lamellar and flaky liquid crystals, vesicles and the like. Therefore, the complex formulation of the long-chain alkyl quaternary ammonium salt surfactant and the organic anionic surfactant in a proper proportion is adopted as the surfactant, so that the appearance of the transition metal sulfide crystal can be effectively controlled. Wherein the quaternary ammonium salt and MS in the excessive quaternary ammonium salt cationic surfactant4 2+And forming an electron pair, conveying a crystal growth unit, enabling the transition metal sulfide to uniformly and stably grow, effectively reducing Critical Micelle Concentration (CMC) and surface tension (IFT) values, obtaining more stable micelles, and coating the formed micelles on the surfaces of the formed transition metal sulfides while controlling the crystal shapes of the transition metal sulfides as a microreactor and a template to prevent agglomeration.
Wherein the mass ratio of the transition metal source (calculated by the transition metal), the sulfur source (calculated by sulfur), the reducing agent and the surfactant is 1:1-10: 1-5: 0.1-0.5, preferably 1: 3-5: 2-3: 0.1-0.2.
The structure-function integrated carbon fiber/epoxy composite material provided by the invention is a composite material product obtained by growing petal-shaped tungsten sulfide microstructures on the surface of carbon fiber cloth by a hydrothermal method, taking the modified carbon fiber cloth as a reinforcement, taking epoxy resin as a polymer matrix, then compounding the epoxy resin matrix and the carbon fiber cloth together, and finally curing.
The invention provides a preparation method of a structure function integrated carbon fiber/epoxy composite material, which comprises the following steps:
1) growing transition metal sulfide on the surface of the carbon fiber cloth: uniformly mixing a transition metal source, a sulfur source, a reducing agent and a surfactant in water according to a certain proportion to obtain a transition metal sulfide precursor solution, adding the transition metal sulfide precursor solution into the carbon fiber cloth subjected to desizing and surface cleaning, reacting at the temperature of 150-200 ℃ for 12-36h, cooling, washing and drying to obtain the carbon fiber cloth with the transition metal sulfide growing on the surface;
2) compounding carbon fibers and epoxy resin: compounding the carbon fiber cloth with the surface growing transition metal sulfide obtained in the step 1) with an epoxy resin matrix material by a vacuum assisted resin transfer molding method, and finally curing to obtain a carbon fiber/epoxy composite material product.
Vacuum Assisted Resin Transfer Moulding (VARTM) is a process whereby resin is injected into a closed mould to wet out the reinforcement material and cure. The technology is suitable for products with high quality requirements, small batches and larger sizes, has the outstanding characteristics of low mould cost, resin room temperature curing, almost unlimited product size and the like compared with the traditional autoclave forming process, and is one of the most extensive forming methods for manufacturing composite material parts.
The pretreatment of the carbon fiber cloth and the post-treatment of the carbon fiber cloth with transition metal sulfide growing on the surface are well known in the field, and the method specifically comprises the steps of soaking the carbon fiber cloth cut into a proper size in an organic solvent, keeping the carbon fiber cloth at room temperature for 48 hours for desizing treatment, then repeatedly washing the carbon fiber cloth after desizing with ethanol and deionized water, washing away residual sizing agent and acetone on the surface, and drying; and the post-treatment is to take out the carbon fiber cloth after naturally cooling to room temperature, wash the carbon fiber cloth for a plurality of times by using ethanol and deionized water, wash the residual tungsten sulfide powder on the surface of the carbon fiber cloth, and dry the carbon fiber cloth in a drying oven at the temperature of 60-80 ℃ to obtain the carbon fiber cloth with tungsten sulfide nanoflowers growing on the surface.
The invention has the advantages and characteristics that:
a layer of tungsten sulfide nanoflowers with functionality grows on the surface of the carbon fiber cloth through hydrothermal reaction, and the interface of matrix resin and carbon fibers is combined more tightly while the contact area of the carbon fibers and an epoxy resin matrix is increased by utilizing a nanoflower microstructure. Thereby enabling the composite material to show excellent interlaminar shear performance. And because of the existence of the tungsten sulfide nanoflowers, the composite material is endowed with a certain electromagnetic absorption function, and the influence caused by electromagnetic radiation is reduced or avoided, for example, the protective material for reducing the harm of electromagnetic waves or the material for preventing electromagnetic waves is needed, so that the prepared carbon fiber/epoxy composite material has excellent mechanical property and electromagnetic shielding function, and can be applied and significant in stealth airplanes, radioactive medical instruments, electronic equipment shells (shielding cases and shielding dark rooms), electromagnetic pollution reduction (the energy carried by the electromagnetic waves affects sensitive organs of human bodies), electromagnetic stealth (stealth airplanes or naval vessels), special communication (high transmittance in specific wave bands and shielding in other wave bands).
Drawings
FIG. 1 is an SEM photograph of a carbon fiber composite material prepared in example 1;
FIG. 2 is an SEM photograph of a carbon fiber composite material prepared in example 2;
FIG. 3 is an SEM photograph of a carbon fiber composite material prepared in example 3;
FIG. 4 is an SEM photograph of a carbon fiber composite material prepared in example 4.
Detailed Description
Example 1
1) Soaking carbon fiber cloth cut into 7 x 3cm in acetone solution, keeping for 48 hours at room temperature for desizing, then repeatedly washing the carbon fiber cloth after desizing by using ethanol and deionized water, washing away residual sizing agent and acetone on the surface of the carbon fiber cloth, and drying to obtain the carbon fiber cloth after desizing; soaking the desized carbon fiber cloth in an ethanol solution, ultrasonically cleaning the carbon fiber cloth for 1 hour by using ultrasonic equipment with the power of 600W, repeatedly washing the carbon fiber cloth by using ethanol and deionized water, washing off impurities and dust remained on the surface of the carbon fiber cloth, and drying the carbon fiber cloth; respectively weighing 10mmol, 40mmol and 20mmol of sodium tungstate hexahydrate, thiourea and hydroxylamine hydrochloride to dissolve in 40mL of deionized water to prepare a mixed solution A, then weighing 0.375g of Cetyl Trimethyl Ammonium Bromide (CTAB) and 0.125g of fatty alcohol hydroxyethyl sodium sulfonate to dissolve in 40mL of deionized water to prepare a mixed solution B, and the solute in A and B is ensured to be completely dissolved and mixed evenly by magnetic stirring for 30 minutes, then, the uniformly mixed solution A, B is poured into a 100mL inner lining of the hydrothermal kettle together, adding carbon fiber cloth which is ultrasonically cleaned and dried, putting the lining into a hydrothermal kettle, screwing, putting the kettle into an oven at 180 ℃ for reaction for 24 hours, after naturally cooling to room temperature, taking out the carbon fiber cloth, washing the carbon fiber cloth for several times by using ethanol and deionized water, cleaning the residual tungsten sulfide powder on the surface of the carbon fiber cloth, and drying the carbon fiber cloth in an oven at 80 ℃ to obtain the carbon fiber cloth with tungsten sulfide nanoflowers growing on the surface;
2) taking out 8 carbon fiber cloth (WS) with tungsten sulfide nanoflower2@ CF) and weighed to determine the mass of the carbon cloth to be 5 g. Coating release agent on the glass plate, and coating 8 WS blocks2The @ CF is paved and a vacuum resin transfer molding device is built, so that the good tightness of the whole system is ensured. Weighing 10g of epoxy resin and 3g of 593 g of curing agent, mixing with the epoxy resin and uniformly stirring to obtain a mixed solution. Removing bubbles in the mixed solution by using a vacuum pump, pumping the solution with the bubbles removed into the built resin transfer molding device by using the vacuum pump, sealing the two end ports after the solution is completely soaked in 8 layers of carbon cloth, and curing at room temperature for 5 hours to obtain WS2@ CF/EP composite laminates. Cutting each carbon plate into test sample strips with the thickness of 6 multiplied by 20mm, and carrying out subsequent interlaminar shear test; and cutting into 22.86 multiplied by 10.16mm test strips, and carrying out subsequent electromagnetic shielding test.
The interlaminar shear strength of the carbon fiber composite material obtained in the embodiment is 55.3MPa, and the minimum reflection loss value of 4GHz electromagnetic absorption reaches-23 dB.
Example 2
The other conditions and operation were the same as in example 1 except that in step 1), the amount of the surfactant was changed to 0.42g of cetyltrimethylammonium bromide and 0.08g of sodium fatty alcohol isethionate. The interlaminar shear strength of the carbon fiber composite material obtained in the embodiment is 52.4MPa, and the minimum reflection loss value of 4GHz electromagnetic absorption reaches-22 dB.
Example 3
The other conditions and operation were the same as in example 1 except that in step 1), the amount of the surfactant was changed to 0.25g of cetyltrimethylammonium bromide and 0.25g of sodium fatty alcohol isethionate.
The interlaminar shear strength of the carbon fiber composite material obtained in the embodiment is 48.2MPa, and the minimum reflection loss value of 4GHz electromagnetic absorption reaches-21 dB.
Example 4
The other conditions and operation were the same as in example 1 except that in step 1), the amount of the surfactant was changed to 0.5g of cetyltrimethylammonium bromide.
The interlaminar shear strength of the carbon fiber composite material obtained in the embodiment is 41.7MPa, and the minimum reflection loss value of 4GHz electromagnetic absorption reaches-20 dB.
FIGS. 1 to 4 are SEM images of the carbon fiber composite materials obtained in examples 1 to 4, respectively. It can be seen that the composite materials obtained in examples 1 and 2 form nanoflowers, the size and structure of the nanoflowers are uniform and stable, and no obvious agglomeration and accumulation phenomena are caused except a small amount of impurities, which indicates that under a proper proportion, the CTAB and the fatty alcohol hydroxyethyl sodium sulfonate are compounded to form more stable micelles, so that more favorable conditions are provided for subsequent reactions. In example 3, the surfactant ratio is not in the preferred range, and stable micelles are not formed by the cations and the anions due to electrostatic adsorption, so that part of WS2 does not form a flaky nanoflower structure. Example 4 uses a single cationic quaternary ammonium salt surfactant, and does not form a stable nanoflower structure with uniform shape and size, which indicates that a single cationic surfactant is difficult to form a stable textbook, and further a uniform and stable nanoflower structure cannot be formed, so that the interlaminar shear strength is reduced.
Comparative example 1
The other conditions and operations are the same as those in example 1, except that the carbon fiber cloth is not subjected to surface growth of tungsten sulfide nanoflowers, and the carbon fiber cloth is subjected to desizing and cleaning, and then directly subjected to compounding of the step 2) and the epoxy resin.
The interlaminar shear strength of the obtained carbon fiber composite material is 35.8MPa, and the minimum reflection loss value of 4GHz electromagnetic absorption reaches-12 dB.

Claims (10)

1. The structure-function integrated carbon fiber/epoxy composite material is characterized by comprising the following raw materials: carbon fiber cloth with nano transition metal sulfide modified on the surface, epoxy resin and curing agent.
2. The carbon fiber/epoxy composite material as claimed in claim 1, wherein the mass ratio of the carbon fiber cloth, the epoxy resin and the curing agent is 1: 2-5: 0.2-0.3.
3. The carbon fiber/epoxy composite material as claimed in claim 1, wherein the carbon fiber cloth has a grammage of 200-300; the epoxy resin is bisphenol epoxy resin, such as bisphenol A epoxy resin, bisphenol S epoxy resin and bisphenol F epoxy resin, and the epoxy value is 0.30-0.51; the curing agent is selected from at least one of 593 and 591.
4. The carbon fiber/epoxy composite material according to claim 1, wherein the transition metal sulfide is selected from at least one of tungsten sulfide, molybdenum sulfide, chromium sulfide, and nickel sulfide.
5. The carbon fiber/epoxy composite material as claimed in claim 1, wherein the transition metal sulfide is in the form of nanoflower, stacked two-dimensional sheet structure with a diameter of about 3-5 μm.
6. The carbon fiber/epoxy composite material as claimed in claim 1, wherein the transition metal sulfide is obtained by in-situ growth on the surface of the carbon fiber cloth reinforcing material through a hydrothermal reaction, and specifically, the carbon fiber material with the surface cleaned and a transition metal sulfide precursor solution are reacted at 150 ℃ to 200 ℃ for 12 to 36 hours.
7. The carbon fiber/epoxy composite material as claimed in claim 6, wherein the transition metal sulfide precursor solution is obtained by uniformly mixing a transition metal source, a sulfur source, a reducing agent and a surfactant.
8. Carbon fiber/epoxy composite material according to claim 7, characterized in that the source of the transition metal element is a salt of at least one of tungsten, molybdenum, chromium, nickel, such as the sodium, potassium/ammonium salt of the transition metal oxo acid (A)2MO4A is Na, K or NH4M is W, Mo, Ni or Cr), a halogen of a transition metalCompound (MX)nM is W, Mo, Ni or Cr, X is a halogen atom, and n is an integer of 2 to 6); and/or
The thiourea is at least one of thiourea and thioacetamide; the reducing agent is selected from at least one of hydroxylamine hydrochloride and oxalic acid.
9. The carbon fiber/epoxy composite material as claimed in claim 7, wherein the surfactant is a combination of a quaternary ammonium salt cationic surfactant and sodium fatty alcohol isethionate in a mass ratio of 3-5:1, and the quaternary ammonium salt cationic surfactant can be represented by a general formula [ AB [ ]3N]+X-Wherein A is a long-chain alkyl group of 12 to 20 carbon atoms, B is a methyl or ethyl group, and X is a halogen atom such as chlorine or bromine; preferably, the quaternary ammonium salt cationic surfactant is selected from at least one of cetyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium bromide;
preferably, the ratio of the transition metal source (calculated by the transition metal), the sulfur source (calculated by sulfur), the reducing agent and the surfactant is 1:1-10: 1-5: 0.1 to 0.5, more preferably 1: 3-5: 2-3: 0.1-0.2.
10. A method of making a carbon fiber/epoxy composite as claimed in any one of claims 1 to 9, comprising the steps of:
1) growing transition metal sulfide on the surface of the carbon fiber cloth: uniformly mixing a transition metal source, a sulfur source, a reducing agent and a surfactant in water according to a certain proportion to obtain a transition metal sulfide precursor solution, adding the transition metal sulfide precursor solution into the carbon fiber cloth subjected to desizing and surface cleaning, reacting at the temperature of 150-200 ℃ for 12-36h, cooling, washing and drying to obtain the carbon fiber cloth with the transition metal sulfide growing on the surface;
2) compounding carbon fibers and epoxy resin: compounding the carbon fiber cloth with the surface growing transition metal sulfide obtained in the step 1) with an epoxy resin matrix material by a vacuum assisted resin transfer molding method, and finally curing to obtain a carbon fiber/epoxy composite material product.
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CN107459771A (en) * 2016-06-03 2017-12-12 南京中赢纳米新材料有限公司 The preparation method of Nano diamond and functionalized carbon fiber reinforced epoxy composite

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CN105839398A (en) * 2016-04-26 2016-08-10 复旦大学 Nanosheet-layer tungsten disulfide reinforced carbon fiber sizing agent and preparation method thereof
CN107459771A (en) * 2016-06-03 2017-12-12 南京中赢纳米新材料有限公司 The preparation method of Nano diamond and functionalized carbon fiber reinforced epoxy composite
CN107188232A (en) * 2017-05-11 2017-09-22 苏州大学 A kind of petal-shaped tungsten sulfide nanosphere, preparation method and applications

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