CN113583267A - Method for improving interface bonding strength of fiber reinforced thermoplastic composite material - Google Patents

Method for improving interface bonding strength of fiber reinforced thermoplastic composite material Download PDF

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CN113583267A
CN113583267A CN202111018445.9A CN202111018445A CN113583267A CN 113583267 A CN113583267 A CN 113583267A CN 202111018445 A CN202111018445 A CN 202111018445A CN 113583267 A CN113583267 A CN 113583267A
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hot
press molding
thermoplastic resin
fiber
mpa
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CN113583267B (en
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李仁宏
王刚
杜雷雷
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Shaoxing Keqiao Research Institute Co Ltd Of Zhejiang University Of Technology
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Shaoxing Keqiao Research Institute Co Ltd Of Zhejiang University Of Technology
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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
    • 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
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
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    • 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
    • C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
    • C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • 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
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids

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Abstract

The invention relates to the field of composite materials, and discloses a method for improving the interface bonding strength of a fiber reinforced thermoplastic composite material, which comprises the following steps: firstly, preparing a Tris solution; adding modifiers such as polyvinyl alcohol, cationic starch, dopamine hydrochloride, ethylene-vinyl acetate copolymer, carboxymethyl cellulose, waterborne polyurethane and the like, and N, N-dimethylformamide, 4-aminophenol, 4-dimethylaminopyridine into a Tris solution, and performing ultrasonic treatment to obtain a solution; thirdly, desizing the fibers to obtain desized fibers; fourthly, placing the desized fiber in the solution to attach a polymer film on the surface of the fiber; and fifthly, compounding the fibers and the thermoplastic resin to obtain the fiber reinforced thermoplastic composite material. The invention adopts the steps of desizing the fiber, then soaking the fiber by using the modifier, and attaching a layer of polymer film on the surface of the fiber to increase the surface energy of the fiber and improve the interface bonding strength of the fiber and the thermoplastic resin matrix.

Description

Method for improving interface bonding strength of fiber reinforced thermoplastic composite material
Technical Field
The invention relates to the field of composite materials, in particular to a method for improving the interface bonding strength of a fiber reinforced thermoplastic composite material.
Background
The fiber reinforced thermoplastic composite material is a novel high-grade lightweight material, and is prepared by compounding fibers such as glass fibers, carbon fibers, copper fibers, stainless steel fibers, natural plant fibers and the like in thermoplastic resin to improve the strength of the material. With the continuous development of manufacturing industry and new material technology, fiber reinforced thermoplastic composite materials are widely applied to the fields of automobile industry, aerospace, electronic and electric appliances, sports facilities, household appliances and the like due to the characteristics of high tensile rigidity, high strength and other mechanical properties, higher chemical softening point, good high-temperature melting fluidity, repeated recycling and the like.
However, the strength of the fiber reinforced thermoplastic composite material is often lower than that of the fiber reinforced thermosetting composite material, which limits the application fields of the fiber reinforced thermoplastic composite material requiring high strength and high hardness, so that it is necessary to improve the strength of the fiber reinforced thermoplastic composite material, and one of the key factors influencing the strength is the magnitude of the interfacial bonding force between the fiber and the thermoplastic matrix resin. The fiber presents chemical inertness due to smooth surface, so that the interface compatibility between the fiber and a thermoplastic matrix is poor, the interface bonding force is small, the overall mechanical property of the composite material is not high, and the practical application of the fiber reinforced thermoplastic composite material is influenced.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for improving the interface bonding strength of a fiber reinforced thermoplastic composite material.
The specific technical scheme of the invention is as follows:
a method of increasing the interfacial bond strength of a fiber reinforced thermoplastic composite comprising the steps of:
adding Tris (hydroxymethyl) aminomethane, absolute ethyl alcohol and a hydrochloric acid buffer solution into an aqueous solution to obtain a Tris solution;
adding one or more modifiers of polyvinyl alcohol, cationic starch, dopamine hydrochloride, ethylene-vinyl acetate copolymer, carboxymethyl cellulose and waterborne polyurethane, N-dimethylformamide, 4-aminophenol and 4-dimethylaminopyridine into the Tris solution obtained in the step one, and performing ultrasonic treatment to obtain a uniformly mixed solution;
thirdly, preparing a mixed solution from acetone and absolute ethyl alcohol, placing one or more fibers of carbon fibers, glass fibers and basalt fibers in the mixed solution, standing, washing and drying to obtain desized fibers;
fourthly, placing the desized fiber obtained in the third step into the solution prepared in the second step, standing, taking out, washing and drying to obtain the fiber with a layer of polymer film attached to the surface;
fifthly, the fiber reinforced thermoplastic composite material is obtained by carrying out one or more molding processes of hot press molding, pultrusion molding, transfer molding and 3D printing molding on the fiber obtained in the fourth step and one or more thermoplastic resins of polyimide, nylon 6, nylon 66, polypropylene, polyether-ether-ketone and acrylonitrile-butadiene-styrene copolymer.
In the first step to the second step, the invention prepares the dipping solution for the fiber surface modification; the purpose of preparing the Tris solution in the step one is to provide an alkaline environment to enable a modifier to accelerate the polymerization reaction in the solution so as to improve the rate of the high molecular polymerization reaction; in the second step, substances such as N, N-dimethylformamide, 4-aminophenol, 4-Dimethylaminopyridine (DMAP) and the like are used for providing an environment which is rich in amino and can improve the stability and uniformity of the load of the polymer film, so that the production period can be shortened and the production stability can be improved in practical application. Desizing the fiber in the third step to improve the adhesion effect of the modifier in the impregnating solution on the fiber surface. In the fourth step, after the fiber is immersed in the solution containing the modifier, the modifier is attached to the surface of the fiber and forms a layer of polymer film, and the polymer film has many active functional groups such as amino groups, hydroxyl groups and the like, and the active functional groups can increase the surface energy of the fiber and improve the compatibility of the fiber and the thermoplastic matrix, so that the interface bonding force between the fiber and the resin can be obviously enhanced.
In conclusion, the invention improves the bonding force between the fiber and the thermoplastic resin by attaching a layer of polymer film on the surface of the fiber, and compared with the traditional methods such as strong acid oxidation and the like, the method not only effectively avoids the damage to the fiber caused by the strong acid oxidation, but also repairs the defects on the surface of the fiber, so that the monofilament tensile strength of the fiber is slightly improved.
Preferably, the concentration of Tris in the Tris solution is 0.005-0.1 mol/L. Preferably, the Tris concentration is 0.01 mol/L.
Preferably, in the second step, the mass concentration of the modifier is 1-5 g/L; preferably, the mass concentration of the modifier is 2 g/L. The time of ultrasonic treatment is 1-3 hours.
Preferably, the modifier is a mixed solution of polyvinyl alcohol and dopamine hydrochloride, and more preferably, the modifier is dopamine hydrochloride.
Preferably, in the third step, the standing time is 6-48 h. Preferably, the fibers are carbon fibers.
Preferably, in step four, the bath ratio of the desized fiber to the solution is 0.8-1.2: 1.
Preferably, in step five, the ratio of the fibers to the thermoplastic resin is 7: 10-15.
Preferably, in step five:
the hot-press molding reaction temperature of the nylon 6 thermoplastic resin is 100-500 ℃; the hot-press forming pressure is 3-20 MPa; the hot-press molding time is 3-30 min; further preferably, the hot-press forming reaction temperature is 200-350 ℃; the hot-press forming pressure is 5-15 MPa; the hot-press molding time is 5-20 min; further preferably, the hot-press forming reaction temperature is 250-280 ℃; the hot-press forming pressure is 10-13 MPa; the hot-press forming time is 10-15 min.
The hot press molding reaction temperature of the nylon 66 thermoplastic resin is 150-450 ℃; the hot-press forming pressure is 3-20 MPa; the hot-press molding time is 3-30 min; further preferably, the reaction temperature is 200-350 ℃; the hot-press forming pressure is 5-15 MPa; the hot-press molding time is 5-20 min; further preferably, the hot-press molding reaction temperature is 250-300 ℃; the hot-press forming pressure is 10-13 MPa; the hot-press forming time is 10-15 min.
The hot-press molding reaction temperature of the polypropylene thermoplastic resin is 100-450 ℃; the hot-press forming pressure is 3-20 MPa; the hot-press molding time is 3-30 min; further preferably, the hot-press forming reaction temperature is 150-300 ℃; the hot-press forming pressure is 5-15 MPa; the hot-press molding time is 5-20 min; further preferably, the hot-press forming reaction temperature is 200-250 ℃; the hot-press forming pressure is 8-12 MPa; the hot-press forming time is 8-13 min.
The hot press molding reaction temperature of the polyether-ether-ketone thermoplastic resin is 200-600 ℃; the hot pressing pressure is 3-20 MPa; the hot-press molding time is 3-30 min; further preferably, the hot-press forming reaction temperature is 250-500 ℃; the hot pressing pressure is 5-15 MPa; the hot-press molding time is 5-20 min; further preferably, the hot-press molding reaction temperature is 300-450 ℃; the hot pressing pressure is 9-12 MPa; the hot-press forming time is 9-13 min.
The hot press molding reaction temperature of the acrylonitrile-butadiene-styrene copolymer thermoplastic resin is 100-600 ℃; the hot-press forming pressure is 3-20 MPa; the hot-press molding time is 3-30 min; further preferably, the hot-press forming reaction temperature is 150-500 ℃; the hot pressing pressure is 5-15 MPa; the hot-press molding time is 5-20 min; further preferably, the reaction temperature is 230-300 ℃; the hot pressing pressure is 9-12 MPa; the hot-press forming time is 9-13 min.
Preferably, the thermoplastic resin is nylon 6 and nylon 66, and more preferably, the thermoplastic resin is nylon 6.
The fiber reinforced thermoplastic composite material obtained by the method is applied to the fields of automobile industry, aerospace, electronic appliances, sports facilities and household appliances.
Compared with the prior art, the invention has the beneficial effects that: the invention carries out the dipping treatment of the modifier after the fiber desizing treatment, so that a layer of polymer film is attached to the surface of the fiber, the polymer film contains a plurality of active functional groups such as amino, hydroxyl and the like, and the active functional groups can increase the surface energy of the fiber and improve the compatibility of the fiber and a thermoplastic matrix, thereby obviously enhancing the interface bonding force of the fiber and resin. Compared with the traditional methods such as strong acid oxidation and the like, the method not only effectively avoids the damage to the fiber caused by the strong acid oxidation, but also repairs the defects on the surface of the fiber, so that the monofilament tensile strength of the fiber is slightly improved. The interlaminar shear strength of the fiber reinforced thermoplastic composite material is improved by about 20-200%, and the bending strength is improved by about 19-60%.
Drawings
FIG. 1 is a scanning electron microscope image of T300 carbon fibers without loading polydopamine film obtained in step two of test example 1;
FIG. 2 is a scanning electron microscope image of the polydopamine-loaded T300 carbon fiber obtained in step four of test example 1;
FIG. 3 is a graph comparing the tensile strength of different modified carbon fiber monofilaments of test example 1;
FIG. 4 is a graph of interlaminar shear strength force versus displacement for the composites of test example 1 and comparative example 1;
FIG. 5 is a graph of flexural strength force versus displacement for the composite materials of test example 1 and comparative example 1;
FIG. 6 is a thermogravimetric plot of carbon fiber reinforced nylon 6 composites of test example 1 and comparative example 1;
FIG. 7 is a thermogravimetric plot of carbon fiber reinforced polypropylene composites of test example 2 and comparative example 2;
FIG. 8 is an atomic force microscope photograph of T300 carbon fibers without loading polydopamine film obtained in step two of test example 3;
fig. 9 is an atomic force microscope photograph of the polymer film-supporting T300 carbon fiber obtained in step four of test example 3.
Detailed Description
The invention is further illustrated below with reference to specific embodiments. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Furthermore, various changes or modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the appended claims.
The first embodiment is as follows:
firstly, 0.48456g of Tris (hydroxymethyl) aminomethane (Tris), 50ml of absolute ethanol and 1M hydrochloric acid buffer solution were added to 400ml of an aqueous solution to obtain a Tris solution with a concentration of 0.01M.
And secondly, adding 0.8g of dopamine hydrochloride, N-dimethylformamide, 4-aminophenol and 4-Dimethylaminopyridine (DMAP) into the Tris solution obtained in the first step according to the mass concentration of 2g/L, and performing ultrasonic treatment for 30min to obtain a uniformly mixed solution.
And thirdly, preparing a mixed solution of 200ml of acetone and 200ml of absolute ethyl alcohol according to the ratio of 1: 1, then placing the commercial carbon fiber in the solution, standing for 24 hours, washing and drying to obtain the carbon fiber without the sizing agent.
And fourthly, mixing the carbon fiber desized in the third step with the solution prepared in the second step according to the bath ratio of 1: 1, standing for 18 hours, taking out, washing and drying to obtain the carbon fiber with the surface attached with a layer of polydopamine film.
And fifthly, alternately stacking the carbon fibers attached with the polydopamine film obtained in the step four and a nylon 6(PA6) thermoplastic resin film according to the mass ratio of 7: 13, then carrying out hot pressing at 250 ℃ and 10MPa for 10min, and carrying out cold press molding to obtain the carbon fiber reinforced nylon 6 composite material.
The second embodiment is as follows: this embodiment is different from the first embodiment in that the thermoplastic matrix in the fifth step is polypropylene (PP), the temperature in the fifth step is 200 ℃, and the rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment differs from the first embodiment in that the thermoplastic matrix in step five is nylon 66(PA66), the temperature in step five is 260 ℃, and the other embodiments are the same as the first embodiment.
The fourth concrete implementation mode: the difference between this embodiment and the first embodiment is that the thermoplastic matrix in the fifth step is polyether ether ketone (PEEK), the temperature in the fifth step is 375 ℃, and the other steps are the same as the first embodiment.
The fifth concrete implementation mode: this embodiment is different from the first embodiment in that the thermoplastic matrix in the fifth step is acrylonitrile-butadiene-styrene copolymer (ABS), the temperature in the fifth step is 230 ℃, and the rest is the same as the first embodiment.
The sixth specific implementation mode: the difference between this embodiment and the first embodiment is that the reinforcement in step three is glass fiber, and the other steps are the same as the first embodiment.
The seventh embodiment: this embodiment is different from the second embodiment in that the reinforcement member in the third step is made of glass fiber, and the other steps are the same as the second embodiment.
The specific implementation mode is eight: this embodiment is different from the third embodiment in that the reinforcement member in the third step is made of glass fiber, and the other steps are the same as the third embodiment.
The specific implementation method nine: the present embodiment is different from the fourth embodiment in that the reinforcement member described in the third step is a glass fiber, and the other steps are the same as the fourth embodiment.
The detailed implementation mode is ten: the present embodiment is different from the fifth embodiment in that the reinforcement member in the third step is made of glass fiber, and the rest is the same as the fifth embodiment.
The concrete implementation mode eleven: the present embodiment is different from the first embodiment in that the reinforcement member in the third step is basalt fiber, and the other embodiments are the same as the first or sixth embodiments.
The specific implementation mode twelve: the present embodiment is different from the second embodiment in that the reinforcement member in the third step is basalt fiber, and the other embodiments are the same as the second or seventh embodiment.
The specific implementation mode is thirteen: the present embodiment is different from the third embodiment in that the reinforcement member in the third step is basalt fiber, and the other embodiments are the same as the third or eighth embodiment.
The specific implementation mode is fourteen: the fourth embodiment is different from the fourth embodiment in that the reinforcement member in the third step is basalt fiber, and the other embodiments are the same as the fourth or ninth embodiment.
The concrete implementation mode is fifteen: the present embodiment is different from the fifth embodiment in that the reinforcement member in the third step is basalt fiber, and the other embodiments are the same as or similar to the fifth or tenth embodiment.
The specific implementation mode is sixteen:
firstly, 0.48456 Tris (hydroxymethyl) aminomethane (Tris), 50ml absolute ethyl alcohol and 1M hydrochloric acid buffer solution were added to an aqueous solution to obtain a Tris solution with a concentration of 0.01M.
And secondly, adding 0.8g of polyvinyl alcohol and N, N-dimethylformamide, 4-aminophenol, 4-Dimethylaminopyridine (DMAP) into the Tris solution obtained in the first step according to the mass concentration of 2g/L, and performing ultrasonic treatment for 30min to obtain a uniformly mixed solution.
And thirdly, preparing a mixed solution of 200ml of acetone and 200ml of absolute ethyl alcohol according to the ratio of 1: 1, then placing the commercial carbon fiber in the solution, standing for 24 hours, washing and drying to obtain the carbon fiber without the sizing agent.
And fourthly, mixing the carbon fiber desized in the third step with the solution prepared in the second step according to the bath ratio of 1: 1, standing for 18 hours, taking out, washing and drying to obtain the carbon fiber with the surface attached with the polyvinyl alcohol film.
Fifthly, alternately stacking the carbon fibers attached with the polyvinyl alcohol film obtained in the fourth step and a nylon 6(PA6) thermoplastic resin film according to the mass ratio of 7: 13, then carrying out hot pressing at 250 ℃ and 10MPa for 10min, and carrying out cold press molding to obtain the carbon fiber reinforced nylon 6 composite material.
Seventeenth embodiment: this embodiment differs from the sixteenth embodiment in that the thermoplastic matrix in step five is polypropylene (PP), the temperature in step five is 200 ℃, and the rest is the same as the sixteenth embodiment.
The specific implementation mode is eighteen: this embodiment differs from the first embodiment in that the thermoplastic matrix in step five is nylon 66(PA66), the temperature in step five is 260 ℃, and the rest is the same as the sixteenth embodiment.
The detailed embodiment is nineteen: this embodiment is different from the sixteenth embodiment in that the thermoplastic matrix in the fifth step is polyether ether ketone (PEEK), the temperature in the fifth step is 375 ℃, and the rest is the same as the sixteenth embodiment.
The specific implementation mode twenty: sixteenth, this embodiment is different from the first embodiment in that the thermoplastic matrix in the fifth step is acrylonitrile-butadiene-styrene (ABS), the temperature in the fifth step is 230 ℃, and the rest is the same as the first embodiment.
The specific implementation mode is twenty one: this embodiment is different from the sixteenth embodiment in that the reinforcement member in the third step is made of glass fiber, and the rest is the same as the sixteenth embodiment.
Specific embodiment twenty-two: this embodiment is different from the seventeenth embodiment in that the reinforcement member in the third step is a glass fiber, and the other steps are the same as those of the seventeenth embodiment.
Specific embodiment twenty-three: this embodiment is different from the eighteen embodiments in that the reinforcement member in the third step is a glass fiber, and the other embodiments are the same as the eighteen embodiments.
Twenty-four specific embodiments: this embodiment is different from the nineteenth embodiment in that the reinforcement in the third step is made of glass fiber, and the other steps are the same as the nineteenth embodiment.
The specific implementation mode is twenty five: this embodiment is different from the twenty embodiment in that the reinforcement member in the third step is a glass fiber, and the other steps are the same as the twenty embodiment.
The specific implementation mode is twenty-six: the sixteenth embodiment is different from the sixteenth embodiment in that the reinforcement member in the third step is basalt fiber, and the rest is the same as the sixteenth or twenty-first embodiment.
The specific implementation mode is twenty-seven: this embodiment is different from the seventeenth embodiment in that the reinforcement member in the third step is basalt fiber, and the other embodiments are the same as the seventeenth or twenty-two embodiments.
The specific implementation mode is twenty-eight: the present embodiment is different from the eighteen embodiment in that the reinforcement member in the third step is basalt fiber, and the other embodiments are the same as the eighteen or twenty-three embodiments.
The specific implementation mode is twenty-nine: this embodiment is different from the nineteen embodiment in that the reinforcement member in step three is basalt fiber, and the others are the same as the nineteen or twenty-four embodiment.
The specific implementation mode is thirty: this embodiment is different from the twenty embodiment in that the reinforcement member in the third step is basalt fiber, and the other embodiments are the same as the twenty or twenty-five embodiment.
The specific implementation mode is thirty-one:
firstly, 0.48456 Tris (hydroxymethyl) aminomethane (Tris), 50ml absolute ethyl alcohol and 1M hydrochloric acid buffer solution were added to an aqueous solution to obtain a Tris solution with a concentration of 0.01M.
And secondly, adding 0.15g of carboxymethyl cellulose, 0.4g of ethylene-vinyl acetate copolymer, N-dimethylformamide, 4-aminophenol and 4-Dimethylaminopyridine (DMAP) into the solution obtained in the first step according to the mass concentration of 2g/L, and performing ultrasonic treatment for 30min to obtain a uniformly mixed solution.
And thirdly, preparing a mixed solution of 200ml of acetone and 200ml of absolute ethyl alcohol according to the proportion of 1: 1, then placing the commercial carbon fiber in the solution, standing for 24 hours, washing and drying to obtain the carbon fiber without the sizing agent.
And fourthly, mixing the carbon fiber desized in the third step with the solution prepared in the second step according to the bath ratio of 1: 1, standing for 18 hours, taking out, washing and drying to obtain the carbon fiber with a layer of cellulose film attached to the surface.
And fifthly, alternately stacking the carbon fibers attached with the cellulose film obtained in the step four and a nylon 6(PA6) thermoplastic resin film according to the mass ratio of 7: 13, then carrying out hot pressing at 250 ℃ and 10MPa for 10min, and carrying out cold press molding to obtain the carbon fiber reinforced nylon 6 composite material.
The specific implementation mode is thirty-two: this embodiment differs from embodiment thirty-one in that the thermoplastic matrix in step five is polypropylene (PP), the temperature in step five is 200 ℃, and the rest is the same as embodiment thirty-one.
The specific implementation mode is thirty-three: this embodiment differs from embodiment thirty-one in that the thermoplastic matrix in step five is nylon 66(PA66), the temperature in step five is 260 ℃, and the rest is the same as embodiment thirty-one.
The specific implementation mode is thirty-four: this embodiment differs from the embodiment thirty-one in that the thermoplastic matrix in step five is polyether ether ketone (PEEK), the temperature in step five is 375 ℃, and the other steps are the same as the embodiment thirty-one.
The specific implementation mode is thirty-five: this embodiment is different from the embodiment thirty-one in that the thermoplastic matrix in the fifth step is acrylonitrile-butadiene-styrene copolymer (ABS), the temperature in the fifth step is 230 ℃, and the rest is the same as the first embodiment.
The specific implementation mode is thirty-six: this embodiment is different from the thirty-first embodiment in that the reinforcement member in the third step is a glass fiber, and the other embodiments are the same as the thirty-first embodiment.
Embodiment thirty-seven: thirty-two different from the embodiment is that the reinforcement in the third step is made of glass fiber, and the rest is the same as the thirty-two embodiment.
The specific implementation mode is thirty-eight: thirty-three different from the specific embodiment is that the reinforcement in the third step is made of glass fiber, and the rest is the same as the thirty-three specific embodiment.
The specific embodiment is thirty-nine: thirty-four different from the specific embodiment is that the reinforcement in the third step is made of glass fiber, and the rest is the same as the thirty-four specific embodiment.
Embodiment forty: thirty-five of the present embodiment is different from the thirty-five of the specific embodiment in that the reinforcement in the third step is made of glass fiber, and the rest is the same as the thirty-five of the specific embodiment.
The specific implementation mode is forty one: this embodiment is different from the thirty-one embodiment in that the reinforcement member in the step three is basalt fiber, and the other embodiments are the same as the thirty-one or thirty-six embodiments.
The specific implementation mode is forty-two: thirty-two different from the specific embodiment is that the reinforcement member in the third step is basalt fiber, and the other is the same as thirty-two or thirty-seven of the specific embodiment.
The specific implementation mode is forty-three: thirty-three of the present embodiment is different from the specific embodiment in that the reinforcement member in the step three is basalt fiber, and the others are the same as thirty-three or thirty-eight of the specific embodiment.
The specific implementation mode is fourteen: thirty-four of the present embodiment is different from the specific embodiment in that the reinforcement member in the step three is basalt fiber, and the others are the same as thirty-four or thirty-nine of the specific embodiment.
The specific implementation mode is forty-five: thirty-five of the present embodiment is different from the specific embodiment in that the reinforcement member in the step three is basalt fiber, and the other embodiments are the same as thirty-five or forty of the specific embodiment.
The specific implementation mode is forty-six:
firstly, 0.48456 Tris (hydroxymethyl) aminomethane (Tris), 50ml absolute ethyl alcohol and 1M hydrochloric acid buffer solution were added to an aqueous solution to obtain a Tris solution with a concentration of 0.01M.
And secondly, adding 0.2g of cationic starch, 0.8g of dopamine hydrochloride, N-dimethylformamide, 4-aminophenol and 4-Dimethylaminopyridine (DMAP) into the solution obtained in the first step according to the mass concentration of 2g/L, and performing ultrasonic treatment for 30min to obtain a uniformly mixed solution.
Thirdly, preparing a mixed solution from acetone and absolute ethyl alcohol according to the ratio of 1: 1, then placing the commercial carbon fiber in the solution, standing for 24 hours, washing and drying to obtain the carbon fiber without the sizing agent.
And fourthly, mixing the carbon fiber desized in the third step with the solution prepared in the second step according to the bath ratio of 1: 1, standing for 18 hours, taking out, washing and drying to obtain the carbon fiber with a layer of polymer film attached to the surface.
Fifthly, mixing the carbon fiber attached with the polymer film obtained in the step four with nylon 6(PA6) thermoplastic resin powder, setting parameters in a 3D printer to be 100 in filling density, setting the printing temperature to be 250 ℃, the platform temperature to be 100 ℃, the fan speed to be 2, setting the printing speed to be slower, and processing and molding to obtain the carbon fiber reinforced nylon 6 composite material.
Embodiment forty-seven: this embodiment is forty-six different from the embodiment in that the thermoplastic matrix in step five is polypropylene (PP), the printing temperature in step five is 200 ℃, and the rest is the same as the embodiment forty-six.
The specific implementation mode is forty-eight: this embodiment is forty-six different from the embodiment in that the thermoplastic matrix in step five is nylon 66(PA66), the printing temperature in step five is 260 ℃, and the rest is the same as the embodiment forty-six.
Detailed description forty-nine: this embodiment is forty-six different from the embodiment in that the thermoplastic matrix in step five is polyether ether ketone (PEEK), the printing temperature in step five is 375 ℃, and the rest is the same as the embodiment forty-six.
Embodiment fifty: this embodiment differs from embodiment forty-six in that the thermoplastic matrix in step five is acrylonitrile-butadiene-styrene copolymer (ABS), the printing temperature in step five is 230 ℃, and the rest is the same as embodiment one.
The specific implementation mode is fifty one: this embodiment is forty-six different from the embodiment in that the reinforcement in step three is made of glass fiber, and the other steps are the same as the embodiment forty-six.
The specific implementation mode is fifty-two: this embodiment is different from forty-seven in that the reinforcement member in step three is made of glass fiber, and the other steps are the same as forty-seven in the embodiment.
The specific implementation mode is fifty three: this embodiment is the same as embodiment forty-eight except that the reinforcement in step three is made of glass fiber.
The specific implementation mode is fifty-four: this embodiment is the same as forty-nine embodiment except that the reinforcement in step three is made of glass fiber.
The specific implementation manner is fifty-five: this embodiment differs from embodiment fifty in that the reinforcement in step three is glass fiber, and the rest is the same as embodiment fifty.
The specific implementation manner is fifty-six: this embodiment is different from forty-six of the embodiment in that the reinforcement member in step three is basalt fiber, and the other embodiments are the same as forty-six or fifty-one of the embodiment.
Embodiment fifty-seven: forty-seven of the present embodiment is different from the embodiment in that the reinforcement member in the third step is basalt fiber, and the other embodiments are the same as forty-seven or fifty-two of the embodiment.
The specific implementation mode is fifty-eight: this embodiment is forty-eight different from the embodiment in that the reinforcement member in step three is basalt fiber, and the other embodiments are the same as the embodiments in forty-eight or fifty-eight.
The specific implementation mode is fifty-nine: this embodiment is different from forty-nine embodiment in that the reinforcement member in step three is basalt fiber, and the other embodiments are the same as forty-nine or fifty-four embodiment.
The specific implementation mode is sixty: this embodiment differs from embodiment fifty in that the reinforcement member described in step three is basalt fiber, and the other embodiments are the same as embodiment fifty or fifty-five.
Test example 1:
firstly, 0.48456g of Tris (hydroxymethyl) aminomethane (Tris), 50ml of absolute ethanol and 1M hydrochloric acid buffer solution are added into 400ml of aqueous solution to obtain a Tris solution with the concentration of 0.01M;
secondly, adding 0.8g of dopamine hydrochloride, N-dimethylformamide, 4-aminophenol and 4-Dimethylaminopyridine (DMAP) into the Tris solution obtained in the first step according to the mass concentration of 2g/L, and performing ultrasonic treatment for 30min to obtain a uniformly mixed solution;
preparing a mixed solution of 200ml of acetone and 200ml of absolute ethyl alcohol according to the ratio of 1: 1, then placing the commercial carbon fiber in the solution, standing for 24 hours, washing and drying to obtain the carbon fiber with the sizing agent removed;
fourthly, mixing the carbon fiber desized in the third step with the solution prepared in the second step according to the bath ratio of 1: 1, standing for 18h, taking out, washing and drying to obtain the carbon fiber with a layer of polydopamine film attached to the surface;
and fifthly, alternately stacking the carbon fibers attached with the polydopamine film obtained in the step four and a nylon 6(PA6) thermoplastic resin film according to the mass ratio of 7: 13, then carrying out hot pressing at 250 ℃ and 10MPa for 10min, and carrying out cold press molding to obtain the carbon fiber reinforced nylon 6 composite material.
Comparative example 1:
firstly, preparing a mixed solution of 200ml of acetone and 200ml of absolute ethyl alcohol according to a ratio of 1: 1, then placing commercial carbon fibers in the solution, standing for 24 hours, washing and drying to obtain carbon fibers with sizing agents removed;
and secondly, alternately stacking the desized carbon fibers obtained in the step two and a nylon 6(PA6) thermoplastic resin film according to the mass ratio of 7: 13, then carrying out hot pressing at 250 ℃ and 10MPa for 10min, and carrying out cold press molding to obtain the carbon fiber reinforced nylon 6 composite material.
Example step one the mixed solution containing Tris (hydroxymethyl) aminomethane (Tris), absolute ethanol and hydrochloric acid buffer was prepared in order to provide an alkaline environment that allows the modifier to accelerate the polymerization reaction in solution and thus increase the rate of the high molecular weight polymerization reaction. The substances such as N, N-dimethylformamide, 4-aminophenol and 4-Dimethylaminopyridine (DMAP) contained in the second step are used for providing an environment which is rich in amino and can improve the stability and uniformity of the load of the polymer film, and the production period can be shortened and the production stability can be improved in practical application. As can be seen from fig. 1, the scanning electron microscope picture of the T300 carbon fiber cloth without the polydopamine film in example 1 is shown in fig. 1, and the scanning electron microscope picture of the T300 carbon fiber cloth loaded with the polydopamine film obtained in step three is shown in fig. 2. As can be seen from FIG. 2, the defects such as grooves on the surface of the carbon fiber after loading a layer of film are filled with polydopamine to repair the defects of the carbon fiber, and the roughness of the surface is obviously improved, which is beneficial to mechanical engagement between the fiber and the resin to improve the bonding force of the interface. As can be seen from FIG. 3, the tensile strength of the carbon fiber monofilament of the polydopamine-loaded film in example 1 is 3.176MPa, and the tensile strength of the carbon fiber monofilament of comparative test 1 which is not treated with dopamine is 3.054MPa, so that the tensile strength of the carbon fiber monofilament is slightly increased after modification.
The carbon fiber cloth of comparative example 1 of the carbon fiber cloth of test example 1 was subjected to a contact angle test and a surface free energy test, and the results are shown in tables 1 to 2 below.
TABLE 1 contact Angle of the materials
Figure BDA0003240503850000111
TABLE 2 surface free energy of the materials
Sample (I) Surface free energy (mN/m)
Test example 1 carbon fiber cloth loaded with polydopamine film 49.14
Comparative example 1 carbon fiber cloth without dopamine treatment 27.85
As can be seen from table 1, the contact angle of the carbon fiber cloth of comparative example 1 without dopamine treatment was 95.4 ° in the case of water as a solvent, and 67.7 ° in the case of ethylene glycol as a solvent, while the contact angle of the carbon fiber cloth of test example 1 supporting the polydopamine film was 76.4 ° in the case of water as a solvent, and 31.5 ° in the case of ethylene glycol as a solvent. The contact angle of the modified carbon fiber cloth is greatly reduced, so that the modification method improves the wettability of the carbon fiber cloth and liquid. According to table 2, the surface free energy of the carbon fiber cloth of comparative example 1 without dopamine treatment is 27.85mN/m, while the surface free energy of the carbon fiber cloth loaded with the polydopamine film of test example 1 is increased to 49.14mN/m, because the polydopamine has many active groups such as hydroxyl, amino and the like, so that the surface free energy of the carbon fiber cloth is increased, and thus it can be speculated that the modified carbon fiber cloth and the resin have good wettability, and the mechanical properties of the composite material are further improved.
The carbon fiber reinforced nylon 6 composite material in comparative example 1 of the carbon fiber reinforced nylon 6 composite material in test example 1 was subjected to an interlaminar shear property test and a bending property test, and the results are shown in table 3 below.
TABLE 3 interlaminar shear strength and flexural Strength of carbon fiber reinforced Nylon 6 composites
Figure BDA0003240503850000121
FIG. 4 is a graph of interlaminar shear strength and flexural strength force versus displacement, respectively, for a composite material. From table 3, fig. 4 and fig. 5, it can be seen that the carbon fiber reinforced nylon 6 composite of comparative example 1, which was not treated with dopamine, had an interlaminar shear strength (ILSS) of only 10.2MPa and a flexural strength of only 171.1MPa, while the carbon fiber reinforced nylon 6 composite of test example 1, which was loaded with a polydopamine film, had an interlaminar shear strength (ILSS) of 28.8MPa and a flexural strength of 268.4 MPa. Compared with the unmodified carbon fiber reinforced nylon 6 composite material, the shear strength of the modified carbon fiber reinforced nylon 6 composite material is improved by 182%, the bending strength is improved by 56.9%, and the improvement is great.
According to the thermogravimetric graphs of the carbon fiber reinforced nylon 6 composite materials in the test example 1 and the comparative example 1 in fig. 6, the decomposition temperature of the carbon fiber reinforced nylon 6 composite material without dopamine treatment is 434.1 ℃, while the decomposition temperature of the carbon fiber reinforced nylon 6 composite material loaded with the polydopamine film is 439.7 ℃, so that the thermal stability of the modified carbon fiber thermoplastic composite material is slightly improved, and the influence is small overall.
Test example 2:
firstly, 0.48456g of Tris (hydroxymethyl) aminomethane (Tris), 50ml of absolute ethanol and 1M hydrochloric acid buffer solution are added into 400ml of aqueous solution to obtain a Tris solution with the concentration of 0.01M;
secondly, adding 0.3g of waterborne polyurethane, 0.8g of dopamine hydrochloride, N-dimethylformamide, 4-aminophenol and 4-Dimethylaminopyridine (DMAP) into the Tris solution obtained in the first step according to the mass concentration of 2g/L, and performing ultrasonic treatment for 30min to obtain a uniformly mixed solution;
preparing a mixed solution of 200ml of acetone and 200ml of absolute ethyl alcohol according to the ratio of 1: 1, then placing the commercial carbon fiber in the solution, standing for 24 hours, washing and drying to obtain the carbon fiber with the sizing agent removed;
fourthly, mixing the carbon fiber desized in the third step with the solution prepared in the second step according to the bath ratio of 1: 1, standing for 18 hours, taking out, washing and drying to obtain the carbon fiber with a layer of polymer film attached to the surface;
and fifthly, alternately stacking the carbon fibers attached with the polymer film and the polypropylene (PP) thermoplastic film according to the mass ratio of 7: 13, hot-pressing at 200 ℃ and 10MPa for 10min, and then cold-pressing and molding to obtain the carbon fiber reinforced polypropylene composite material.
Comparative example 2:
firstly, preparing a mixed solution of 200ml of acetone and 200ml of absolute ethyl alcohol according to a ratio of 1: 1, then placing commercial carbon fibers in the solution, standing for 24 hours, washing and drying to obtain carbon fibers with sizing agents removed;
and secondly, alternately stacking the desized carbon fibers obtained in the step two and a polypropylene (PP) thermoplastic film according to the mass ratio of 7: 13, hot-pressing at 200 ℃ and 10MPa for 10min, and then cold-pressing and molding to obtain the carbon fiber reinforced polypropylene composite material.
The carbon fiber reinforced polypropylene composite material of example 2 and the carbon fiber reinforced polypropylene composite material of comparative example 2 were subjected to an interlaminar shear property test and a bending property test, and the results are shown in table 4 below.
TABLE 4 interlaminar shear strength and flexural Strength of carbon fiber reinforced Polypropylene composites
Figure BDA0003240503850000131
It can be seen from table 4 that the interlaminar shear strength (ILSS) of the carbon fiber reinforced polypropylene of comparative example 2 without dopamine treatment was only 6.9MPa and the flexural strength was only 73MPa, while the interlaminar shear strength (ILSS) of the carbon fiber reinforced polypropylene of test example 2 loaded with polydopamine film was 8.9MPa and the flexural strength was 87 MPa. Compared with the unmodified carbon fiber reinforced polypropylene composite material, the shear strength of the modified carbon fiber reinforced polypropylene composite material is improved by 28.9%, the bending strength is improved by 19.2%, and the performance is better improved.
According to the thermogravimetric graphs of the carbon fiber reinforced polypropylene composite materials of the test example 2 and the comparative example 2 in fig. 7, the decomposition temperature of the carbon fiber reinforced polypropylene composite material without dopamine treatment is 453.9 ℃, while the decomposition temperature of the carbon fiber reinforced polypropylene composite material loaded with the polydopamine film is 459.5 ℃, which is relatively slightly higher than that of the modified carbon fiber thermoplastic composite material.
Test example 3:
firstly, 0.48456g of Tris (hydroxymethyl) aminomethane (Tris), 50ml of absolute ethanol and 1M hydrochloric acid buffer solution are added into 400ml of aqueous solution to obtain a Tris solution with the concentration of 0.01M;
adding 0.2g of cationic starch, 0.8g of dopamine hydrochloride, N-dimethylformamide, 4-aminophenol and 4-Dimethylaminopyridine (DMAP) into the Tris solution obtained in the step one according to the mass concentration of 2g/L, and performing ultrasonic treatment for 30min to obtain a uniformly mixed solution;
preparing a mixed solution of 200ml of acetone and 200ml of absolute ethyl alcohol according to the ratio of 1: 1, then placing the commercial carbon fiber in the solution, standing for 24 hours, washing and drying to obtain the carbon fiber with the sizing agent removed;
fourthly, mixing the carbon fiber desized in the third step with the solution prepared in the second step according to the bath ratio of 1: 1, standing for 18 hours, taking out, washing and drying to obtain the carbon fiber with a layer of polymer film attached to the surface;
fifthly, alternately stacking the carbon fibers attached with the polymer films obtained in the step four and the nylon 66(PA66) thermoplastic resin films according to the mass ratio of 7: 13, then carrying out hot pressing at 260 ℃ and 10MPa for 10min, and carrying out cold press molding to obtain the carbon fiber reinforced nylon 66 composite material.
Comparative example 3:
firstly, preparing a mixed solution of 200ml of acetone and 200ml of absolute ethyl alcohol according to a ratio of 1: 1, then placing commercial carbon fibers in the solution, standing for 24 hours, washing and drying to obtain carbon fibers with sizing agents removed;
and secondly, alternately stacking the desized carbon fibers obtained in the step two and a nylon 66(PA66) thermoplastic resin film according to the mass ratio of 7: 13, then carrying out hot pressing at 260 ℃ and 10MPa for 10min, and carrying out cold press molding to obtain the carbon fiber reinforced nylon 66 composite material.
Fig. 8 shows an atomic force microscope photograph of the T300 carbon fiber cloth without the polymer film loaded in test example 3, and fig. 9 shows an atomic force microscope photograph of the T300 carbon fiber cloth with the polymer film loaded in step three. As can be seen from fig. 8, the untreated carbon fiber has some defects such as grooves on the surface thereof, and the surface thereof is relatively smooth, and it can be seen that the surface thereof contains a small amount of commercial sizing agent, and as can be seen from fig. 9, the defects such as some grooves on the surface of the carbon fiber after loading a layer of polymer film are filled with the polymer film to repair some defects of the carbon fiber itself, and the roughness of the surface is also significantly improved, which is beneficial to mechanical engagement between the fiber and the resin to improve the bonding force of the interface. The polymer film has certain water absorption, so that the surface of the polymer film has some water marks, and the successful loading of the polymer film on the surface of the carbon fiber is also laterally proved.
The carbon fiber reinforced nylon 66 composite material in test example 3 and the carbon fiber reinforced nylon 66 composite material in comparative example 3 were subjected to an interlaminar shear property test and a bending property test, and the results are shown in table 5 below.
TABLE 5 interlaminar shear strength and flexural Strength of carbon fiber reinforced Nylon 66 composites
Figure BDA0003240503850000141
From table 5, it can be seen that the interlaminar shear strength (ILSS) of the carbon fiber reinforced nylon 66 composite material without the modifier treatment in comparative example 3 is only 13.5MPa and the flexural strength is only 190.3MPa, while the interlaminar shear strength (ILSS) of the carbon fiber reinforced nylon 66 composite material loaded with the polymer film in example 3 is 27.4MPa and the flexural strength is 278.7 MPa. Compared with the unmodified carbon fiber reinforced nylon 66 composite material, the shear strength of the modified carbon fiber reinforced nylon 66 composite material is improved by 103%, the bending strength is improved by 46.5%, and the improvement is great.
Test example 4:
firstly, 0.48456g of Tris (hydroxymethyl) aminomethane (Tris), 50ml of absolute ethanol and 1M hydrochloric acid buffer solution are added into 400ml of aqueous solution to obtain a Tris solution with the concentration of 0.01M;
adding 0.15g of carboxymethyl cellulose, 0.4g of ethylene-vinyl acetate copolymer, N-dimethylformamide, 4-aminophenol and 4-Dimethylaminopyridine (DMAP) into the Tris solution obtained in the step one according to the mass concentration of 2g/L, and performing ultrasonic treatment for 30min to obtain a uniformly mixed solution;
preparing a mixed solution of 200ml of acetone and 200ml of absolute ethyl alcohol according to the ratio of 1: 1, then placing the commercial carbon fiber in the solution, standing for 24 hours, washing and drying to obtain the carbon fiber with the sizing agent removed;
fourthly, mixing the carbon fiber desized in the third step with the solution prepared in the second step according to the bath ratio of 1: 1, standing for 18 hours, taking out, washing and drying to obtain the carbon fiber with a layer of cellulose film attached to the surface;
and fifthly, alternately stacking the carbon fibers attached with the cellulose film obtained in the step four and an acrylonitrile-butadiene-styrene copolymer (ABS) thermoplastic resin film, hot-pressing at 230 ℃ and 10MPa for 11min, and then cold-pressing and molding to obtain the carbon fiber reinforced ABS composite material.
Comparative example 4:
firstly, preparing a mixed solution of 200ml of acetone and 200ml of absolute ethyl alcohol according to a ratio of 1: 1, then placing commercial carbon fibers in the solution, standing for 24 hours, washing and drying to obtain carbon fibers with sizing agents removed;
and secondly, alternately stacking the desized carbon fibers obtained in the step two and acrylonitrile-butadiene-styrene copolymer (ABS) thermoplastic resin films, hot-pressing at 230 ℃ and 10MPa for 11min, and then carrying out cold press molding to obtain the carbon fiber reinforced ABS composite material.
The carbon fiber reinforced ABS composite in test example 4 and the carbon fiber reinforced ABS composite in comparative example 4 were subjected to an interlaminar shear performance test and a bending performance test, and the results are shown in table 6 below.
TABLE 6 interlaminar shear strength and flexural strength of carbon fiber reinforced ABS composites
Figure BDA0003240503850000151
From table 6, it can be seen that the carbon fiber reinforced ABS composite material of comparative example 4 without the modifier treatment has an interlaminar shear strength (ILSS) of only 16.1MPa and a flexural strength of only 248.7MPa, while the carbon fiber reinforced ABS composite material of test example 4 carrying a polymer film has an interlaminar shear strength (ILSS) of 28.1MPa and a flexural strength of 350.2 MPa. Compared with the unmodified carbon fiber reinforced ABS composite material, the shear strength of the modified carbon fiber reinforced ABS composite material is improved by 74.5%, the bending strength is improved by 40.8%, and the improvement is great.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (10)

1. A method for improving the interface bonding strength of a fiber reinforced thermoplastic composite material is characterized by comprising the following steps:
adding Tris (hydroxymethyl) aminomethane, absolute ethyl alcohol and a hydrochloric acid buffer solution into an aqueous solution to obtain a Tris solution;
adding one or more modifiers of polyvinyl alcohol, cationic starch, dopamine hydrochloride, ethylene-vinyl acetate copolymer, carboxymethyl cellulose and waterborne polyurethane, N-dimethylformamide, 4-aminophenol and 4-dimethylaminopyridine into the Tris solution obtained in the step one, and performing ultrasonic treatment to obtain a uniformly mixed solution;
thirdly, preparing a mixed solution from acetone and absolute ethyl alcohol, placing one or more fibers of carbon fibers, glass fibers and basalt fibers in the mixed solution, standing, washing and drying to obtain desized fibers;
fourthly, placing the desized fiber obtained in the third step into the solution prepared in the second step, standing, taking out, washing and drying to obtain the fiber with a layer of polymer film attached to the surface;
fifthly, the fiber reinforced thermoplastic composite material is obtained by carrying out one or more molding processes of hot press molding, pultrusion molding, transfer molding and 3D printing molding on the fiber obtained in the fourth step and one or more thermoplastic resins of polyimide, nylon 6, nylon 66, polypropylene, polyether-ether-ketone and acrylonitrile-butadiene-styrene copolymer.
2. The method of claim 1, wherein in step one, the concentration of Tris in the Tris solution is 0.005-0.1 mol/L.
3. The method according to claim 1, wherein in the second step, the mass concentration of the modifier is 1-5 g/L; the time of ultrasonic treatment is 1-3 hours.
4. The method according to claim 1, wherein in the third step, the standing time is 6-48 h.
5. The method of claim 1 wherein in step four, the bath ratio of desized fiber to solution is from 0.8 to 1.2: 1.
6. The method of claim 1, wherein in step five, the ratio of fibers to thermoplastic resin is 7: 10-15.
7. The method of claim 1, wherein, in step five,
the hot-press molding reaction temperature of the nylon 6 thermoplastic resin is 100-500 ℃; the hot-press forming pressure is 3-20 MPa; the hot-press molding time is 3-30 min;
the hot press molding reaction temperature of the nylon 66 thermoplastic resin is 150-450 ℃; the hot-press forming pressure is 3-20 MPa; the hot-press molding time is 3-30 min;
the hot-press molding reaction temperature of the polypropylene thermoplastic resin is 100-450 ℃; the hot-press forming pressure is 3-20 MPa; the hot-press molding time is 3-30 min;
the hot press molding reaction temperature of the polyether-ether-ketone thermoplastic resin is 200-600 ℃; the hot pressing pressure is 3-20 MPa; the hot-press molding time is 3-30 min;
the hot press molding reaction temperature of the acrylonitrile-butadiene-styrene copolymer thermoplastic resin is 100-600 ℃; the hot-press forming pressure is 3-20 MPa; the hot-press forming time is 3-30 min.
8. The method of claim 7, wherein, in step five,
the hot-press molding reaction temperature of the nylon 6 thermoplastic resin is 200-350 ℃; the hot-press forming pressure is 5-15 MPa; the hot-press molding time is 5-20 min;
the hot press molding reaction temperature of the nylon 66 thermoplastic resin is 200-350 ℃; the hot-press forming pressure is 5-15 MPa; the hot-press molding time is 5-20 min;
the hot-press molding reaction temperature of the polypropylene thermoplastic resin is 150-300 ℃; the hot-press forming pressure is 5-15 MPa; the hot-press molding time is 5-20 min;
the hot press molding reaction temperature of the polyether-ether-ketone thermoplastic resin is 250-500 ℃; the hot pressing pressure is 5-15 MPa; the hot-press molding time is 5-20 min;
the hot press molding reaction temperature of the acrylonitrile-butadiene-styrene copolymer thermoplastic resin is 150-500 ℃; the hot pressing pressure is 5-15 MPa; the hot-press forming time is 5-20 min.
9. The method of claim 8, wherein, in step five,
the hot press molding reaction temperature of the nylon 6 thermoplastic resin is 250-280 ℃; the hot-press forming pressure is 10-13 MPa; the hot-press molding time is 10-15 min;
the hot press molding reaction temperature of the nylon 66 thermoplastic resin is 250-300 ℃; the hot-press forming pressure is 10-13 MPa; the hot-press molding time is 10-15 min;
the hot-press molding reaction temperature of the polypropylene thermoplastic resin is 200-250 ℃; the hot-press forming pressure is 8-12 MPa; the hot press molding time is 8-13 min;
the hot press molding reaction temperature of the polyether-ether-ketone thermoplastic resin is 300-450 ℃; the hot pressing pressure is 9-12 MPa; the hot press molding time is 9-13 min;
the reaction temperature of the acrylonitrile-butadiene-styrene copolymer thermoplastic resin hot press molding is 230-300 ℃; the hot pressing pressure is 9-12 MPa; the hot-press forming time is 9-13 min.
10. Use of the fiber-reinforced thermoplastic composite obtained by the process according to claim 1 in the automotive industry, in the aerospace field, in electronic appliances, in sports equipment, in the household appliance field.
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