CN113583267B - Method for improving interfacial bonding strength of fiber-reinforced thermoplastic composite material - Google Patents

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

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CN113583267B
CN113583267B CN202111018445.9A CN202111018445A CN113583267B CN 113583267 B CN113583267 B CN 113583267B CN 202111018445 A CN202111018445 A CN 202111018445A CN 113583267 B CN113583267 B CN 113583267B
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press molding
fiber
hot
hot press
thermoplastic resin
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CN113583267A (en
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李仁宏
王刚
杜雷雷
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Zhejiang University Of Technology Shaoxing Keqiao Research Institute Co ltd
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Zhejiang University Of Technology Shaoxing Keqiao Research Institute Co ltd
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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
    • 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
    • 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

Abstract

The invention relates to the field of composite materials, and discloses a method for improving the interfacial bonding strength of a fiber-reinforced thermoplastic composite material, which comprises the following steps: 1. preparing a Tris solution; 2. adding polyvinyl alcohol, cationic starch, dopamine hydrochloride, ethylene-vinyl acetate copolymer, carboxymethyl cellulose, aqueous polyurethane and other modifiers, N-dimethylformamide, 4-aminophenol and 4-dimethylaminopyridine into a Tris solution, and carrying out ultrasonic treatment to obtain a solution; 3. desizing the fiber to obtain a desized fiber; 4. placing the desized fiber in a solution to attach a polymer film on the surface of the fiber; 5. and compounding the fiber with thermoplastic resin to obtain the fiber reinforced thermoplastic composite material. According to the invention, after desizing treatment of the fiber, the fiber is impregnated with the modifier, and a layer of polymer film is attached to 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 interfacial 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 interfacial 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 field, electronic appliances, sports facilities, household appliances and the like due to the characteristics of high tensile rigidity, strength and other mechanical properties, high chemical softening point, good high-temperature melt fluidity, repeated recycling and the like.
However, the strength of the fiber-reinforced thermoplastic composite is often lower than that of the fiber-reinforced thermosetting composite, so that the fiber-reinforced thermoplastic composite is limited in many application fields requiring high strength and high hardness, and thus it is necessary to improve the strength of the fiber-reinforced thermoplastic composite, and one of the key factors affecting the strength thereof is the magnitude of interfacial bonding force between the fiber and the thermoplastic matrix resin. The surface of the fiber is smooth and presents chemical inertia, so that the interface compatibility with the thermoplastic matrix is poor, and the interface binding force is small, so that the overall mechanical property of the composite material is not high, and the practical application of the fiber reinforced thermoplastic composite material is affected.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for improving the interfacial bonding strength of a fiber-reinforced thermoplastic composite material, which comprises the steps of performing modifier dipping treatment after fiber desizing treatment to enable a layer of polymer film to be attached to the surface of a fiber so as to increase the surface energy of the fiber and improve the interfacial bonding strength of the fiber and a thermoplastic resin matrix.
The specific technical scheme of the invention is as follows:
a method of improving interfacial bond strength of a fiber-reinforced thermoplastic composite comprising the steps of:
1. adding Tris (hydroxymethyl) aminomethane, absolute ethyl alcohol and a hydrochloric acid buffer solution into an aqueous solution to obtain a Tris solution;
2. adding one or more modifiers of polyvinyl alcohol, cationic starch, dopamine hydrochloride, ethylene-vinyl acetate copolymer, carboxymethyl cellulose and aqueous polyurethane, N-dimethylformamide, 4-aminophenol and 4-dimethylaminopyridine into the Tris solution obtained in the step one, and carrying out ultrasonic treatment to obtain a uniformly mixed solution;
3. preparing a mixed solution from acetone and absolute ethyl alcohol, and then placing one or more fibers of carbon fibers, glass fibers and basalt fibers into the mixed solution, standing, washing and drying to obtain desized fibers;
4. 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 a fiber with a layer of polymer film attached to the surface;
5. and (3) 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 step (IV) and one or more thermoplastic resins of polyimide, nylon 6, nylon 66, polypropylene, polyether-ether-ketone and acrylonitrile-butadiene-styrene copolymer to obtain the fiber reinforced thermoplastic composite material.
In steps one to two, the present invention produces an impregnating solution for modifying the surface of a fiber; wherein the purpose of preparing the Tris solution in step one is to provide an alkaline environment capable of accelerating the polymerization of the modifier in the solution to increase the rate of the polymer polymerization; 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 groups and can improve the stability and uniformity of the high polymer film load, and in practical application, the production period can be shortened and the production stability can be improved. In the third step, the fiber is subjected to desizing treatment so as to improve the adhesion effect of the modifier in the impregnating solution on the surface of the fiber. 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 to form a layer of polymer film, and the polymer film is provided with a plurality of 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 a thermoplastic matrix so as to remarkably enhance the interfacial bonding force between the fiber and the resin.
In summary, the bonding force between the fiber and the thermoplastic resin is improved by attaching a layer of polymer film on the surface of the fiber, and compared with the traditional methods such as strong acid oxidation, the method not only effectively avoids the damage to the fiber caused by the strong acid oxidation, but also repairs the defect 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 to 0.1mol/L. Preferably, the Tris concentration is 0.01mol/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 2g/L. The ultrasonic treatment time 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 to 48 hours. Preferably, the fibers are carbon fibers.
Preferably, in step four, the bath ratio of the desized fiber and 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 the fifth step:
The hot-press molding reaction temperature of the nylon 6 thermoplastic resin is 100-500 ℃; the hot press molding pressure is 3-20 MPa; the hot press molding time is 3-30 min; further preferably, the reaction temperature of the hot press molding is 200-350 ℃; the hot press molding pressure is 5-15 MPa; the hot press molding time is 5-20 min; still more preferably, the hot press forming reaction temperature is 250-280 ℃; the hot press molding 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 150-450 ℃; the hot press molding pressure is 3-20 MPa; the hot press molding time is 3-30 min; further preferably, the reaction temperature is 200 to 350 ℃; the hot press molding pressure is 5-15 MPa; the hot press molding time is 5-20 min; still more preferably, the hot press forming reaction temperature is 250-300 ℃; the hot press molding 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 100-450 ℃; the hot press molding pressure is 3-20 MPa; the hot press molding time is 3-30 min; further preferably, the reaction temperature of the hot press molding is 150-300 ℃; the hot press molding pressure is 5-15 MPa; the hot press molding time is 5-20 min; still more preferably, the reaction temperature of the hot press molding is 200-250 ℃; the hot press molding 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 200-600 ℃; the hot pressing pressure is 3-20 MPa; the hot press molding time is 3-30 min; further preferably, the reaction temperature of the hot press molding is 250-500 ℃; the hot pressing pressure is 5-15 MPa; the hot press molding time is 5-20 min; still more preferably, the reaction temperature of the hot press molding is 300-450 ℃; the hot pressing pressure is 9-12 MPa; the hot press molding time is 9-13 min.
The hot-press molding reaction temperature of the thermoplastic resin of the acrylonitrile-butadiene-styrene copolymer is 100-600 ℃; the hot press molding pressure is 3-20 MPa; the hot press molding time is 3-30 min; further preferably, the reaction temperature of the hot press molding is 150-500 ℃; the hot pressing pressure is 5-15 MPa; the hot press molding time is 5-20 min; still more preferably, the reaction temperature is 230 to 300 ℃; the hot pressing pressure is 9-12 MPa; the hot press molding 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: according to the invention, the fiber is subjected to desizing treatment and then is subjected to modifier dipping treatment, so that a layer of polymer film is attached to the surface of the fiber, and the polymer film is provided with a plurality of 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 a thermoplastic matrix, so that the interfacial binding force of the fiber and resin can be obviously enhanced. Compared with the traditional methods such as strong acid oxidation, the method of the invention not only effectively avoids the damage to the fiber caused by the strong acid oxidation, but also repairs the defect of the fiber surface, 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 the polydopamine film loaded obtained in the step two of test example 1;
FIG. 2 is a scanning electron microscope image of the T300 carbon fiber loaded with the polydopamine film obtained in the fourth step of test example 1;
FIG. 3 is a graph of tensile strength versus carbon fiber monofilaments of test example 1 with different modifications;
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 plot of flexural strength force versus displacement for the composites of test example 1 and comparative example 1;
FIG. 6 is a thermogravimetric plot of the carbon fiber reinforced nylon 6 composite of test example 1 and comparative example 1;
FIG. 7 is a thermogravimetric plot of the carbon fiber reinforced polypropylene composite of test example 2 and comparative example 2;
FIG. 8 is an atomic force microscope photograph of T300 carbon fibers of the non-supported polydopamine film obtained in the step two of test example 3;
FIG. 9 is an atomic force microscope photograph of T300 carbon fibers of the polymer-supported thin film obtained in the fourth step of test example 3.
Detailed Description
The application is further illustrated below in conjunction with specific embodiments. These examples are only for illustrating the present application and are not intended to limit the scope of the present application. Further, after reading the teachings of the present application, those skilled in the art may make various changes or modifications to the present application, which equivalent forms also fall within the scope of the present application as defined in the appended claims.
The first embodiment is as follows:
1. 0.48456g of Tris (hydroxymethyl) aminomethane (Tris), 50ml of absolute ethanol and 1M hydrochloric acid buffer were added to 400ml of an aqueous solution to give a Tris solution having a concentration of 0.01M.
2. Adding 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 carrying out ultrasonic treatment for 30min to obtain a uniformly mixed solution.
3. 200ml of acetone and 200ml of absolute ethyl alcohol are prepared into a mixed solution according to the ratio of 1:1, and then commercial carbon fibers are placed in the solution for standing for 24 hours, washed and dried to obtain the carbon fibers with sizing agent removed.
4. And (3) mixing the desized carbon fiber in the step (III) with the solution prepared in the step (II) according to the bath ratio of 1:1, standing for 18 hours, and taking out, washing and drying to obtain the carbon fiber with the surface attached with the polydopamine film.
5. And (3) alternately stacking the carbon fibers attached with the polydopamine film and the nylon 6 (PA 6) thermoplastic resin film obtained in the step (IV) according to the mass ratio of 7:13, and then performing hot pressing at 250 ℃ and 10MPa for 10min, and performing cold press molding to obtain the carbon fiber reinforced nylon 6 composite material.
The second embodiment is as follows: the difference between this embodiment and the first embodiment is that the thermoplastic matrix in the fifth step is polypropylene (PP), the temperature in the fifth step is 200 ℃, and the other steps are the same as those in the first embodiment.
And a third specific embodiment: this embodiment differs from the first embodiment in that the thermoplastic matrix described in step five is nylon 66 (PA 66), the temperature described in step five is 260 ℃, and the other is the same as the first embodiment.
The specific embodiment IV is as follows: the difference between this embodiment and the first embodiment is that the thermoplastic matrix in the fifth step is Polyetheretherketone (PEEK), the temperature in the fifth step is 375 ℃, and the other steps are the same as those in the first embodiment.
Fifth embodiment: this embodiment differs from the first embodiment in that the thermoplastic matrix in step five is an acrylonitrile-butadiene-styrene copolymer (ABS), and in step five the temperature is 230 ℃, otherwise the same as in the first embodiment.
Specific embodiment six: the present embodiment differs from the first embodiment in that the reinforcement member described in the third step is glass fiber, and the other steps are the same as the first embodiment.
Seventh embodiment: the present embodiment differs from the second embodiment in that the reinforcement member described in the third step is glass fiber, and the other steps are the same as those in the second embodiment.
Eighth embodiment: this embodiment differs from the third embodiment in that the reinforcement member described in the third step is glass fiber, and the other steps are the same as those in the third embodiment.
Detailed description nine: the present embodiment differs from the fourth embodiment in that the reinforcement member described in the third step is glass fiber, and the other steps are the same as those in the fourth embodiment.
Detailed description ten: the present embodiment differs from the fifth embodiment in that the reinforcement member described in the third step is glass fiber, and the other steps are the same as those in the fifth embodiment.
Eleventh embodiment: the first difference between this embodiment and the first embodiment is that the reinforcement in the third step is basalt fiber, and the other is the same as the first or sixth embodiment.
Twelve specific embodiments: the second embodiment is different from the second embodiment in that the reinforcement in the third embodiment is basalt fiber, and the other reinforcement is the same as the second or seventh embodiment.
Thirteen specific embodiments: the difference between the present embodiment and the third embodiment is that the reinforcement in the third step is basalt fiber, and the other steps are the same as those in the third or eighth embodiment.
Fourteen specific embodiments: the fourth embodiment is different from the fourth embodiment in that the reinforcement in the third step is basalt fiber, and the other reinforcement is the same as the fourth or ninth embodiment.
Fifteen embodiments: the fifth embodiment is different from the fifth embodiment in that the reinforcement in the third step is basalt fiber, and the other reinforcement is the same as the fifth or tenth embodiment.
Sixteen specific embodiments:
1. tris (hydroxymethyl) aminomethane (Tris) of 0.48456, 50ml of absolute ethanol and 1M hydrochloric acid buffer were added to the aqueous solution to give a Tris solution at a concentration of 0.01M.
2. 0.8g of polyvinyl alcohol, N-dimethylformamide, 4-aminophenol and 4-Dimethylaminopyridine (DMAP) are added into the Tris solution obtained in the step one according to the mass concentration of 2g/L, and the solution is treated by ultrasonic waves for 30min to obtain a uniformly mixed solution.
3. 200ml of acetone and 200ml of absolute ethyl alcohol are prepared into a mixed solution according to the ratio of 1:1, and then commercial carbon fibers are placed in the solution for standing for 24 hours, washed and dried to obtain the carbon fibers with sizing agent removed.
4. And (3) mixing the desized carbon fiber in the step (III) with the solution prepared in the step (II) according to the bath ratio of 1:1, standing for 18 hours, and taking out, washing and drying to obtain the carbon fiber with the surface attached with the polyvinyl alcohol film.
5. And (3) alternately stacking the carbon fibers attached with the polyvinyl alcohol film obtained in the step (IV) and a nylon 6 (PA 6) thermoplastic resin film according to the mass ratio of 7:13, and then performing hot pressing at 250 ℃ and 10MPa for 10min, and performing cold press molding to obtain the carbon fiber reinforced nylon 6 composite material.
Seventeenth embodiment: this embodiment differs from embodiment sixteen in that the thermoplastic matrix described in step five is polypropylene (PP), the temperature described in step five is 200 ℃, and the other is the same as embodiment sixteen.
The concrete implementation mode is eighteen: the first difference between this embodiment and the second embodiment is that the thermoplastic matrix in the fifth step is nylon 66 (PA 66), the temperature in the fifth step is 260 ℃, and the other steps are the same as those in the sixteenth embodiment.
Detailed description nineteenth embodiment: this embodiment differs from embodiment sixteen in that the thermoplastic matrix described in step five is Polyetheretherketone (PEEK), the temperature described in step five is 375 ℃, and the other is the same as embodiment sixteen.
Twenty specific embodiments: this embodiment is sixteen different from the first embodiment in that the thermoplastic matrix in the fifth step is an acrylonitrile-butadiene-styrene (ABS), the temperature in the fifth step is 230 ℃, and the other steps are the same as in the first embodiment.
Detailed description twenty-one: this embodiment is different from the sixteenth embodiment in that the reinforcement member in the third step is glass fiber, and the other is the same as the sixteenth embodiment.
Detailed description twenty-two: this embodiment differs from the seventeenth embodiment in that the reinforcement member in the third step is glass fiber, and the other steps are the same as the seventeenth embodiment.
The concrete implementation mode is twenty-third: the eighteenth embodiment is different from the eighteenth embodiment in that the reinforcement member in the third step is glass fiber, and the other reinforcement members are the same as the eighteenth embodiment.
Twenty-four of the embodiments: this embodiment differs from the nineteenth embodiment in that the reinforcement member in the third step is glass fiber, and the other steps are the same as the nineteenth embodiment.
Twenty-five of the embodiments: this embodiment differs from the second embodiment in that the reinforcement member described in the third step is glass fiber, and the other steps are the same as the second embodiment.
Detailed description twenty-six embodiments: the difference between the present embodiment and the sixteenth embodiment is that the reinforcement in the third step is basalt fiber, and the other steps are the same as those in the sixteenth or twenty-first embodiment.
Twenty-seven of the embodiments: the difference between the present embodiment and the seventeenth embodiment is that the reinforcement in the third step is basalt fiber, and the other is the same as the seventeenth embodiment or the twenty-two embodiments.
The twenty-eighth embodiment: the eighteenth embodiment is different from the eighteenth embodiment in that the reinforcement in the third step is basalt fiber, and the other reinforcement is the same as eighteen or twenty-third embodiments.
Detailed description twenty-nine: this embodiment differs from the nineteenth embodiment in that the reinforcement in step three is basalt fiber, and the other is the same as the nineteenth or twenty-fourth embodiment.
Detailed description thirty: the twenty-difference between this embodiment and the twenty-second embodiment is that the reinforcement in the third step is basalt fiber, and the other reinforcement is the same as the twenty-or twenty-fifth embodiment.
Detailed description thirty-one:
1. tris (hydroxymethyl) aminomethane (Tris) of 0.48456, 50ml of absolute ethanol and 1M hydrochloric acid buffer were added to the aqueous solution to give a Tris solution at a concentration of 0.01M.
2. 0.15g of carboxymethyl cellulose, 0.4g of ethylene-vinyl acetate copolymer, N-dimethylformamide, 4-aminophenol and 4-Dimethylaminopyridine (DMAP) are added into the solution obtained in the step one according to the mass concentration of 2g/L, and the solution is treated by ultrasonic waves for 30min to obtain a uniformly mixed solution.
3. 200ml of acetone and 200ml of absolute ethyl alcohol are prepared into a mixed solution according to the ratio of 1:1, and then commercial carbon fibers are placed in the solution for standing for 24 hours, washed and dried to obtain the carbon fibers with sizing agent removed.
4. And (3) mixing the desized carbon fiber in the step (III) with the solution prepared in the step (II) according to the bath ratio of 1:1, standing for 18 hours, and taking out, washing and drying to obtain the carbon fiber with a layer of cellulose film attached to the surface.
5. And (3) alternately stacking the carbon fibers attached with the cellulose film obtained in the step (IV) and a nylon 6 (PA 6) thermoplastic resin film according to the mass ratio of 7:13, and then performing hot pressing at 250 ℃ and 10MPa for 10min, and performing cold press molding to obtain the carbon fiber reinforced nylon 6 composite material.
Detailed description thirty-two: this embodiment differs from the thirty-one embodiment in that the thermoplastic matrix in step five is polypropylene (PP), the temperature in step five is 200 ℃, and the other is the same as the thirty-one embodiment.
Detailed description thirty-three embodiments: this embodiment differs from the thirty-one embodiment in that the thermoplastic matrix described in step five is nylon 66 (PA 66), and in step five the temperature is 260 ℃, otherwise the same as the thirty-one embodiment.
Detailed description thirty-four embodiments: this embodiment differs from the thirty-one embodiment in that the thermoplastic matrix in step five is Polyetheretherketone (PEEK), and in step five the temperature is 375 ℃, otherwise the same as the thirty-one embodiment.
Thirty-five of the embodiments: this embodiment differs from the thirty-one embodiment in that the thermoplastic matrix described in step five is an acrylonitrile-butadiene-styrene copolymer (ABS), the temperature described in step five is 230 ℃, and the other is the same as in embodiment one.
Detailed description thirty-six embodiments: this embodiment differs from the thirty-first embodiment in that the reinforcement member in step three is glass fiber, and the other is the same as the thirty-first embodiment.
Thirty-seven of the embodiments: the present embodiment differs from the thirty-two embodiments in that the reinforcement member in the third step is glass fiber, and the other steps are the same as the thirty-two embodiments.
The concrete implementation mode is thirty-eight: this embodiment differs from the thirty-third embodiment in that the reinforcement member described in step three is glass fiber, and the other is the same as the thirty-third embodiment.
Detailed description thirty-nine: this embodiment differs from the thirty-fourth embodiment in that the reinforcement member described in step three is glass fiber, and the other is the same as the thirty-fourth embodiment.
Description of the embodiments forty: this embodiment differs from the thirty-fifth embodiment in that the reinforcement member described in step three is glass fiber, and the other is the same as the thirty-fifth embodiment.
Detailed description forty-one: this embodiment differs from the thirty-first embodiment in that the reinforcement in step three is basalt fiber, otherwise identical to the thirty-first or thirty-sixth embodiments.
Detailed description forty-two: the thirty-two different from the concrete embodiment is that the reinforcement in the third step is basalt fiber, and the other reinforcement is the same as the thirty-two or thirty-seven of the concrete embodiment.
Detailed description forty-third embodiment: the difference between the present embodiment and the thirty-third embodiment is that the reinforcement in the third step is basalt fiber, and the other is the same as the thirty-third or thirty-eighth embodiment.
Detailed description forty-four: this embodiment differs from the thirty-fourth embodiment in that the reinforcement in step three is basalt fiber, and the other is the same as the thirty-fourth or thirty-ninth embodiment.
Description of the preferred embodimentsforty-five: this embodiment differs from the thirty-fifth embodiment in that the reinforcement described in step three is basalt fiber, otherwise identical to the thirty-fifth or forty embodiments.
Detailed description forty-six embodiments:
1. tris (hydroxymethyl) aminomethane (Tris) of 0.48456, 50ml of absolute ethanol and 1M hydrochloric acid buffer were added to the aqueous solution to give a Tris solution at a concentration of 0.01M.
2. 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 step one according to the mass concentration of 2g/L, and carrying out ultrasonic treatment for 30min to obtain a uniformly mixed solution.
3. Preparing a mixed solution of acetone and absolute ethyl alcohol according to the ratio of 1:1, then placing commercial carbon fibers in the solution, standing for 24 hours, washing and drying to obtain the carbon fibers from which sizing agents are removed.
4. And (3) mixing the desized carbon fiber in the step (III) with the solution prepared in the step (II) according to the bath ratio of 1:1, standing for 18 hours, and taking out, washing and drying to obtain the carbon fiber with the surface attached with the polymer film.
5. And (3) mixing the carbon fiber attached with the polymer film obtained in the step (IV) with nylon 6 (PA 6) thermoplastic resin powder, setting the parameter filling density as 100 in a 3D printer, setting the printing temperature as 250 ℃, setting the platform temperature as 100 ℃, setting the fan speed as 2, setting the printing speed as slower, and carrying out processing molding to obtain the carbon fiber reinforced nylon 6 composite material.
Forty-seven embodiments: the difference between this embodiment and the forty-six embodiments is that the thermoplastic matrix in the fifth step is polypropylene (PP), the printing temperature in the fifth step is 200 ℃, and the other steps are the same as those in the forty-six embodiments.
Forty-eight specific embodiments: the difference between this embodiment and the forty-six embodiments is that the thermoplastic matrix in the fifth step is nylon 66 (PA 66), the printing temperature in the fifth step is 260 ℃, and the other steps are the same as those in the forty-six embodiments.
Detailed description forty-nine: the difference between the present embodiment and the forty-six embodiments is that the thermoplastic matrix in the fifth step is polyether ether ketone (PEEK), the printing temperature in the fifth step is 375 ℃, and the other steps are the same as those in the forty-six embodiments.
Detailed description fifty: the difference between this embodiment and the forty-six embodiments is that the thermoplastic matrix in the fifth step is acrylonitrile-butadiene-styrene (ABS), the printing temperature in the fifth step is 230 ℃, and the other steps are the same as those in the first embodiment.
Detailed description of the invention fifty one: the present embodiment differs from the forty-six embodiments in that the reinforcement member described in the third step is glass fiber, and the other steps are the same as the forty-six embodiments.
Specific embodiment fifty-two: the forty-seven difference between this embodiment and the specific embodiment is that the reinforcement member described in the third step is glass fiber, and the other is the same as the forty-seven of the specific embodiment.
Detailed description of the invention fifty-three: the forty-eight difference between this embodiment and the specific embodiment is that the reinforcement member in the third step is glass fiber, and the other is forty-eight.
Detailed description fifty-four: this embodiment differs from the forty-nine embodiments in that the reinforcement described in step three is glass fiber, and the other is the same as the forty-nine embodiments.
Detailed description of the preferred embodimentsfifty-five: this embodiment differs from embodiment fifty in that the reinforcement member described in step three is glass fiber, and the other is the same as embodiment fifty.
Specific embodiment fifty-six: this embodiment differs from the forty-six embodiments in that the reinforcement described in step three is basalt fiber, otherwise identical to the forty-six or fifty-one embodiments.
Seventeenth embodiment: the forty-seven difference between this embodiment and the specific embodiment is that the reinforcement in the third step is basalt fiber, and the other is the same as the forty-seventy-seven or fifty of the specific embodiment.
Specific embodiment fifty-eight: the forty-eight difference between the present embodiment and the specific embodiment is that the reinforcement in the third step is basalt fiber, and the other steps are the same as forty-eight or fifty-three steps of the specific embodiment.
Detailed description of the preferred embodimentsfifty-nine: this embodiment differs from the forty-nine embodiments in that the reinforcement described in step three is basalt fiber, otherwise identical to the forty-nine or fifty-four embodiments.
Detailed description sixty: this embodiment differs from the fifty embodiments in that the reinforcement in step three is basalt fiber, otherwise identical to the fifty or fifty-five embodiments.
Test example 1:
1. 0.48456g of Tris (hydroxymethyl) aminomethane (Tris), 50ml of absolute ethanol and 1M hydrochloric acid buffer were added to 400ml of an aqueous solution to obtain a Tris solution having a concentration of 0.01M;
2. adding 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;
3. preparing 200ml of acetone and 200ml of absolute ethyl alcohol into a mixed solution according to the ratio of 1:1, then placing commercial carbon fibers into the solution, standing for 24 hours, washing and drying to obtain the carbon fibers from which sizing agents are removed;
4. mixing the desized carbon fiber in the third step with the solution prepared in the second step according to the bath ratio of 1:1, standing for 18 hours, and taking out, washing and drying to obtain the carbon fiber with a layer of polydopamine film attached to the surface;
5. and (3) alternately stacking the carbon fiber attached with the polydopamine film and a nylon 6 (PA 6) thermoplastic resin film according to the mass ratio of 7:13, hot-pressing at 250 ℃ and 10MPa for 10min, and cold-pressing to obtain the carbon fiber reinforced nylon 6 composite material.
Comparative example 1:
1. preparing 200ml of acetone and 200ml of absolute ethyl alcohol into a mixed solution according to the ratio of 1:1, then placing commercial carbon fibers into the solution, standing for 24 hours, washing and drying to obtain the carbon fibers from which sizing agents are removed;
2. and (3) alternately stacking the desized carbon fibers obtained in the step (II) and nylon 6 (PA 6) thermoplastic resin films according to the mass ratio of 7:13, and then carrying out hot pressing for 10min at the temperature of 250 ℃ and the pressure of 10MPa, and then carrying out cold press molding to obtain the carbon fiber reinforced nylon 6 composite material.
Example step one a mixed solution containing Tris (hydroxymethyl) aminomethane (Tris), absolute ethanol and hydrochloric acid buffer was prepared in order to provide an alkaline environment enabling the modifier to accelerate the polymerization reaction in the solution and thus to increase the rate of the polymer polymerization reaction. The substances such as N, N-dimethylformamide, 4-aminophenol, 4-Dimethylaminopyridine (DMAP) and the like contained in the second step are used for providing an environment which is rich in amino groups 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. The scanning electron microscope picture of the T300 carbon fiber cloth without the polydopamine film in the embodiment 1 is shown in fig. 1, the scanning electron microscope picture of the T300 carbon fiber cloth with the polydopamine film obtained by the third step is shown in fig. 2, and as can be seen from fig. 1, the untreated carbon fiber has some defects such as grooves and the like, and the surface is smoother. As can be seen from fig. 2, after a layer of film is loaded, some defects such as grooves on the surface of the carbon fiber are filled with polydopamine, so that some defects of the carbon fiber are repaired, the surface roughness is obviously improved, and mechanical engagement between the fiber and the resin is facilitated, so that the bonding force of an interface is improved. As can be seen from fig. 3, the tensile strength of the carbon fiber monofilaments of the polydopamine-loaded film of example 1 is 3.176MPa, the tensile strength of the carbon fiber monofilaments of the carbon fiber untreated by the comparative test 1 is 3.054MPa, and the tensile strength of the monofilaments of the modified carbon fiber are slightly increased.
The carbon fiber cloth of comparative example 1 was subjected to contact angle test and surface free energy test, and the results are shown in tables 1 to 2 below.
TABLE 1 contact angle of materials
TABLE 2 surface free energy of materials
Sample of 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
It can be seen from table 1 that the carbon fiber cloth of comparative example 1, which was not treated with dopamine, had a contact angle of 95.4 ° with water as a solvent and 67.7 ° with ethylene glycol as a solvent, whereas the carbon fiber cloth of test example 1, which was loaded with a polydopamine film, had a contact angle of 76.4 ° with water as a solvent and 31.5 ° with ethylene glycol as a solvent. The contact angle of the modified carbon fiber cloth is reduced greatly, so that the wettability of the carbon fiber cloth and liquid is improved by the modification method. According to table 2, the surface free energy of the carbon fiber cloth of the comparative example 1, which was not treated with dopamine, was 27.85mN/m, whereas the surface free energy of the carbon fiber cloth of the test example 1, which was loaded with the polydopamine film, was increased to 49.14mN/m, because polydopamine has many active groups such as hydroxyl groups, amino groups, etc., so that the surface free energy of the carbon fiber cloth was improved, and it was presumed that the modified carbon fiber cloth had good wettability with the resin, and further improved the mechanical properties of the composite material.
The carbon fiber-reinforced nylon 6 composite of test example 1, the carbon fiber-reinforced nylon 6 composite of comparative example 1, was subjected to an interlaminar shear property test and a flexural 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 composite
Fig. 4 and 5 are graphs of interlaminar shear strength and flexural strength force versus displacement, respectively, of a composite material. From table 3, fig. 4 and fig. 5, it can be seen that the carbon fiber reinforced nylon 6 composite material 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, whereas the carbon fiber reinforced nylon 6 composite material 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 268.4MPa. Compared with the unmodified carbon fiber reinforced nylon 6 composite material, the modified carbon fiber reinforced nylon 6 composite material has the advantages that the shearing strength is improved by 182%, the bending strength is improved by 56.9%, and the improvement is very high.
As can be seen from the thermogravimetric graphs of the carbon fiber reinforced nylon 6 composite of test example 1 and comparative example 1 in fig. 6, the decomposition temperature of the carbon fiber reinforced nylon 6 composite without the dopamine treatment was 434.1 ℃, while the decomposition temperature of the carbon fiber reinforced nylon 6 composite loaded with the polydopamine film was 439.7 ℃, compared with the modified carbon fiber thermoplastic composite, the thermal stability was slightly improved, and the overall effect was not great.
Test example 2:
1. 0.48456g of Tris (hydroxymethyl) aminomethane (Tris), 50ml of absolute ethanol and 1M hydrochloric acid buffer were added to 400ml of an aqueous solution to obtain a Tris solution having a concentration of 0.01M;
2. adding 0.3g of aqueous polyurethane, 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 carrying out ultrasonic treatment for 30min to obtain a uniformly mixed solution;
3. preparing 200ml of acetone and 200ml of absolute ethyl alcohol into a mixed solution according to the ratio of 1:1, then placing commercial carbon fibers into the solution, standing for 24 hours, washing and drying to obtain the carbon fibers from which sizing agents are removed;
4. mixing the desized carbon fiber in the third step with the solution prepared in the second step according to the bath ratio of 1:1, standing for 18 hours, and taking out, washing and drying to obtain the carbon fiber with a layer of polymer film attached to the surface;
5. and (3) alternately stacking the carbon fiber attached with the polymer film obtained in the step (IV) and a polypropylene (PP) thermoplastic film according to the mass ratio of 7:13, and then performing hot pressing for 10min at 200 ℃ and 10MPa, and performing cold press molding to obtain the carbon fiber reinforced polypropylene composite material.
Comparative example 2:
1. preparing 200ml of acetone and 200ml of absolute ethyl alcohol into a mixed solution according to the ratio of 1:1, then placing commercial carbon fibers into the solution, standing for 24 hours, washing and drying to obtain the carbon fibers from which sizing agents are removed;
2. And (3) alternately stacking the desized carbon fibers obtained in the step (II) and a polypropylene (PP) thermoplastic film according to the mass ratio of 7:13, and then performing hot pressing for 10min at 200 ℃ and 10MPa, and performing cold press molding to obtain the carbon fiber reinforced polypropylene composite material.
The carbon fiber-reinforced polypropylene composite material of comparative example 2 of example 2 was 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 composite materials
It can be seen from table 4 that the carbon fiber reinforced polypropylene of comparative example 2, which was not treated with dopamine, had an interlaminar shear strength (ILSS) of only 6.9MPa and a flexural strength of only 73MPa, whereas the carbon fiber reinforced polypropylene of test example 2, which was loaded with a polydopamine film, had an interlaminar shear strength (ILSS) of 8.9MPa and a flexural strength of 87MPa. Compared with the unmodified carbon fiber reinforced polypropylene composite material, the modified carbon fiber reinforced polypropylene composite material has the advantages that the shearing strength is improved by 28.9%, the bending strength is improved by 19.2%, and the performance is better improved.
As can be seen from the thermogravimetric graphs of the carbon fiber reinforced polypropylene composite materials of test example 2 and comparative example 2 in fig. 7, the decomposition temperature of the carbon fiber reinforced polypropylene composite material without the dopamine treatment is 453.9 ℃, and the decomposition temperature of the carbon fiber reinforced polypropylene composite material loaded with the polydopamine film is 459.5 ℃, compared with the modified carbon fiber thermoplastic composite material, the thermal stability is slightly improved.
Test example 3:
1. 0.48456g of Tris (hydroxymethyl) aminomethane (Tris), 50ml of absolute ethanol and 1M hydrochloric acid buffer were added to 400ml of an aqueous solution to obtain a Tris solution having a concentration of 0.01M;
2. 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 carrying out ultrasonic treatment for 30min to obtain a uniformly mixed solution;
3. preparing 200ml of acetone and 200ml of absolute ethyl alcohol into a mixed solution according to the ratio of 1:1, then placing commercial carbon fibers into the solution, standing for 24 hours, washing and drying to obtain the carbon fibers from which sizing agents are removed;
4. mixing the desized carbon fiber in the third step with the solution prepared in the second step according to the bath ratio of 1:1, standing for 18 hours, and taking out, washing and drying to obtain the carbon fiber with a layer of polymer film attached to the surface;
5. and (3) alternately stacking the carbon fiber attached with the polymer film obtained in the step (IV) and a nylon 66 (PA 66) thermoplastic resin film according to the mass ratio of 7:13, and then performing hot pressing at 260 ℃ and 10MPa for 10min, and performing cold press molding to obtain the carbon fiber reinforced nylon 66 composite material.
Comparative example 3:
1. preparing 200ml of acetone and 200ml of absolute ethyl alcohol into a mixed solution according to the ratio of 1:1, then placing commercial carbon fibers into the solution, standing for 24 hours, washing and drying to obtain the carbon fibers from which sizing agents are removed;
2. And (3) alternately stacking the desized carbon fibers obtained in the step (II) and nylon 66 (PA 66) thermoplastic resin films according to the mass ratio of 7:13, and then carrying out hot pressing for 10min at 260 ℃ and 10MPa, and then carrying out cold press molding to obtain the carbon fiber reinforced nylon 66 composite material.
An atomic force microscope picture of the T300 carbon fiber cloth without the polymer film is shown in fig. 8, and an atomic force microscope picture of the T300 carbon fiber cloth with the polymer film is shown in fig. 9. As can be seen from FIG. 8, the untreated carbon fiber has some defects such as grooves on the surface, and the surface is smooth, and it can be seen that the surface contains some 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 are filled with a polymer film after a layer of polymer film is loaded, so that some defects of the carbon fiber are repaired, the roughness of the surface is obviously improved, and the mechanical engagement between the fiber and the resin is facilitated, so that the bonding force of the interface is improved. Because the polymer film has certain water absorption, water waves appear on the surface, and the successful loading of the polymer film on the surface of the carbon fiber is also laterally demonstrated.
The carbon fiber-reinforced nylon 66 composite of test example 3 and the carbon fiber-reinforced nylon 66 composite of comparative example 3 were subjected to an interlaminar shear property test and a flexural 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 composite
It can be seen from table 5 that the carbon fiber reinforced nylon 66 composite of comparative example 3, which was not treated with the modifier, had an interlaminar shear strength (ILSS) of only 13.5MPa and a flexural strength of only 190.3MPa, whereas the carbon fiber reinforced nylon 66 composite of example 3, which was loaded with a polymer film, had an interlaminar shear strength (ILSS) of 27.4MPa and a flexural strength of 278.7MPa. 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 method has great improvement.
Test example 4:
1. 0.48456g of Tris (hydroxymethyl) aminomethane (Tris), 50ml of absolute ethanol and 1M hydrochloric acid buffer were added to 400ml of an aqueous solution to obtain a Tris solution having a concentration of 0.01M;
2. 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 carrying out ultrasonic treatment for 30min to obtain a uniformly mixed solution;
3. preparing 200ml of acetone and 200ml of absolute ethyl alcohol into a mixed solution according to the ratio of 1:1, then placing commercial carbon fibers into the solution, standing for 24 hours, washing and drying to obtain the carbon fibers from which sizing agents are removed;
4. Mixing the desized carbon fiber in the third step with the solution prepared in the second step according to the bath ratio of 1:1, standing for 18 hours, and taking out, washing and drying to obtain the carbon fiber with a layer of cellulose film attached to the surface;
5. and (3) alternately stacking the carbon fiber attached with the cellulose film obtained in the step (IV) and an acrylonitrile-butadiene-styrene (ABS) thermoplastic resin film, and then performing hot pressing at 230 ℃ and 10MPa for 11min, and performing cold press molding to obtain the carbon fiber reinforced ABS composite material.
Comparative example 4:
1. preparing 200ml of acetone and 200ml of absolute ethyl alcohol into a mixed solution according to the ratio of 1:1, then placing commercial carbon fibers into the solution, standing for 24 hours, washing and drying to obtain the carbon fibers from which sizing agents are removed;
2. and (3) alternately stacking the desized carbon fibers obtained in the step (II) and an acrylonitrile-butadiene-styrene (ABS) thermoplastic resin film, and then carrying out hot pressing for 11min at 230 ℃ and 10MPa, and then carrying out cold press molding to obtain the carbon fiber reinforced ABS composite material.
The carbon fiber-reinforced ABS composite of test example 4 was subjected to an interlayer shear property test and a bending property test as shown in table 6 below.
TABLE 6 interlaminar shear Strength and flexural Strength of carbon fiber reinforced ABS composite
It can be seen from Table 6 that the carbon fiber reinforced ABS composite material of comparative example 4, which was not treated with the modifier, had an interlaminar shear strength (ILSS) of only 16.1MPa and a flexural strength of only 248.7MPa, whereas the carbon fiber reinforced ABS composite material of test example 4, which was loaded with a polymer film, had an interlaminar shear strength (ILSS) of 28.1MPa and a flexural strength of 350.2MPa. Compared with the unmodified carbon fiber reinforced ABS composite material, the modified carbon fiber reinforced ABS composite material has the advantages that the shearing strength is improved by 74.5%, the bending strength is improved by 40.8%, and the improvement is relatively large.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.

Claims (6)

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