A carbon fiber reinforced thermoplastic resin-based composite material and its preparation method and application

Abstract

The present invention belongs to the technical field of composite materials, and in particular to a carbon fiber reinforced thermoplastic resin-based composite material and its preparation method and application. The material preparation steps are as follows: preparing a polyetherketoneketone suspension, using the polyetherketoneketone suspension to prepare carbon fiber reinforced polyetherketoneketone prepregs with carbon fiber contents of 60-80wt%, 40-60wt% and 20-40wt% respectively; mixing polyetherketoneketone powder and nanofiller, and spraying them onto the surface of the obtained carbon fiber reinforced polyetherketoneketone prepreg; laying the obtained carbon fiber reinforced polyetherketoneketone prepregs in the order of carbon fiber content from low to high on a surface layer without carbon fiber; and forming by hot pressing with the aid of infrared radiation heating to obtain the carbon fiber reinforced thermoplastic composite material; the carbon fiber reinforced thermoplastic composite material of the present invention has both anti-low temperature medium leakage, anti-static function and excellent mechanical strength.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite materials, and in particular relates to a carbon fiber reinforced thermoplastic resin-based composite material and a preparation method and application thereof. Background Art

[0002] The development of space launch vehicle tank materials has primarily progressed through aluminum-magnesium alloys, aluminum-copper alloys, and aluminum-lithium alloys, ultimately evolving towards carbon fiber composites. Carbon fiber composites offer significantly higher specific strength and stiffness than metals, and possess excellent fatigue and vibration resistance, as well as excellent molding processability. They are particularly well-suited for large and monolithic structures, reducing the number of parts and joining steps, making them ideal for achieving high-performance and lightweight structures in advanced aerospace equipment. Compared to metal tanks, carbon fiber composites can reduce the weight of liquid oxygen tank structures by approximately 25%. The weight reduction increases with the size of cryogenic medium tanks, further reducing overall launch costs. Therefore, the development of carbon fiber composite tanks has become an inevitable trend.

[0003] Due to the significant difference in thermal expansion coefficient between carbon fiber and the resin matrix, carbon fiber composites experience significant temperature differences when cooled from molding temperature to room temperature, or when used in cryogenic storage tanks such as liquid oxygen (-183°C) and liquid hydrogen (-252°C). This thermal expansion mismatch causes mismatched deformation between the carbon fiber and epoxy resin, leading to high residual stresses in the carbon fiber composite during cryogenic cooling. Coupled with internal mechanical stresses, these stresses can easily cause microcracks in the resin matrix and at the carbon fiber-resin interface. Under continuous or cyclic exposure to low temperatures and stress, these microcracks propagate until they form single-layer transverse cracks and interlaminar cracks, creating leakage paths and leading to tank leakage. Carbon fiber composites inherently offer excellent properties such as light weight and high strength, but when exposed to cryogenic media, leakage failure in carbon fiber composite cryogenic storage tanks can precede structural failure. Therefore, effectively suppressing leakage in carbon fiber composites exposed to cryogenic media is key to their application in cryogenic storage tanks.

[0004] To improve the low-temperature medium leakage resistance of carbon fiber composites, existing technologies generally introduce flexible polymers (such as thermoplastic resins, nano-rubbers, etc.) or dope nanomaterials (such as carbon nanotubes, graphene, silica, etc.) into the resin matrix to improve the toughness of the resin matrix, thereby improving the ability to resist crack propagation and reducing the risk of leakage. For example, articles such as Polymer Testing, 2019, 74: 45-56, Polymer, 2007, 48 (1): 302-10, and patent CN 113861619 A introduce flexible polymers into the resin matrix. The articles Composites Part A: Applied Science and Manufacturing, 2018, 108: 12-22, Composites Part A: Applied Science and Manufacturing, 2018, 108: 12-22, Composites science and technology, 2014, 104: 59-65, as well as patents CN103435975A and CN117887211A introduce nanomaterials into the resin matrix to improve the ability to resist crack propagation and reduce the risk of leakage.

[0005] However, the above methods cannot fundamentally solve the problem of residual stress causing microcracks. The introduction of flexible polymers will increase the thermal expansion coefficient of the epoxy resin matrix. When the ambient temperature of the carbon fiber reinforced resin-based composite material drops from room temperature to ultra-low temperature, the thermal expansion coefficient of the resin matrix is ​​large, which causes the temperature stress of the resin / fiber interface to rise sharply, which in turn easily leads to the initiation of microcracks at the resin / fiber interface, and ultimately may reduce the low-temperature medium leakage resistance of the carbon fiber resin-based composite material. The addition of nanomaterials cannot guarantee the dispersibility of the nanomaterials in the resin matrix, and is prone to agglomeration, resulting in a decrease in the mechanical properties of the carbon fiber composite material. In addition, the surface of the nanomaterials may have no active functional groups, which will result in no covalent bonding between the nanomaterials and the resin matrix, thereby making the interface binding between the nanomaterials and the resin matrix weaker. Summary of the Invention

[0006] In view of the above problems, the present invention adopts high-toughness and high-performance thermoplastic resin to design a carbon fiber reinforced thermoplastic resin-based composite material that is resistant to low-temperature medium leakage, so as to effectively solve the problem of low-temperature medium leakage in carbon fiber composite materials.

[0007] One of the purposes of the present invention is to provide a method for preparing a carbon fiber reinforced thermoplastic resin-based composite material. The method has strong feasibility and is suitable for industrial and large-scale applications, providing new technical support for the preparation of carbon fiber reinforced thermoplastic resin-based composite materials that are resistant to low-temperature medium leakage.

[0008] To achieve the above object, the present invention adopts the following technical solutions:

[0009] A method for preparing a carbon fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0010] (1) Preparing a polyetherketoneketone suspension: mixing polyethylene glycol monooctylphenyl ether, polyethylene glycol, a dispersant, polyetherketoneketone and water to obtain a polyetheretherketone suspension;

[0011] (2) Preparation of carbon fiber reinforced polyetherketoneketone prepreg tapes: using polyetherketoneketone suspension, carbon fiber reinforced polyetherketoneketone prepreg tapes with carbon fiber contents of 60-80wt%, 40-60wt% and 20-40wt% of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg tapes were prepared respectively;

[0012] (3) Preparation of nanofillers: Aminated carbon nanotubes, nickel-coated carbon nanotubes, and MXene nanosheets are mixed and heated to obtain nanofillers;

[0013] (4) Spraying: mixing the polyetherketoneketone and the nanofiller, and spraying the mixture onto the surface of the carbon fiber reinforced polyetherketoneketone prepreg obtained in step (2);

[0014] (5) Preparation of a carbon fiber-free surface layer: polyetherketoneketone and nanofiller are mixed and melt-extruded to obtain a carbon fiber-free surface layer;

[0015] (6) Hot pressing molding: The carbon fiber reinforced polyetherketone ketone prepreg tapes sprayed in step (4) are sequentially laid on the surface layer without carbon fiber in the order of carbon fiber content from low to high; and hot pressing assisted infrared radiation heating molding is performed to obtain the product.

[0016] Furthermore, in step (1), the particle size of the polyetherketoneketone is 5-25 μm, and the polyetheretherketone suspension comprises the following components in percentage by mass: 10-35 wt% polyetherketoneketone, 0.3-1.2 wt% polyethylene glycol monooctylphenyl ether, 0.3-0.9 wt% polyethylene glycol, 0.5-2.5 wt% dispersant, and the balance is water.

[0017] Furthermore, in step (2), the specific preparation method of the carbon fiber reinforced polyetherketoneketone prepreg is as follows: the carbon fiber after being pulled and desizing is impregnated with a polyetherketoneketone suspension, and after heat treatment, the prepreg is obtained by melting, extruding, and calendering;

[0018] When the polyetherketoneketone content in the polyetheretherketone suspension is 10-20 wt%, the obtained carbon fiber content accounts for 60-80 wt% of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg;

[0019] When the polyetherketoneketone content in the polyetheretherketone suspension is 20-25 wt%, the obtained carbon fiber content accounts for 40-60 wt% of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg;

[0020] When the polyetherketoneketone content in the polyetheretherketone suspension is 25-35 wt%, the obtained carbon fiber content accounts for 20-40 wt% of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg;

[0021] The thickness of the carbon fiber reinforced polyetherketoneketone prepreg tape is 0.1-0.2 mm.

[0022] Furthermore, the desizing temperature is 400°C and the time is 0.5-1 min; the traction speed is 0.2~1 m / min; the impregnation time is 10-20 s; the heat treatment temperature is 250-350°C and the time is 20-30 s; the melting temperature is 380-420°C and the time is 10-20 s; the extrusion temperature is 380-420°C; and the calendering temperature is 250-320°C.

[0023] Furthermore, in step (3), the mass ratio of the amino-treated carbon nanotubes, nickel-plated carbon nanotubes and MXene nanosheets is (2-5): (0.5-2): (0.5-1); the heating temperature is 75-85°C and the time is 2h; the nanofiller is plasma treated before spraying; the MXene nanosheet is Ti3C2T X Nanosheets.

[0024] Furthermore, the mass ratio of the polyetherketoneketone powder and the nanofiller in step (4) and step (5) is 100:(3-10); in step (4), the thickness of the carbon fiber reinforced polyetherketoneketone prepreg obtained after spraying is 0.11-0.25 mm;

[0025] The thickness of the carbon fiber reinforced polyetherketoneketone prepreg obtained after spraying is 0.01-0.05 mm thicker than the thickness of the carbon fiber reinforced polyetherketoneketone prepreg before spraying.

[0026] In step (5), the melting temperature is 400° C.; and the thickness of the surface layer free of carbon fibers is 0.1-0.2 mm.

[0027] Furthermore, in step (6), the hot pressing molding conditions are: heating to 300°C at a rate of 2°C / min, maintaining at 0.5 MPa for 10 min; then heating to 350°C at a rate of 1°C / min, maintaining at 1.5 MPa for 10 min; then heating to 400°C at a rate of 1°C / min, maintaining at 2.5 MPa for 20 min; finally cooling to 150°C at a rate of 2°C / min and releasing the pressure.

[0028] A second object of the present invention is to provide a carbon fiber reinforced thermoplastic resin-based composite material having excellent anti-seepage performance, mechanical strength and anti-static function in low-temperature media.

[0029] To achieve the above object, the present invention adopts the following technical solutions:

[0030] A carbon fiber reinforced thermoplastic resin-based composite material is prepared by the above preparation method.

[0031] A third object of the present invention is to provide an application of a carbon fiber reinforced thermoplastic resin-based composite material.

[0032] The application of the above carbon fiber reinforced thermoplastic resin-based composite material in the preparation of high and low temperature boxes.

[0033] Furthermore, the operating temperature range of the high and low temperature box is -260°C to 230°C.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] 1. The present invention provides a carbon fiber reinforced thermoplastic resin-based composite material, which adopts a high-performance resin matrix to be melt-sealed on the inner surface. On the one hand, it can effectively block the leakage of low-temperature media; on the other hand, with the help of the high toughness of the resin, it can significantly inhibit the generation of microcracks, solve the leakage problem of carbon fiber composite materials in low-temperature media, and improve the overall anti-seepage performance of carbon fiber composite materials; the outside adopts a prepreg with a high carbon fiber content, and the outermost high carbon fiber surface layer resin forms an interpenetrating network interface through melt penetration during infrared heating, forming a molecular chain entanglement structure with the innermost layer of matrix resin, increasing interface bonding, which can significantly improve the mechanical strength of the carbon fiber composite material and improve the overall mechanical properties of the box.

[0036] 2. The present invention provides a method for preparing a carbon fiber reinforced thermoplastic resin-based composite material, which is simple and easy to implement and suitable for industrial and large-scale applications.

[0037] 3. The carbon fiber-reinforced thermoplastic resin-based composite material provided by the present invention can be used in the preparation of aerospace propellant tanks, high- and low-temperature tanks, etc. The research and development of this carbon fiber composite material provides strong support for technological innovation and industrial upgrading in related fields.

[0038] 4. After the carbon fiber reinforced thermoplastic resin composite material of the present invention has been subjected to 50 thermal cycles from -196°C to 230°C, the helium mass spectrometry leak detection rate remains at a high level. , and it also has anti-static function (conductivity ≥ 50S / m), which can solve the problem of static electricity accumulation during the transportation of liquid hydrocarbon media. DETAILED DESCRIPTION

[0039] The following describes the embodiments of the present invention through specific examples. Those skilled in the art will readily understand the other advantages and benefits of the present invention from the disclosure herein. The present invention may also be implemented or applied through various other specific embodiments, and the details in this specification may be modified or altered based on different viewpoints and applications without departing from the spirit of the present invention.

[0040] Before further describing the specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below; it should also be understood that the terms used in the examples of the present invention are for describing specific embodiments rather than for limiting the scope of protection of the present invention.

[0041] When numerical ranges are given in the examples, it should be understood that, unless otherwise specified herein, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention belongs.

[0042] Reagents used in the embodiments of the present invention:

[0043] Polyetherketoneketone: purchased from Suzhou Paike Technology Co., Ltd., model 8020, particle size 5-25 μm;

[0044] Carbon fiber: purchased from Zhongfu Shenying Carbon Fiber Co., Ltd., model SYT49S;

[0045] Aminated carbon nanotubes: purchased from Chengdu Organic Chemistry Co., Ltd., Chinese Academy of Sciences, product number TNMN2;

[0046] Nickel-coated carbon nanotubes: purchased from Chengdu Organic Chemistry Co., Ltd., Chinese Academy of Sciences, product number TNNiM8;

[0047] Ti3C2T X Nanosheets: purchased from Foshan Xinxin Technology Co., Ltd., model is multilayer Ti3C2T X .

[0048] Dispersant ZXSPERSE®112: purchased from Dalian Jersey International Trade Co., Ltd.

[0049] Example 1

[0050] A method for preparing a carbon fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0051] (1) Preparation of polyetherketoneketone suspension: The polyetheretherketone suspension includes the following components in percentage by mass: 10-32 wt% polyetherketoneketone, 0.8 wt% polyethylene glycol monooctylphenyl ether, 0.5 wt% polyethylene glycol, 2 wt% dispersant ZXSPERSE®112, and the balance is water.

[0052] Premix polyethylene glycol monooctylphenyl ether, polyethylene glycol, ZXSPERSE®112, one-quarter the mass of polyetherketoneketone and water, stir at 5000 rpm for 30 min, then add the remaining mass of polyetherketoneketone, increase the stirring speed to 10000 rpm, and continue stirring for 3 h to obtain a polyetheretherketone suspension, which is kept stirring at 5000 rpm.

[0053] (2) Preparation of carbon fiber reinforced polyetherketone ketone prepreg:

[0054] By controlling the content of polyetherketoneketone in the polyetherketoneketone suspension, polyetherketoneketone prepreg tapes with different carbon fiber contents were prepared.

[0055] (2-1) Preparation of carbon fiber reinforced polyetherketoneketone prepreg A: The carbon fiber is treated at 400°C for 0.5 min to remove the sizing; the desized carbon fiber is pulled at a speed of 0.5 m / min and impregnated through a polyetherketoneketone suspension (the content of polyetherketoneketone in the corresponding polyetherketoneketone suspension in step (1) is 32 wt%) for 15 s; then heat-treated at 300°C for 20 s to dry; then treated at 400°C for 10 s to melt the polyetherketoneketone, and extruded at 400°C; then calendered at 300°C by a double-roll calender; and finally rolled up.

[0056] The mass of the carbon fibers in the obtained carbon fiber reinforced polyetherketoneketone prepreg tape A is 25 wt % of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg tape; the thickness of the obtained carbon fiber reinforced polyetherketoneketone prepreg tape A is 0.18 mm;

[0057] (2-2) Preparation of carbon fiber reinforced polyetherketoneketone prepreg B: The carbon fiber is treated at 400°C for 0.5 min to remove the sizing; the desized carbon fiber is pulled at a speed of 0.5 m / min and impregnated through a polyetherketoneketone suspension (the content of polyetherketoneketone in the corresponding polyetherketoneketone suspension in step (1) is 22 wt%) for 15 s; the remaining heat treatment, melting, extrusion, and calendaring steps are the same as those in (2-1);

[0058] The mass of the carbon fibers in the obtained carbon fiber reinforced polyetherketoneketone prepreg tape B is 50 wt % of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg tape; the thickness of the obtained carbon fiber reinforced polyetherketoneketone prepreg tape A is 0.15 mm;

[0059] (2-3) Preparation of carbon fiber reinforced polyetherketoneketone prepreg C: The carbon fiber is treated at 400°C for 0.5 min to remove the sizing; the desized carbon fiber is pulled at a speed of 0.5 m / min and impregnated through a polyetherketoneketone suspension (the content of polyetherketoneketone in the corresponding polyetherketoneketone suspension in step (1) is 10 wt%) for 15 s; the remaining heat treatment, melting, extrusion, and calendaring steps are the same as those in (2-1);

[0060] The mass of the carbon fibers in the obtained carbon fiber reinforced polyetherketoneketone prepreg tape C is 75 wt % of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg tape; the thickness of the obtained carbon fiber reinforced polyetherketoneketone prepreg tape A is 0.12 mm;

[0061] (3) Preparation of nanofillers: Aminated carbon nanotubes, nickel-plated carbon nanotubes and MXene (Ti3C2T X ) nanosheets were plasma treated with oxygen plasma at 300W power for 5 minutes to improve the interfacial compatibility with polyetherketoneketone; the three were heated to 80°C and mixed by mechanical vibration for 2 hours to obtain nanofillers; among them, amino-treated carbon nanotubes, nickel-plated carbon nanotubes and MXene (Ti3C2T X ) The mass ratio of nanosheets is 3:1:1;

[0062] (4) Spraying: Polyetherketoneketone powder and nanofiller were mixed in a mass ratio of 100:8 and sprayed onto the surface of carbon fiber reinforced polyetherketoneketone prepreg tape A, carbon fiber reinforced polyetherketoneketone prepreg tape B, and carbon fiber reinforced polyetherketoneketone prepreg tape C, respectively. After spraying, the thickness of the obtained carbon fiber reinforced polyetherketoneketone prepreg tape increased by 0.02 mm.

[0063] (5) Preparation of surface layer D:

[0064] Preparation of a surface layer D without carbon fiber: melt-extrude the raw material used for spraying in step (4) at 400°C, and use a double roller to control the thickness and surface flatness to prepare a surface layer D with a thickness of 0.15 mm;

[0065] (6) Hot pressing:

[0066] The carbon fiber reinforced polyetherketone ketone prepregs sprayed in step (4) are sequentially spread on the surface of the surface layer D according to the carbon fiber content from low to high;

[0067] The autoclave process is assisted by medium- and short-wave infrared radiation heating molding. The molding conditions of the autoclave process are: heating to 300°C at a rate of 5°C / min and maintaining at 0.5MPa for 10 minutes; then heating to 350°C at a rate of 2°C / min and maintaining at 1.5MPa for 10 minutes; then heating to 400°C at a rate of 2°C / min and maintaining at 2.5MPa for 20 minutes; finally cooling to 150°C at a rate of 2°C / min and releasing the pressure to obtain a carbon fiber reinforced thermoplastic resin-based composite material.

[0068] The specific laying method of the carbon fiber reinforced thermoplastic resin-based composite material is as follows: the innermost layer is the surface layer D with 0% carbon fiber content, the second layer is the carbon fiber reinforced polyetherketoneketone prepreg tape A, the third layer is the carbon fiber reinforced polyetherketoneketone prepreg tape B, and the outermost layer is the carbon fiber reinforced polyetherketoneketone prepreg tape C.

[0069] Example 2

[0070] A method for preparing a carbon fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0071] (1) Preparation of polyetherketoneketone suspension: The polyetheretherketone suspension includes the following components in percentage by mass: 12-30 wt% polyetherketoneketone, 0.5 wt% polyethylene glycol monooctylphenyl ether, 0.3 wt% polyethylene glycol, 0.8 wt% dispersant ZXSPERSE®112, and the balance is water.

[0072] Premix polyethylene glycol monooctylphenyl ether, polyethylene glycol, ZXSPERSE®112, one-quarter the mass of polyetherketoneketone and water, stir at 5000 rpm for 30 min, then add the remaining mass of polyetherketoneketone, increase the stirring speed to 10000 rpm, and continue stirring for 3 h to obtain a polyetheretherketone suspension, which is kept stirring at 3000 rpm.

[0073] (2) Preparation of carbon fiber reinforced polyetherketone ketone prepreg:

[0074] By controlling the content of polyetherketoneketone in the polyetherketoneketone suspension, polyetherketoneketone prepreg tapes with different carbon fiber contents were prepared.

[0075] (2-1) Preparation of carbon fiber reinforced polyetherketoneketone prepreg tape A:

[0076] The carbon fibers were treated at 400°C for 0.5 min to remove the sizing; the desized carbon fibers were pulled at a speed of 0.2 m / min and impregnated with a polyetherketoneketone suspension (the content of polyetherketoneketone in the corresponding polyetherketoneketone suspension in step (1) was 30 wt%) for 15 s; then heat-treated at 310°C for 20 s to dry; then treated at 410°C for 10 s to melt the polyetherketoneketone, and extruded at 420°C; then calendered at 300°C by a double-roll calender; and finally rolled up.

[0077] The mass of the carbon fibers in the obtained carbon fiber reinforced polyetherketoneketone prepreg tape A is 26 wt % of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg tape; the thickness of the obtained carbon fiber reinforced polyetherketoneketone prepreg tape A is 0.17 mm;

[0078] (2-2) Preparation of carbon fiber reinforced polyetherketoneketone prepreg tape B:

[0079] The carbon fibers were treated at 400°C for 0.5 min to remove the sizing; the desized carbon fibers were pulled at a speed of 0.2 m / min and impregnated with a polyetherketoneketone suspension (the content of polyetherketoneketone in the corresponding polyetherketoneketone suspension in step (1) was 20 wt%) for 15 s; the remaining heat treatment, melting, extrusion, and calendering steps were the same as those in (2-1);

[0080] The mass of the carbon fibers in the obtained carbon fiber reinforced polyetherketoneketone prepreg tape B is 52 wt % of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg tape; the thickness of the obtained carbon fiber reinforced polyetherketoneketone prepreg tape A is 0.15 mm;

[0081] (2-3) Preparation of carbon fiber reinforced polyetherketoneketone prepreg tape C:

[0082] The carbon fiber was treated at 400°C for 0.5 min to desize; the desized carbon fiber was pulled at a speed of 0.2 m / min and impregnated with a polyetherketoneketone suspension (the content of polyetherketoneketone in the corresponding polyetherketoneketone suspension in step (1) was 12 wt%) for 15 s; the remaining heat treatment, melting, extrusion, and calendering steps were the same as (2-1).

[0083] The mass of the carbon fibers in the obtained carbon fiber reinforced polyetherketoneketone prepreg tape C is 72 wt % of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg tape; the thickness of the obtained carbon fiber reinforced polyetherketoneketone prepreg tape A is 0.12 mm;

[0084] (3) Preparation of nanofillers: Aminated carbon nanotubes, nickel-plated carbon nanotubes and MXene (Ti3C2T X) nanosheets were plasma treated with oxygen plasma at 300W power for 5 minutes to improve the interfacial compatibility with polyetherketoneketone; the three were heated to 80°C and mixed by mechanical vibration for 2 hours to obtain nanofillers; among them, amino-treated carbon nanotubes, nickel-plated carbon nanotubes and MXene (Ti3C2T X ) The mass ratio of nanosheets is 4:2:1;

[0085] (4) Spraying: PEEK powder and nanofiller were mixed in a mass ratio of 100:5 and sprayed onto the surface of carbon fiber reinforced PEEK prepreg tape A, carbon fiber reinforced PEEK prepreg tape B, and carbon fiber reinforced PEEK prepreg tape C, respectively. The thickness of the obtained carbon fiber reinforced PEEK prepreg tape increased by 0.03 mm after spraying.

[0086] (5) Preparation of surface layer D: The raw materials used for spraying in step (4) were melt-extruded at 400°C, and the thickness and surface flatness were controlled by a double roller to prepare a surface layer D with a thickness of 0.15 mm;

[0087] (6) Hot pressing:

[0088] The carbon fiber reinforced polyetherketone ketone prepregs sprayed in step (4) are sequentially spread on the surface of the surface layer D according to the carbon fiber content from low to high;

[0089] The autoclave process is assisted by medium- and short-wave infrared radiation heating molding. The molding conditions of the autoclave process are: heating to 300°C at a rate of 5°C / min and maintaining at 0.5MPa for 10 minutes; then heating to 350°C at a rate of 2°C / min and maintaining at 1.5MPa for 10 minutes; then heating to 400°C at a rate of 2°C / min and maintaining at 2.5MPa for 20 minutes; finally cooling to 150°C at a rate of 2°C / min and releasing the pressure to obtain a carbon fiber reinforced thermoplastic resin-based composite material.

[0090] The specific laying method of the carbon fiber reinforced thermoplastic resin-based composite material is as follows: the innermost layer is the surface layer D with 0% carbon fiber content, the second layer is the carbon fiber reinforced polyetherketoneketone prepreg tape A, the third layer is the carbon fiber reinforced polyetherketoneketone prepreg tape B, and the outermost layer is the carbon fiber reinforced polyetherketoneketone prepreg tape C.

[0091] Example 3

[0092] A method for preparing a carbon fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0093] (1) Preparation of polyetherketoneketone suspension: The polyetheretherketone suspension includes the following components in percentage by mass: 13-35 wt% polyetherketoneketone, 1.3 wt% polyethylene glycol monooctylphenyl ether, 0.8 wt% polyethylene glycol, 2.3 wt% dispersant ZXSPERSE®112, and the balance is water.

[0094] Premix polyethylene glycol monooctylphenyl ether, polyethylene glycol, ZXSPERSE®112, one-quarter the mass of polyetherketoneketone and water, stir at 5000 rpm for 30 min, then add the remaining mass of polyetherketoneketone, increase the stirring speed to 10000 rpm, and continue stirring for 3 h to obtain a polyetheretherketone suspension, which is kept stirring at 5000 rpm.

[0095] (2) Preparation of carbon fiber reinforced polyetherketone ketone prepreg:

[0096] By controlling the content of polyetherketoneketone ketone particles in the polyetherketoneketone ketone suspension, polyetherketoneketone ketone prepregs with different carbon fiber contents were prepared.

[0097] (2-1) Preparation of carbon fiber reinforced polyetherketoneketone prepreg tape A:

[0098] The carbon fibers were treated at 400°C for 0.5 min to remove the sizing; the desizing carbon fibers were pulled at a speed of 1 m / min and impregnated with a polyetherketoneketone suspension (the content of polyetherketoneketone in the corresponding polyetherketoneketone suspension in step (1) was 35 wt%) for 15 s; the fibers were heat treated at 300°C for 20 s and dried; the fibers were then treated at 400°C for 10 s to melt the polyetherketoneketone, and extruded at 400°C; the fibers were then calendered at 300°C by a double-roll calender; and finally rolled up to obtain the obtained carbon fiber reinforced polyetherketoneketone prepreg A, wherein the mass of the carbon fibers in the obtained carbon fiber reinforced polyetherketoneketone prepreg was 22 wt% of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg; and the thickness of the obtained carbon fiber reinforced polyetherketoneketone prepreg A was 0.18 mm.

[0099] (2-2) Preparation of carbon fiber reinforced polyetherketoneketone prepreg B: The carbon fiber is treated at 400°C for 0.5 min to remove the sizing; the desized carbon fiber is pulled at a speed of 1 m / min and impregnated through a polyetherketoneketone suspension (the content of polyetherketoneketone in the corresponding polyetherketoneketone suspension in step (1) is 25 wt%) for 15 s; the remaining heat treatment, melting, extrusion, and calendaring steps are the same as those in (2-1);

[0100] The mass of the carbon fibers in the obtained carbon fiber reinforced polyetherketoneketone prepreg tape B is 48 wt % of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg tape; the thickness of the obtained carbon fiber reinforced polyetherketoneketone prepreg tape A is 0.16 mm;

[0101] (2-3) Preparation of carbon fiber reinforced polyetherketoneketone prepreg C The carbon fiber was treated at 400°C for 0.5 min to remove the sizing; the desized carbon fiber was pulled at a speed of 1 m / min and impregnated through a polyetherketoneketone suspension (the content of polyetherketoneketone in the corresponding polyetherketoneketone suspension in step (1) was 13 wt%) for 15 s; the remaining heat treatment, melting, extrusion, and calendering steps were the same as in (2-1);

[0102] The mass of the carbon fibers in the obtained carbon fiber reinforced polyetherketoneketone prepreg tape C is 71 wt % of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg tape; the thickness of the obtained carbon fiber reinforced polyetherketoneketone prepreg tape A is 0.12 mm;

[0103] (3) Preparation of nanofillers: Aminated carbon nanotubes, nickel-plated carbon nanotubes and MXene (Ti3C2T X ) nanosheets were plasma treated with oxygen plasma at 300W power for 5 minutes to improve the interfacial compatibility with polyetherketoneketone; the three were heated to 80°C and mixed by mechanical vibration for 2 hours to obtain nanofillers; among them, amino-treated carbon nanotubes, nickel-plated carbon nanotubes and MXene (Ti3C2T X ) The mass ratio of nanosheets is 2:2:1;

[0104] (4) Spraying: PEEK powder and nanofiller were mixed in a mass ratio of 100:3 and sprayed onto the surface of carbon fiber reinforced PEEK prepreg tape A, carbon fiber reinforced PEEK prepreg tape B, and carbon fiber reinforced PEEK prepreg tape C, respectively. The thickness of the obtained carbon fiber reinforced PEEK prepreg tape increased by 0.02 mm after spraying.

[0105] (5) Preparation of surface layer D: The raw materials used for spraying in step (4) were melt-extruded at 400°C, and the thickness and surface flatness were controlled by a double roller to prepare a surface layer D with a thickness of 0.15 mm;

[0106] (6) Hot pressing:

[0107] The carbon fiber reinforced polyetherketone ketone prepregs sprayed in step (4) are sequentially spread on the surface of the surface layer D according to the carbon fiber content from low to high;

[0108] The autoclave process is assisted by medium- and short-wave infrared radiation heating molding. The molding conditions of the autoclave process are: heating to 300°C at a rate of 5°C / min and maintaining at 0.5MPa for 10 minutes; then heating to 350°C at a rate of 2°C / min and maintaining at 1.5MPa for 10 minutes; then heating to 400°C at a rate of 2°C / min and maintaining at 2.5MPa for 20 minutes; finally cooling to 150°C at a rate of 2°C / min and releasing the pressure to obtain a carbon fiber reinforced thermoplastic resin-based composite material.

[0109] The specific laying method of the carbon fiber reinforced thermoplastic resin-based composite material is as follows: the innermost layer is the surface layer D with 0% carbon fiber content, the second layer is the carbon fiber reinforced polyetherketoneketone prepreg tape A, the third layer is the carbon fiber reinforced polyetherketoneketone prepreg tape B, and the outermost layer is the carbon fiber reinforced polyetherketoneketone prepreg tape C.

[0110] Comparative Example 1

[0111] This comparative example 1 is basically the same as Example 1, except that the carbon fiber reinforced polyetherketoneketone prepreg tape A and the carbon fiber reinforced polyetherketoneketone prepreg tape B in step (2) are omitted, and the rest are consistent with Example 1.

[0112] The specific laying method of the carbon fiber reinforced thermoplastic resin matrix composite material is as follows: the innermost layer is a surface layer D with 0% carbon fiber content, and the outermost layer is a carbon fiber reinforced polyetherketoneketone prepreg tape C.

[0113] Comparative Example 2

[0114] Comparative Example 2 is basically the same as Example 1, except that the carbon fiber reinforced polyetherketoneketone prepreg tape B and the carbon fiber reinforced polyetherketoneketone prepreg tape C in step (2) are omitted, and the rest are consistent with Example 1.

[0115] The specific laying method of the carbon fiber reinforced thermoplastic resin-based composite material is as follows: the innermost layer is the surface layer D with 0% carbon fiber content, the second layer is the carbon fiber reinforced polyetherketoneketone prepreg tape A, the third layer is the carbon fiber reinforced polyetherketoneketone prepreg tape A, and the outermost layer is the carbon fiber reinforced polyetherketoneketone prepreg tape A.

[0116] Comparative Example 3

[0117] Comparative Example 3 is basically the same as Example 1, except that the carbon fiber reinforced polyetherketoneketone prepreg tape A and the carbon fiber reinforced polyetherketoneketone prepreg tape B in step (2) are omitted, and the rest are consistent with Example 1.

[0118] The specific laying method of the carbon fiber reinforced thermoplastic resin-based composite material is as follows: the innermost layer is a surface layer with 0% carbon fiber content, the second layer is a carbon fiber reinforced polyetherketoneketone prepreg tape C, the third layer is a carbon fiber reinforced polyetherketoneketone prepreg tape C, and the outermost layer is a carbon fiber reinforced polyetherketoneketone prepreg tape C.

[0119] Comparative Example 4

[0120] Comparative Example 4 is basically the same as Example 1, except that the thicknesses of the carbon fiber reinforced polyetherketoneketone prepreg tape A, the carbon fiber reinforced polyetherketoneketone prepreg tape B, and the carbon fiber reinforced polyetherketoneketone prepreg tape C in step (2) are different.

[0121] In this comparative example, the thicknesses of carbon fiber reinforced polyetherketoneketone prepreg tape A, carbon fiber reinforced polyetherketoneketone prepreg tape B, and carbon fiber reinforced polyetherketoneketone prepreg tape C are 0.25 mm, 0.23 mm, and 0.22 mm, respectively;

[0122] Comparative Example 5

[0123] Comparative Example 5 is basically the same as Example 1, except that the amino-treated carbon nanotubes and nickel-plated carbon nanotubes in the nanofiller in step (3) are replaced by carbon nanotubes, and the rest are consistent with Example 1.

[0124] Comparative Example 6

[0125] Comparative Example 6 is basically the same as Example 1, except that the amino-treated carbon nanotubes in the nanofiller in step (3) are replaced with nickel-plated carbon nanotubes; the rest are consistent with Example 1.

[0126] Comparative Example 7

[0127] Comparative Example 7 is basically the same as Example 1, except that the nickel-plated carbon nanotubes in the nanofiller in step (3) are replaced by amino-treated carbon nanotubes; the rest are consistent with Example 1.

[0128] Comparative Example 8

[0129] This comparative example 8 is basically the same as Example 1, except that the infrared radiation in the autoclave process-assisted infrared radiation heating molding is omitted, and the rest is consistent with Example 1.

[0130] Test example

[0131] The carbon fiber reinforced polyetherketoneketone composite materials obtained in Examples 1-3 of the present invention and Comparative Examples 1-8 were cycled 50 times at -196°C to 230°C. The bending properties of the materials were tested according to ASTM D7264, the interlaminar shear strength was tested according to ASTM D2344, the helium leakage rate was tested according to GB / T 1038.1-2022, and the conductivity was tested by a broadband dielectric impedance spectrometer. The experimental results are recorded in Tables 1 and 2, as shown below.

[0132] Table 1

[0133]

[0134] Table 2

[0135]

[0136] The comprehensive performance of the carbon fiber reinforced thermoplastic resin-based composite materials obtained in Examples 1-3 of the present invention is generally better than that of Comparative Examples 1-8, especially the composite material of Example 1. After enduring 50 thermal cycles from -196°C to 230°C, the helium mass spectrometry leak detection rate still remains at a high level. , indicating that the material has fewer internal defects; and its surface layer has anti-static function (conductivity ≥ 50S / m), which can solve the problem of static electricity accumulation during the transportation of liquid hydrocarbon media.

[0137] The above embodiments are only preferred embodiments of the present invention and cannot be used to limit the scope of protection of the present invention. Any non-substantial changes and replacements made by technicians in this field on the basis of the present invention fall within the scope of protection required by the present invention.

Claims

1. A method for preparing a carbon fiber reinforced thermoplastic resin-based composite material, characterized in that: The steps include: (1) Preparing a polyetherketoneketone suspension: mixing polyethylene glycol monooctylphenyl ether, polyethylene glycol, a dispersant, polyetherketoneketone and water to obtain a polyetheretherketone suspension; (2) Preparation of carbon fiber reinforced polyetherketoneketone prepreg tapes: using polyetherketoneketone suspension, carbon fiber reinforced polyetherketoneketone prepreg tapes with carbon fiber contents of 60-80wt%, 40-60wt% and 20-40wt% of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg tapes were prepared respectively; (3) Preparation of nanofillers: Mix and heat amino-treated carbon nanotubes, nickel-plated carbon nanotubes, and MXene nanosheets to obtain nanofillers; (4) Spraying: mixing the polyetherketoneketone and the nanofiller, and spraying the mixture onto the surface of the carbon fiber reinforced polyetherketoneketone prepreg obtained in step (2); (5) Preparation of a carbon fiber-free surface layer: polyetherketoneketone and nanofiller are mixed and melt-extruded to obtain a carbon fiber-free surface layer; (6) Hot pressing molding: The carbon fiber reinforced polyetherketone ketone prepreg tapes sprayed in step (4) are sequentially laid on the surface layer without carbon fiber in the order of carbon fiber content from low to high; and hot pressing assisted infrared radiation heating molding is performed to obtain the product.

2. The method for preparing a carbon fiber reinforced thermoplastic resin-based composite material according to claim 1, characterized in that: In step (1), the particle size of the polyetherketoneketone is 5-25 μm, and the polyetheretherketone suspension comprises the following components in percentage by mass: 10-35 wt% of polyetherketoneketone, 0.3-1.2 wt% of polyethylene glycol monooctylphenyl ether, 0.3-0.9 wt% of polyethylene glycol, 0.5-2.5 wt% of a dispersant, and the balance is water.

3. The method for preparing a carbon fiber reinforced thermoplastic resin-based composite material according to claim 2, characterized in that: In step (2), the specific preparation method of the carbon fiber reinforced polyetherketoneketone prepreg is as follows: the carbon fiber after being pulled and desizing is impregnated with a polyetherketoneketone suspension, and after heat treatment, the prepreg is obtained by melting, extruding, and calendering; When the polyetherketoneketone content in the polyetheretherketone suspension is 10-20 wt%, the obtained carbon fiber content accounts for 60-80 wt% of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg; When the polyetherketoneketone content in the polyetheretherketone suspension is 20-25 wt%, the obtained carbon fiber content accounts for 40-60 wt% of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg; When the polyetherketoneketone content in the polyetheretherketone suspension is 25-35 wt%, the obtained carbon fiber content accounts for 20-40 wt% of the total mass of the carbon fiber reinforced polyetherketoneketone prepreg; The thickness of the carbon fiber reinforced polyetherketoneketone prepreg tape is 0.1-0.2 mm.

4. The method for preparing a carbon fiber reinforced thermoplastic resin-based composite material according to claim 3, characterized in that: The desizing temperature is 400°C and the time is 0.5-1 min; the pulling speed is 0.2~1 m / min; the impregnation time is 10-20 s; the heat treatment temperature is 250-350°C and the time is 20-30 s; the melting temperature is 380-420°C and the time is 10-20 s; the extrusion temperature is 380-420°C; and the calendering temperature is 250-320°C.

5. The method for preparing a carbon fiber reinforced thermoplastic resin-based composite material according to claim 1, characterized in that: In step (3), the mass ratio of the amino-treated carbon nanotubes, nickel-plated carbon nanotubes and MXene nanosheets is (2-5): (0.5-2): (0.5-1); the heating temperature is 75-85°C and the heating time is 2 hours; the nanofiller is plasma treated before spraying; the MXene nanosheets are Ti3C2T X Nanosheets.

6. The method for preparing a carbon fiber reinforced thermoplastic resin-based composite material according to claim 1, characterized in that: The mass ratio of the polyetherketoneketone powder to the nanofiller in step (4) and step (5) is 100:(3-10); in step (4), the thickness of the carbon fiber reinforced polyetherketoneketone prepreg obtained after spraying is 0.11-0.25 mm; In step (5), the melting temperature is 400° C.; and the thickness of the surface layer free of carbon fibers is 0.1-0.2 mm.

7. The method for preparing a carbon fiber reinforced thermoplastic resin-based composite material according to claim 1, characterized in that: In step (6), the hot pressing molding conditions are as follows: heating to 300°C at a rate of 5°C / min and maintaining at 0.5 MPa for 10 min; then heating to 350°C at a rate of 2°C / min and maintaining at 1.5 MPa for 10 min; then heating to 400°C at a rate of 2°C / min and maintaining at 2.5 MPa for 20 min; finally cooling to 150°C at a rate of 2°C / min and releasing the pressure.

8. A carbon fiber reinforced thermoplastic resin matrix composite material, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 7.

9. Use of the carbon fiber reinforced thermoplastic resin-based composite material according to claim 8 in the preparation of high and low temperature boxes.

10. The use according to claim 9, characterized in that The operating temperature range of the high and low temperature box is -260℃~230℃.

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