A high-performance carbon fiber composite material and its preparation method and application

Abstract

The present invention belongs to the technical field of polymer materials, and specifically relates to a high-performance carbon fiber composite material, a preparation method thereof, and an application thereof. The preparation steps of the high-performance carbon fiber composite material are as follows: an ethanol solution of AEAPTMS, an ethanol solution of PFDTES, and an ethanol solution of DOPO are sequentially added step by step to a MXene dispersion to react to obtain a multi-modified MXene; the multi-modified MXene ethanol dispersion is added to ethanol to obtain a multi-modified MXene, and the dispersion is mixed with a modified epoxy resin and a curing agent to obtain a MXene / epoxy resin solution; after removing the sizing agent on the surface of the carbon fiber, the carbon fiber is immersed in a multi-modified MXene ethanol dispersion, dried, and prepared into a carbon fiber prepreg with the MXene / epoxy resin solution; after heating and curing under the coupling of a magnetic field and an electric field, the obtained material is obtained. The material obtained by the present invention has excellent liquid oxygen compatibility, anti-leakage ability and mechanical properties.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and in particular relates to a high-performance carbon fiber 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 larger the cryogenic medium tank structure, the more significant the weight reduction, and overall launch costs are reduced. Therefore, the development of carbon fiber composite tanks has become an inevitable trend.

[0003] While carbon fiber composites exhibit some antioxidant properties, their key thermal properties, such as ignition point, flash point, and thermal decomposition temperature, are lower than those of metals. When subjected to high-energy transient impacts, carbon fiber composites can experience rapid localized heating, posing a fire hazard and potentially even explosion risks. Therefore, improving the compatibility of carbon fiber composites with liquid oxygen is a key issue that needs to be addressed. Furthermore, 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, and when used in cryogenic tanks such as liquid oxygen (-183°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 the continuous or cyclic effects of low temperature and stress, these microcracks propagate until they form single-layer transverse cracks and interlaminar cracks, creating leakage paths and causing tank leaks. Under the action of low-temperature media, leakage failure of carbon fiber composite cryogenic storage tanks will occur before structural bearing failure.

[0004] Therefore, how to effectively improve the liquid oxygen compatibility of carbon fiber composite materials and effectively suppress their leakage in cryogenic media is the key to the application of carbon fiber composite materials in cryogenic medium storage tanks. Summary of the Invention

[0005] To address the shortcomings of the existing technology, the present invention introduces multi-component modified MXene, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and nano-boron nitride into the resin matrix of the carbon fiber composite material. By coordinating the components, the present invention solves the problems of compatibility between the carbon fiber composite material and liquid oxygen, leakage in low-temperature media, and high mechanical properties, thereby realizing the application of the carbon fiber composite material in liquid oxygen storage tanks.

[0006] One of the objectives of the present invention is to provide a method for preparing a high-performance carbon fiber composite material. The method is easy to operate, highly feasible, and conducive to industrial production.

[0007] By introducing multi-modified MXene into DOPO and nano-boron nitride modified epoxy resin, and then preparing a composite material with carbon fiber surface treated with multi-modified MXene, the synergistic effect of multi-modified MXene, DOPO and nano-boron nitride effectively improves the liquid oxygen compatibility and resistance to low-temperature medium leakage of the carbon fiber composite material, while significantly improving the mechanical properties of the carbon fiber composite material.

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

[0009] A method for preparing a high-performance carbon fiber composite material comprises the following steps:

[0010] (1) Under a nitrogen atmosphere, an ethanol solution of 3-aminopropyltriethoxysilane, an ethanol solution of perfluorodecyltriethoxysilane, and an ethanol solution of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are sequentially added dropwise to the MXene dispersion, and the reaction is continued. After the reaction, the mixture is centrifuged and washed to obtain a multi-modified MXene.

[0011] (2) dispersing the multi-modified MXene in anhydrous ethanol to obtain a multi-modified MXene ethanol dispersion;

[0012] (3) The multi-modified MXene ethanol dispersion, modified epoxy resin, and curing agent are uniformly mixed to obtain a MXene / epoxy resin solution;

[0013] (4) First remove the sizing agent on the surface of the carbon fiber, then immerse it in the multi-modified MXene ethanol dispersion, and then dry it for use; mix the treated carbon fiber with the MXene / epoxy resin solution to obtain a carbon fiber prepreg;

[0014] (5) Under the coupling induction of magnetic field and electric field, the carbon fiber prepreg is heated and cured to obtain a carbon fiber composite material.

[0015] Furthermore, in step (1), the mass ratio of the MXene dispersion, the ethanol solution of 3-aminopropyltriethoxysilane, the ethanol solution of perfluorodecyltriethoxysilane and the ethanol solution of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is (17-19): (2-3): (2-3): (2-3);

[0016] In step (3), the ratio of the multi-modified MXene ethanol dispersion, the modified epoxy resin, and the curing agent is (5-15):100:50; the curing agent is 4,4'-diaminodiphenyl sulfone.

[0017] Furthermore, in step (3), the preparation method of the modified epoxy resin is: mixing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, nano boron nitride, and epoxy resin to obtain the modified epoxy resin; the mass ratio of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, nano boron nitride, and epoxy resin is (2-3.5): (0.3-0.8):100.

[0018] Furthermore, in step (5), the direction of the magnetic field is at an angle of 45° to the direction of the carbon fiber, and the direction of the electric field is at an angle of 45° to the carbon fiber; the intensity of the magnetic field is 1-3 T; the current density of the electric field is 10 KV / m;

[0019] The specific steps of curing are: starting from 30°C and curing at a heating rate of 1.5°C / min, curing at this temperature for 2 hours when reaching 130°C, continuing to heat up to 160°C and curing at this temperature for 2 hours, and finally continuing to heat up to 180°C and curing at this temperature for 2 hours; at the beginning of curing, only the electric field is applied, and when the temperature rises to 75°C, the magnetic field and electric field are applied simultaneously.

[0020] The present invention adopts magnetic field and electric field coupling induction. When the direction of the electric field is at a 45° angle to the carbon fiber, the carbon fiber is acted upon by the dielectrophoretic force, which can promote the orientation of the carbon fiber and make the fiber orientation efficiency better. At the same time, the charge density gradient on the fiber surface is distributed symmetrically along the axis, reducing the stress concentration caused by interface polarization. When the viscosity of the epoxy resin is reduced to 500cP, the movement resistance of MXene is reduced. At this time, a pulsed magnetic field is applied, and the magnetizing force is greater than the resistance, which can achieve effective directional migration of MXene. Electric field-magnetic field coupling can construct structures across scales. Macroscopically, the electric field induces the orientation of carbon fibers to a certain extent. At the mesoscopic level, the magnetic field can reduce MXene agglomeration and drive MXene orientation. The electric field and magnetic field are applied separately at different stages of curing for precise control to synergistically improve the comprehensive performance of carbon fiber composites.

[0021] Furthermore, in step (1), the time for dripping the ethanol solution of 3-aminopropyltriethoxysilane is ≤2h; the time for dripping the ethanol solution of perfluorodecyltriethoxysilane is ≤2h; the time for dripping the ethanol solution of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is ≤2h; and the reaction time is 6-10h;

[0022] The MXene dispersion is prepared by adding the MXene aqueous dispersion to anhydrous ethanol, and then adding acetic acid to adjust the pH to 3.0-4.0.

[0023] Furthermore, the ratio of anhydrous ethanol to MXene aqueous dispersion is 8g:1mL; the concentration of the MXene aqueous dispersion is 3-8mg / mL; the MXene aqueous dispersion is Ti3C2T x MXene aqueous dispersion or T3N2T x MXene aqueous dispersion.

[0024] Furthermore, in step (1), the ethanol solution of 3-aminopropyltriethoxysilane is obtained by mixing 3-aminopropyltriethoxysilane and anhydrous ethanol in a mass ratio of (1-2):20; the ethanol solution of perfluorodecyltriethoxysilane is obtained by mixing perfluorodecyltriethoxysilane and anhydrous ethanol in a mass ratio of (2-3):20; the ethanol solution of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is obtained by mixing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and anhydrous ethanol in a mass ratio of (1-2):20;

[0025] In step (2), the mass ratio of the multi-modified MXene to anhydrous ethanol is (0.001-0.3):1.

[0026] Furthermore, the multi-modified MXene ethanol dispersion in step (3) is obtained by mixing the multi-modified MXene and anhydrous ethanol in a mass ratio of (0.05-0.3):1; and the multi-modified MXene ethanol dispersion in step (4) is obtained by mixing the multi-modified MXene and anhydrous ethanol in a mass ratio of (0.001-0.01):1.

[0027] Furthermore, in step (4), the treatment temperature for removing the sizing agent on the surface of the carbon fiber is 300-400°C, and the time is 0.5-5 min; the mass ratio of the treated carbon fiber to the MXene / epoxy resin solution is (8-10): (3-5).

[0028] A second object of the present invention is to provide a high-performance carbon fiber composite material.

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

[0030] The high-performance carbon fiber composite material is prepared by the above-mentioned preparation method.

[0031] A third object of the present invention is to provide an application of high-performance carbon fiber composite materials in the preparation of aerospace tank materials, which has broad application prospects.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] (1) The present invention provides a high-performance carbon fiber composite material. The present invention adopts a multi-component synergistic modification strategy and utilizes multi-element and multi-physical field modification methods to develop a carbon fiber composite material with excellent liquid oxygen compatibility, resistance to low-temperature medium leakage, and mechanical properties. The nitrogen element introduced into the surface of the multi-element modified MXene of the present invention forms a multi-stage flame retardant barrier with the phosphorus element in DOPO, the nitrogen in 3-aminopropyltriethoxysilane (AEAPTMS), and the fluorine in perfluorodecyltriethoxysilane (PFDTES), which can play a synergistic role, inhibit the progress of the oxidation reaction, and significantly improve the liquid oxygen compatibility of the carbon fiber composite material. In addition, the present invention adds multi-component modified MXene and nano-boron nitride to the resin matrix, which can significantly reduce the thermal expansion coefficient of the resin matrix. At the same time, nano-boron nitride has good thermal conductivity. When the carbon fiber composite material is reduced from high temperature to low temperature, the residual stress is reduced and the generation of cracks is effectively inhibited. In addition, the multi-component modified MXene and nano-boron nitride can also increase the interfacial bonding performance between the resin and the carbon fiber, significantly improving the mechanical properties of the carbon fiber composite material, effectively consuming the energy of crack expansion, inhibiting the expansion of cracks, and achieving the purpose of anti-seepage.

[0034] (2) In the present invention, magnetic field and electric field coupling induction are used to prepare carbon fiber composite materials. The purpose of the multi-physical field is to allow the modified MXene to be oriented in the resin matrix, increase the uniformity of MXene distribution, and improve the thermal conductivity and mechanical properties of the carbon fiber composite materials.

[0035] (3) The present invention provides a method for preparing the above-mentioned high-performance carbon fiber composite material, which is easy to operate, has strong feasibility, and is conducive to industrial production.

[0036] (4) The present invention provides the application of the above-mentioned carbon fiber composite material in the preparation of aerospace propellant tanks, which has broad application prospects; and the research and development of the carbon fiber composite material provides strong support for technological innovation and industrial upgrading in related fields. DETAILED DESCRIPTION

[0037] 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.

[0038] 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.

[0039] 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.

[0040] Ti3C2T x The aqueous dispersion of MXene comes from Foshan Xinxin Technology Co., Ltd., single-layer MXene dispersion, 5 mg / mL, 50 mL / bottle.

[0041] Example 1

[0042] (1) Take 20 mL of Ti3C2T with a concentration of 5 mg / mL x The aqueous dispersion of MXene was diluted with 160 g of anhydrous ethanol, and then acetic acid was added to reduce the pH of the reaction system to about 3.5 to obtain a MXene dispersion;

[0043] 2 g of 3-aminopropyltriethoxysilane (AEAPTMS), 2.4 g of perfluorodecyltriethoxysilane (PFDTES), and 1.6 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) were dissolved in 20 g of anhydrous ethanol to obtain an ethanol solution of AEAPTMS, an ethanol solution of PFDTES, and an ethanol solution of DOPO;

[0044] Under nitrogen atmosphere and stirring at 1000 rpm, the ethanol solution of AEAPTMS was first added dropwise to the MXene dispersion within 2 hours, followed by the ethanol solution of PFDTES, and finally the ethanol solution of DOPO. The reaction was continued at room temperature for 8 hours. After the reaction, the dispersion was centrifuged and washed three times with ethanol at a centrifugal speed of 10,000 rpm for 20 minutes each time to remove unreacted silane, DOPO, and acetic acid, and then vacuum dried to obtain a multi-modified MXene.

[0045] (2) Disperse 0.5 g of multi-modified MXene in 5 g of anhydrous ethanol to obtain multi-modified MXene ethanol dispersion A; disperse 10 mg of multi-modified MXene in 5 g of anhydrous ethanol to obtain multi-modified MXene ethanol dispersion B;

[0046] (3) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, nano boron nitride, and epoxy resin are mixed to obtain a modified epoxy resin; wherein the mass ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, nano boron nitride, and epoxy resin is 3:0.5:100; multi-modified MXene ethanol dispersion A is added to the modified epoxy resin, stirred evenly, and 4,4'-diaminodiphenyl sulfone is added to obtain a multi-modified MXene / epoxy resin solution; wherein the mass ratio of multi-modified MXene ethanol dispersion A, modified epoxy resin, and 4,4'-diaminodiphenyl sulfone is 10:100:50;

[0047] (4) The carbon fiber was de-sizing at 300°C for 2 min, immersed in a multi-modified MXene ethanol dispersion B, and then dried under protective gas to obtain the treated carbon fiber; then 1000 g of the treated carbon fiber was mixed with 500 g of the multi-modified MXene / epoxy resin solution to prepare a carbon fiber prepreg;

[0048] (5) After the carbon fiber prepreg is laid in parallel, a magnetic field (3T pulse) and an electric field (10kV / m) coupling directional technology is used, wherein the direction of the magnetic field is at a 45° angle to the direction of the carbon fiber, and the direction of the electric field is at a 45° angle to the carbon fiber. The temperature is raised from 30°C for curing at a heating rate of 1.5°C / min. When it reaches 130°C, it is cured at this temperature for 2h. When it continues to rise to 160°C, it is cured at this temperature for 2h. Finally, when it continues to rise to 180°C, it is cured at this temperature for 2h (only the electric field is applied at the beginning of curing. When the temperature rises to 75°C, the magnetic field and the electric field are applied at the same time).

[0049] Example 2

[0050] (1) Take 20 mL of Ti3N2T with a concentration of 6 mg / mL x The aqueous dispersion of MXene was diluted with 160 g of anhydrous ethanol, and then acetic acid was added to reduce the pH of the reaction system to about 3.5 to obtain a MXene dispersion;

[0051] 1.6 g of AEAPTMS, 2.0 g of PFDTES, and 1.0 g of DOPO were dissolved in 20 g of anhydrous ethanol to obtain an ethanol solution of AEAPTMS, an ethanol solution of PFDTES, and an ethanol solution of DOPO;

[0052] Under nitrogen atmosphere and stirring at 800 rpm, the ethanol solution of AEAPTMS was first added dropwise to the MXene dispersion within 2 h, followed by the ethanol solution of PFDTES, and finally the ethanol solution of DOPO. The reaction was continued at room temperature for 6 h. After the reaction, the dispersion was centrifuged and washed three times with ethanol at 8000 rpm for 20 min each time to remove unreacted silane, DOPO, and acetic acid, and then vacuum dried to obtain a multi-modified MXene.

[0053] (2) Disperse 0.025 g of multi-modified MXene in 5 g of anhydrous ethanol to obtain multi-modified MXene ethanol dispersion A; disperse 5 mg of multi-modified MXene in 5 g of anhydrous ethanol to obtain multi-modified MXene ethanol dispersion B;

[0054] (3) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, nano boron nitride, and epoxy resin are mixed to obtain a modified epoxy resin; wherein the mass ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, nano boron nitride, and epoxy resin is 2.0:0.3:100; multi-modified MXene ethanol dispersion A is added to the modified epoxy resin, ultrasonically stirred to uniformity, and 4,4'-diaminodiphenyl sulfone is added to obtain a MXene / epoxy resin solution, wherein the mass ratio of multi-modified MXene ethanol dispersion A, modified epoxy resin, and 4,4'-diaminodiphenyl sulfone is 8:100:50;

[0055] (4) The carbon fiber was desized at 400 °C for 1 min, immersed in a multi-modified MXene ethanol dispersion B, and then dried under protective gas to obtain the treated carbon fiber; then 1000 g of the treated carbon fiber was mixed with 500 g of MXene / epoxy resin solution to prepare a carbon fiber prepreg;

[0056] (5) After the carbon fiber prepreg is laid in parallel, a magnetic field (3T pulse) and an electric field (10kV / m) coupling directional technology is used, wherein the direction of the magnetic field is at a 45° angle to the direction of the carbon fiber, and the direction of the electric field is at a 45° angle to the carbon fiber. The temperature is raised from 30°C for curing at a heating rate of 1.5°C / min. When it reaches 130°C, it is cured at this temperature for 2h. When it continues to rise to 160°C, it is cured at this temperature for 2h. Finally, when it continues to rise to 180°C, it is cured at this temperature for 2h (only the electric field is applied at the beginning of curing. When the temperature rises to 75°C, the magnetic field and the electric field are applied at the same time).

[0057] Example 3

[0058] (1) Take 20 mL of Ti3C2T with a concentration of 5 mg / mL x The aqueous dispersion of MXene was diluted with 160 g of ethanol, and then acetic acid was added to reduce the pH of the reaction system to about 3.5 to obtain a MXene dispersion;

[0059] 2.4 g of AEAPTMS, 3.0 g of PFDTES, and 2.0 g of DOPO were dissolved in 20 g of ethanol to obtain an ethanol solution of AEAPTMS, an ethanol solution of PFDTES, and an ethanol solution of DOPO;

[0060] Under nitrogen atmosphere and stirring at 1200 rpm, the ethanol solution of AEAPTMS was first added dropwise to the MXene dispersion within 2 hours, followed by the ethanol solution of PFDTES, and finally the ethanol solution of DOPO. The reaction was continued at room temperature for 10 hours. After the reaction, the dispersion was centrifuged and washed three times with ethanol at a centrifugal speed of 15,000 rpm for 20 minutes each time to remove unreacted silane and DOPO, and then vacuum dried to obtain the multi-modified MXene.

[0061] (2) Disperse 1.5 g of multi-modified MXene in 5 g of anhydrous ethanol to obtain multi-modified MXene ethanol dispersion A; disperse 50 mg of multi-modified MXene in 5 g of anhydrous ethanol to obtain multi-modified MXene ethanol dispersion B;

[0062] (3) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, nano boron nitride, and epoxy resin are mixed to obtain a modified epoxy resin; wherein the mass ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, nano boron nitride, and epoxy resin is 3.5:0.8:100; the multi-modified MXene ethanol dispersion A is added to the modified epoxy resin, ultrasonically stirred, and 4,4'-diaminodiphenyl sulfone is added to obtain a MXene / epoxy resin solution, wherein the mass ratio of the multi-modified MXene ethanol dispersion A, modified epoxy resin, and 4,4'-diaminodiphenyl sulfone is 15:100:50;

[0063] (4) The carbon fibers were desizing at 260°C for 2 min, immersed in a multi-modified MXene ethanol dispersion B, and then dried under protective gas to obtain treated carbon fibers; 900 g of the treated carbon fibers were then mixed with 500 g of MXene / epoxy resin solution to prepare a carbon fiber prepreg;

[0064] (5) After the carbon fiber prepreg is laid in parallel, a magnetic field (3T pulse) and an electric field (10kV / m) coupling directional technology is used, wherein the direction of the magnetic field is at a 45° angle to the direction of the carbon fiber, and the direction of the electric field is at a 45° angle to the carbon fiber. The temperature is raised from 30°C for curing at a heating rate of 1.5°C / min. When it reaches 130°C, it is cured at this temperature for 2h. When it continues to rise to 160°C, it is cured at this temperature for 2h. Finally, when it continues to rise to 180°C, it is cured at this temperature for 2h (only the electric field is applied at the beginning of curing. When the temperature rises to 75°C, the magnetic field and the electric field are applied at the same time).

[0065] Comparative Example 1

[0066] Comparative Example 1 is essentially the same as Example 1, except that the coupled magnetic field (3T pulse) and electric field (10 kV / m) orientation technique is not employed. Specifically, the carbon fiber prepreg is cured starting at 30°C at a rate of 1.5°C / min. Upon reaching 130°C, the material is cured for 2 hours. The temperature is then raised further to 160°C, where it is then cured for 2 hours. Finally, the temperature is further raised to 180°C, where it is then cured for 2 hours. All other conditions remain the same as in Example 1.

[0067] Comparative Example 2

[0068] Comparative Example 2 is basically the same as Example 1, except that the electric field in the magnetic field (3T pulse) and electric field (10 kV / m) coupling orientation is omitted, and the rest is consistent with Example 1.

[0069] Comparative Example 3

[0070] Comparative Example 3 is basically the same as Example 1, except that the magnetic field in the coupling orientation of the magnetic field (3T pulse) and the electric field (10 kV / m) is omitted, and the electric field is applied at the beginning of curing in this comparative example. Other aspects are consistent with Example 1.

[0071] Comparative Example 4

[0072] Comparative Example 4 is substantially the same as Example 1, except that the carbon fiber and the modified epoxy resin are not treated with multi-modified MXene.

[0073] The preparation method of the carbon fiber composite material of this comparative example is:

[0074] (1) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, nano boron nitride, and epoxy resin are mixed to obtain a modified epoxy resin, wherein the mass ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, nano boron nitride, and epoxy resin is 1:0.5:100; 4,4'-diaminodiphenyl sulfone is added to the modified epoxy resin to obtain an epoxy resin solution, wherein the mass ratio of the modified epoxy resin to 4,4'-diaminodiphenyl sulfone is 100:50;

[0075] (2) 1000g of carbon fiber was mixed with 500g of epoxy resin solution to prepare carbon fiber prepreg. After parallel plying, magnetic field (3T pulse) and electric field (10kV / m) coupling directional technology were used, wherein the direction of the magnetic field was at a 45° angle to the direction of the carbon fiber, and the direction of the electric field was at a 45° angle to the carbon fiber. The temperature was raised from 30°C for curing at a heating rate of 1.5°C / min. When the temperature reached 130°C, the prepreg was cured at this temperature for 2h. The temperature was further raised to 160°C and the prepreg was cured at this temperature for 2h. Finally, the prepreg was further raised to 180°C and the prepreg was cured at this temperature for 2h (only the electric field was applied at the beginning of curing, and the magnetic field and electric field were applied simultaneously when the temperature rose to 75°C).

[0076] Comparative Example 5

[0077] Comparative Example 5 is basically the same as Example 1, except that the modified epoxy resin is not treated with the multi-modified MXene, that is, the addition of the multi-modified MXene ethanol dispersion A is omitted in step (3), and the rest is consistent with Example 1.

[0078] Comparative Example 6

[0079] Comparative Example 6 is basically the same as Example 1, except that the carbon fibers are not treated with multi-component modified MXene, that is, in step (4), the carbon fibers are not immersed in the multi-component modified MXene ethanol dispersion B. The rest of the steps remain the same as Example 1.

[0080] Comparative Example 7

[0081] This comparative example 7 is basically the same as Example 1, except that the multi-modified MXene ethanol dispersion is replaced by the MXene dispersion of step (1), and the rest is consistent with Example 1.

[0082] Comparative Example 8

[0083] Comparative Example 8 is basically the same as Example 1, except that the modified epoxy resin is replaced by an epoxy resin that is not modified with DOPO and nano-boron nitride, and the rest is consistent with Example 1.

[0084] Comparative Example 9

[0085] Comparative Example 9 is basically the same as Example 1, except that the multi-modified MXene ethanol dispersion is replaced by the MXene dispersion of step (1), and the modified epoxy resin is replaced by an epoxy resin that is not modified with DOPO and nano-boron nitride. Other differences are consistent with Example 1.

[0086] Comparative Example 10

[0087] This comparative example 10 is basically the same as Example 1, except that no multi-modified MXene is involved, and the modified epoxy resin is replaced by an epoxy resin that is not modified with DOPO and nano-boron nitride.

[0088] The preparation method of the carbon fiber composite material of this comparative example is:

[0089] (1000g) carbon fiber and (500g) epoxy resin were mixed to prepare carbon fiber prepreg. After parallel plying, magnetic field (3T pulse) and electric field (10kV / m) coupling orientation technology was adopted, wherein the direction of the magnetic field was at a 45° angle to the direction of the carbon fiber, and the direction of the electric field was at a 45° angle to the carbon fiber. The temperature was raised from 30°C for curing at a heating rate of 1.5°C / min. When the temperature reached 130°C, the prepreg was cured at this temperature for 2h. The temperature was further raised to 160°C and the prepreg was cured at this temperature for 2h. Finally, the prepreg was further raised to 180°C and the prepreg was cured at this temperature for 2h (only the electric field was applied at the beginning of curing, and the magnetic field and the electric field were applied simultaneously when the temperature was raised to 75°C).

[0090] Test example

[0091] The liquid oxygen compatibility, helium leakage rate at -196°C, thermal conductivity and interlaminar shear strength of the materials obtained in Examples 1-3 of the present invention and Comparative Examples 1-10 were tested. The results are shown in Table 1.

[0092] Table 1

[0093]

[0094] From the results in Table 1, it can be seen that Examples 1-3 of the present invention are superior to the comparative examples in terms of liquid oxygen compatibility, low-temperature sealing, thermal conductivity and mechanical strength. Example 1 shows the best comprehensive performance: good liquid oxygen compatibility and the lowest helium leakage rate at -196°C , thermal conductivity reaches 5.0 W / (m·K), and interlaminar shear strength is as high as 120 MPa, which indicates that it has excellent liquid oxygen compatibility, thermal conductivity and interface bonding strength.

[0095] In summary, the present invention is based on the fact that carbon fiber composite materials themselves have excellent properties such as light weight and high strength, but when preparing liquid oxygen tanks for aerospace propellants, their liquid oxygen compatibility and anti-leakage properties are insufficient to improve the problem. The present invention introduces multi-modified MXene into DOPO and nano-boron nitride modified epoxy resin, and then prepares a composite material with carbon fiber after surface treatment of multi-modified MXene. The synergistic effect of multi-modified MXene, DOPO and nano-boron nitride effectively improves the liquid oxygen compatibility and anti-low temperature medium leakage ability of the carbon fiber composite material, while significantly improving the mechanical properties of the carbon fiber composite material. The research and development of this carbon fiber composite material provides strong support for technological innovation and industrial upgrading in related fields.

[0096] 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 high-performance carbon fiber composite material, characterized in that: The steps include: (1) Under a nitrogen atmosphere, an ethanol solution of 3-aminopropyltriethoxysilane, an ethanol solution of perfluorodecyltriethoxysilane, and an ethanol solution of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are sequentially added dropwise to the MXene dispersion, and the reaction is continued. After the reaction, the mixture is centrifuged and washed to obtain a multi-modified MXene. (2) dispersing the multi-modified MXene in anhydrous ethanol to obtain a multi-modified MXene ethanol dispersion; (3) The multi-modified MXene ethanol dispersion, modified epoxy resin, and curing agent are uniformly mixed to obtain a MXene / epoxy resin solution; (4) First remove the sizing agent on the surface of the carbon fiber, then immerse it in the multi-modified MXene ethanol dispersion, and then dry it for use; mix the treated carbon fiber with the MXene / epoxy resin solution to obtain a carbon fiber prepreg; (5) Under the coupling induction of magnetic field and electric field, the carbon fiber prepreg is heated and cured to obtain a carbon fiber composite material; In step (3), the modified epoxy resin is prepared by mixing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, nano-boron nitride, and epoxy resin to obtain the modified epoxy resin; the mass ratio of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, nano-boron nitride, and epoxy resin is (2-3.5): (0.3-0.8): 100; In step (5), the direction of the magnetic field forms an angle of 45° with the direction of the carbon fiber, and the direction of the electric field forms an angle of 45° with the carbon fiber; the intensity of the magnetic field is 1-3T; the current density of the electric field is 10KV / m; The specific steps of curing are: starting from 30°C and curing at a heating rate of 1.5°C / min, curing at this temperature for 2 hours when reaching 130°C, continuing to heat up to 160°C and curing at this temperature for 2 hours, and finally continuing to heat up to 180°C and curing at this temperature for 2 hours; at the beginning of curing, only the electric field is applied, and when the temperature rises to 75°C, the magnetic field and electric field are applied simultaneously.

2. The method for preparing a high-performance carbon fiber composite material according to claim 1, characterized in that: In step (1), the mass ratio of the MXene dispersion, the ethanol solution of 3-aminopropyltriethoxysilane, the ethanol solution of perfluorodecyltriethoxysilane and the ethanol solution of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is (17-19): (2-3): (2-3): (2-3); In step (3), the ratio of the multi-modified MXene ethanol dispersion, the modified epoxy resin, and the curing agent is (5-15):100:50; the curing agent is 4,4'-diaminodiphenyl sulfone.

3. The method for preparing a high-performance carbon fiber composite material according to claim 1, characterized in that: In step (1), the time for dripping the ethanol solution of 3-aminopropyltriethoxysilane is ≤2h; the time for dripping the ethanol solution of perfluorodecyltriethoxysilane is ≤2h; the time for dripping the ethanol solution of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is ≤2h; the reaction time is 6-10h; The MXene dispersion is prepared by adding the MXene aqueous dispersion to anhydrous ethanol, and then adding acetic acid to adjust the pH to 3.0-4.

0.

4. The method for preparing a high-performance carbon fiber composite material according to claim 3, characterized in that: The dosage ratio of anhydrous ethanol to MXene aqueous dispersion is 8g:1mL; the concentration of the MXene aqueous dispersion is 3-8mg / mL; the MXene aqueous dispersion is Ti3C2T x MXene aqueous dispersion or T3N2T x MXene aqueous dispersion.

5. The method for preparing a high-performance carbon fiber composite material according to claim 1, characterized in that: In step (1), the ethanol solution of 3-aminopropyltriethoxysilane is obtained by mixing 3-aminopropyltriethoxysilane and anhydrous ethanol in a mass ratio of (1-2):20; the ethanol solution of perfluorodecyltriethoxysilane is obtained by mixing perfluorodecyltriethoxysilane and anhydrous ethanol in a mass ratio of (2-3):20; the ethanol solution of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is obtained by mixing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and anhydrous ethanol in a mass ratio of (1-2):20; In step (2), the mass ratio of the multi-modified MXene to anhydrous ethanol is (0.001-0.3):

1.

6. The method for preparing a high-performance carbon fiber composite material according to claim 1, characterized in that: In step (4), the treatment temperature for removing the sizing agent on the surface of the carbon fiber is 300-400°C, and the time is 0.5-5 minutes; the mass ratio of the treated carbon fiber to the MXene / epoxy resin solution is (8-10): (3-5).

7. A high-performance carbon fiber composite material, characterized in that: The product is prepared by the preparation method according to any one of claims 1 to 6.

8. Use of the high-performance carbon fiber composite material according to claim 7 in the preparation of aerospace tank materials.

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