High-temperature ablation resistant carbon fiber composite material and preparation method thereof
By combining the modified silicate resin and the modified filler, the high temperature resistance of the carbon fiber composite material is improved, the problem of softening and decomposition of the resin matrix at high temperature is solved, and high binding strength and excellent heat and corrosion resistance are achieved.
Patent Information
- Application Number
- CN202510588600.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-08
- Publication Date
- 2025-08-01
AI Technical Summary
The high temperature resistance of carbon fiber resin composite materials is low, and the resin matrix is prone to softening and decomposing at high temperatures, resulting in a decline in the overall performance of the composite material.
Modified silicate resin coating is used to promote the hydrolysis and polycondensation reaction of orthosilicate through ethanol to form a stable silicate resin structure, and a silane coupling agent is introduced to chemically bond the surface of carbon fiber, and polyethylene maleic anhydride copolymer is added to form an interpenetrating network structure. At the same time, modified fillers such as mica powder, zirconia and sodium gluconate are used to enhance the mechanical anchoring, chemical stability and physical barrier properties of the coating.
The bonding strength of carbon fiber composite materials is improved, and it has excellent high temperature resistance, heat aging resistance, corrosion resistance and self-cleaning properties.
Smart Images
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Abstract
Description
Technical Field
[0001] This application relates to the technical field of carbon fiber composites, and specifically relates to a high-temperature ablation-resistant carbon fiber composite material and a preparation method thereof. Background Art
[0002] Carbon fiber is a fiber with a very high carbon content, having high strength and high modulus, and is often used in combination with resin materials. Due to the good processability and corrosion resistance of the resin coating, this composite material combines the respective advantages of carbon fiber and resin, and has characteristics such as light weight, high strength, corrosion resistance, and easy processing. Therefore, it has broad application prospects in the fields of aerospace, automobiles, sports equipment, etc.
[0003] However, although carbon fiber resin composite materials have many advantages, their relatively low high-temperature resistance is an undeniable defect. This is mainly because the resin matrix is prone to changes such as softening and decomposition at high temperatures, resulting in a decline in the overall performance of the composite material. Summary of the Invention
[0004] To solve the above technical problems, this application provides a high-temperature ablation-resistant carbon fiber composite material and a preparation method thereof.
[0005] In a first aspect, this application provides a high-temperature ablation-resistant carbon fiber composite material, which is prepared by brush-coating a high-temperature resistant resin coating on a carbon fiber substrate; The high-temperature resistant resin coating specifically includes the following components in parts by weight: 40-50 parts of modified silicate resin, 20-30 parts of modified filler, 8-15 parts of solvent, 0.4-0.9 parts of dispersant, 0.1-0.5 parts of defoaming agent, and 0.2-0.6 parts of leveling agent; The preparation method of the modified silicate resin is as follows: Disperse tetraethyl orthosilicate in ethanol, perform ultrasonic treatment for 30-50 min under the condition of a power of 200-400 W, add a silane coupling agent, adjust the pH to 3-4, and carry out a reflux reaction at 55-65 °C for 4-8 h; then add a polyethylene maleic anhydride copolymer and react at 55-65 °C for 8-16 h, and distill off the solvent to obtain it; the weight ratio of ethanol, tetraethyl orthosilicate, silane coupling agent, and polyethylene maleic anhydride copolymer is 100:20-30:7-11:3-5; The preparation method of the modified filler is as follows: Add mica powder, zirconia, sodium gluconate, and polyethylene wax to water, mix evenly, heat to 70-90 °C in a water bath environment, and stir for 6-10 h; then through centrifugation, drying, and grinding to a fineness ≤ 10 μm to obtain the modified filler; the weight ratio of mica powder, zirconia, sodium gluconate, polyethylene wax, and water is 40-50:15-20:1-7:1-7:100; The solvent is composed of ethanol and butanol.
[0006] In the technical solution provided by this application, ethanol is used as a solvent to promote the hydrolysis and polycondensation reactions of tetraethyl orthosilicate, forming the basic structure of the silicate resin, which can ensure the stability and durability of the coating. The introduced silane coupling agent can chemically react with the functional groups on the surface of carbon fiber to form chemical bonding, thereby improving the adhesion between the coating and the carbon fiber. This chemical bonding can not only enhance the bonding strength but also effectively prevent the coating from peeling and delaminating under harsh environments such as high temperature and high humidity. The addition of the polyethylene maleic anhydride copolymer endows the modified silicate resin with good high-temperature resistance and chemical stability, which can effectively protect the carbon fiber from being eroded by high temperature, moisture, and corrosive media; at the same time, it can also form an interpenetrating network structure with the silicate resin to further improve the comprehensive performance of the coating.
[0007] In the technical solution of the modified filler provided by this application, the lamellar structure of mica powder provides a mechanical anchoring effect, increasing the contact area between the coating and the surface of carbon fiber, and forming hydrogen bonding with the oxygen-containing groups of carbon fiber through surface hydroxyl groups; and it can withstand temperatures above 600 °C. The lamellar structure can block oxygen diffusion and delay the thermal oxidation of the resin matrix; the hydrophobic lamellar arrangement of mica powder can delay the water molecule penetration path, reduce the water absorption rate of the coating, and extend the diffusion path of corrosive media. As high surface energy nanoparticles, zirconia can fill the interface micropores and enhance physical adsorption; the ultra-high melting point and low thermal conductivity of zirconia effectively block thermal degradation and inhibit coating cracking; and zirconia has chemical inertness and can effectively resist the corrosive erosion of water vapor and electrolytes. Sodium gluconate can improve the uniform distribution of the filler in the system and avoid interface defects caused by agglomeration. After melting, polyethylene wax can form a flexible interface layer to relieve stress concentration, and at the same time enhance interface adhesion through van der Waals forces and fill microcracks. The combined action of these substances as a modified filler system comprehensively upgrades the engineering applicability of the coating through multiple ways such as physical barrier, chemical stability, and interface optimization, and further greatly improves the performance of carbon fiber composites.
[0008] Preferably, the high-temperature resistant resin coating specifically includes the following components in parts by weight: 42 - 48 parts of modified silicate resin, 23 - 17 parts of modified filler, 10 - 13 parts of solvent, 0.5 - 0.8 part of dispersant, 0.2 - 0.4 part of defoamer, and 0.3 - 0.5 part of leveling agent.
[0009] Preferably, the weight ratio of the ethanol, tetraethyl orthosilicate, silane coupling agent, and polyethylene maleic anhydride copolymer is 100:22 - 28:8 - 10:3.5 - 4.5.
[0010] Preferably, the silane coupling agent is selected from one or more of γ-aminopropyltriethoxysilane KH-550, γ-methacryloxypropyltrimethoxysilane KH-570, and γ-mercaptopropyltrimethoxysilane KH-592.
[0011] Preferably, the weight ratio of mica powder, zirconia, sodium gluconate, polyethylene wax, and water is 42-48:16-19:2-6:2-6:100.
[0012] Preferably, in the preparation method of the modified filler, the particle size of the mica powder is 400-500 mesh; the polyethylene wax is Licowax PE 520 with a molecular weight of 2000-2500.
[0013] Preferably, the solvent is composed of ethanol and butanol with a weight ratio of 0.5-1.5:3-10.
[0014] Preferably, the dispersant is selected from one or more of BYK-110, BYK-W 692, and SOLSPERSE 32000; the defoaming agent is selected from one or more of BYK-066N, TEGO-932, and BYK141; the leveling agent is selected from one or more of TEGO Glide410, BYK349, and TEGO 2700.
[0015] In a second aspect, the present application provides a method for preparing the above high-temperature ablation-resistant carbon fiber composite material, which is characterized by specifically including the following steps in sequence: Weigh the corresponding raw material components according to the formula amount; add the modified silicate resin and the modified filler to the solvent, stir evenly at 70-90°C and 300-500 rpm, and then cool to room temperature for standby; under stirring conditions, add the dispersant, defoaming agent, and leveling agent, and mix evenly to obtain the high-temperature resistant resin coating; Brush the high-temperature resistant resin coating on the front and back sides of the carbon fiber substrate, first bake at 110-130°C for 2-3 minutes; then keep warm at 150-180°C for 3-6 hours to obtain.
[0016] Preferably, the coating amount of the high-temperature resistant resin coating is 140-160 g / m 2 .
[0017] In summary, the technical solution of the present application has the following effects: The technical solution provided by the present application prepares a modified silicate resin by using ethanol, tetraethyl orthosilicate, silane coupling agent, and polyethylene maleic anhydride copolymer, prepares a modified filler from mica powder, zirconia, sodium gluconate, polyethylene wax, and water, and then prepares a high-temperature resistant resin coating, which is brushed on a carbon fiber substrate to obtain a carbon fiber composite material. The obtained carbon fiber composite material has a high bonding strength at the interface between the carbon fiber and the resin, and has excellent high-temperature resistance, heat aging resistance, corrosion resistance, and self-cleaning properties. Detailed Embodiments
[0018] The present application will be further described in detail below in combination with examples, comparative examples and performance detection tests. These examples should not be construed as limiting the scope claimed by the present application. Examples
[0019] Examples 1 - 5 Examples 1 - 5 respectively provide a high-temperature ablation-resistant carbon fiber composite material and a preparation method thereof. The differences between the above examples are as follows: the dosages of the components of the high-temperature ablation-resistant resin coating in the high-temperature ablation-resistant carbon fiber composite material are different, as specifically shown in Table 1.
[0020] The preparation method of the high-temperature ablation-resistant carbon fiber composite material in the above examples is specifically as follows.
[0021] The preparation method of the modified silicate resin is as follows: Disperse 250 g of tetraethyl orthosilicate in 1000 g of ethanol, perform ultrasonic treatment for 40 min under the condition of a power of 300 W, add 90 g of silane coupling agent KH-550, adjust the pH to 3.5, and carry out a reflux reaction at 60 °C for 6 h; then add 40 g of polyethylene maleic anhydride copolymer and react at 60 °C for 12 h, and distill off the solvent to obtain it; the weight ratio of ethanol, tetraethyl orthosilicate, silane coupling agent, and polyethylene maleic anhydride copolymer (Aladdin, product number P304899) is 100:25:9:4.
[0022] The preparation method of the modified filler is as follows: Add 450 g of mica powder with a particle size of 400 - 500 mesh (product number GW, purchased from Chuzhou Pagoda Sericite Mining Co., Ltd.), 170 g of zirconia, 40 g of sodium gluconate, and 40 g of polyethylene wax (Licowax PE520, molecular weight 2000 - 2500) to 1000 water, mix evenly, heat up to 80 °C in a water bath environment, and stir for 8 h; then carry out centrifugation, drying, and grinding with a three-roll mill until the fineness ≤ 10 μm to obtain the modified filler; the weight ratio of mica powder, zirconia, sodium gluconate, polyethylene wax, and water is 45:17:4:4:100.
[0023] According to Table 1 and the formula amounts, respectively weigh the corresponding raw material components of the corresponding weights; add the modified silicate resin and the modified filler to a solvent (composed of ethanol and butanol mixed in a weight ratio of 1:7), stir evenly at 80 °C and 400 rpm, and then cool to room temperature for standby; under stirring conditions, add a dispersant SOLSPERSE 32000, an antifoaming agent BYK-066N, and a leveling agent TEGO 2700, and mix evenly to obtain the high-temperature ablation-resistant resin coating.
[0024] Cut carbon fiber unidirectional cloth with a cutting strength level of T800 to make a carbon fiber base plate. Lay 6 layers of carbon fiber cloth on each plate, and the laying sequence is 90°, 0°, 90°, 0°, 0°, 90°. The size of each layer of carbon cloth is 10 cm × 10 cm to obtain a T800 carbon fiber base material.
[0025] According to a coating amount of 150 g / m 2 , brush the high-temperature resistant resin coating on the front and back of the T800 carbon fiber base plate respectively. First, bake at 120 °C for 3 min; then keep warm at 165 °C for 4 h to obtain it.
[0026] Table 1 Usage amounts of each component of the high-temperature resistant resin coating in Examples 1-5 Examples 6-9 Examples 6-9 respectively provide a high-temperature resistant ablative carbon fiber composite material and its preparation method The differences between the above examples and Example 3 are specifically as follows: The preparation methods of the modified silicate resins are different, as shown below.
[0027] In Example 6: Use an equal amount of silane coupling agent KH-592 to replace silane coupling agent KH-550.
[0028] In Example 7: The weight ratio of ethanol, tetraethyl orthosilicate, silane coupling agent KH-550, and polyethylene maleic anhydride copolymer is 100:30:7:5.
[0029] In Example 8: The weight ratio of ethanol, tetraethyl orthosilicate, silane coupling agent KH-550, and polyethylene maleic anhydride copolymer is 100:22:10:3.5.
[0030] In Example 9: The weight ratio of ethanol, tetraethyl orthosilicate, silane coupling agent KH-550, and polyethylene maleic anhydride copolymer is 100:28:8:4.5.
[0031] Other process parameters in the above examples are the same as those in Example 3.
[0032] Examples 10-13 Examples 10-13 respectively provide a high-temperature resistant ablative carbon fiber composite material and its preparation method The differences between the above examples and Example 3 are specifically as follows: The preparation methods of the modified fillers are different, as shown below.
[0033] In Example 10: Use an equal amount of Honeywell AC-6A (molecular weight 3000-4500) to replace Licowax PE520 polyethylene wax.
[0034] In Example 11: The weight ratio of mica powder, zirconia, sodium gluconate, polyethylene wax, and water is 50:15:1:7:100.
[0035] In Example 12: The weight ratio of mica powder, zirconia, sodium gluconate, polyethylene wax, and water is 42:19:2:6:100.
[0036] In Example 13: The weight ratio of mica powder, zirconia, sodium gluconate, polyethylene wax, and water is 48:16:6:2:100.
[0037] In the above examples, other process parameters are the same as those in Example 3.
[0038] Examples 14 - 16 Examples 14 - 16 respectively provide a high temperature ablation resistant carbon fiber composite material and a preparation method thereof. The differences between the above examples and Example 3 are specifically as follows: The preparation methods of the modified fillers are different, as shown below.
[0039] In Example 14: The solvent is composed of ethanol and butanol mixed in a weight ratio of 7:1.
[0040] In Example 15: The solvent is composed of ethanol and butanol mixed in a weight ratio of 0.5:10.
[0041] In Example 16: The solvent is composed of ethanol and butanol mixed in a weight ratio of 1.5:3.
[0042] In the above examples, other process parameters are the same as those in Example 3.
[0043] Comparative Examples Comparative Examples 1 - 2 Comparative Examples 1 - 2 respectively provide a high temperature ablation resistant carbon fiber composite material and a preparation method thereof.
[0044] The differences between the above comparative examples and Example 3 are that: The dosages of each component in the high temperature resistant resin coating are different, as specifically shown in Table 1.
[0045] In the above comparative examples, other process parameters are the same as those in Example 3.
[0046] Comparative Examples 3 - 6 Comparative Examples 3 - 5 respectively provide a high temperature ablation resistant carbon fiber composite material and a preparation method thereof.
[0047] The differences between the above comparative examples and Example 3 are specifically as follows.
[0048] In Comparative Example 3: In the preparation method of the modified silicate resin, an equal amount of polystyrene-butadiene copolymer (Aladdin, product number P434453) was used to replace the polyethylene maleic anhydride copolymer.
[0049] In Comparative Example 4: In the preparation method of the modified silicate resin, the weight ratio of ethanol, tetraethyl orthosilicate, silane coupling agent, and polyethylene maleic anhydride copolymer was 100:9:25:1.
[0050] In Comparative Example 5: In the preparation method of the modified filler: Polyethylene wax was not added.
[0051] In Comparative Example 6: The preparation method of the modified filler was as follows: An equal amount of sodium lactate was used to replace sodium gluconate.
[0052] In the above comparative examples, other process parameters were the same as those in Example 3.
[0053] Performance detection test (1) Interlaminar shear strength: According to the detection method specified in ASTM D2344, the bonding strength at the interface between carbon fiber and resin was detected.
[0054] (2) High temperature resistance: The specimen was placed in a muffle furnace and heated at 600 °C for 2 h, then water quenched, and the cycle was repeated 20 times. Whether there were any defects such as fuzzing and peeling on the coating was observed.
[0055] (3) Heat aging resistance: The specimen was placed under static conditions at a high temperature of 400 °C for 100 hours, and the mass loss rate was detected.
[0056] (4) Good corrosion resistance: According to the detection method specified in ASTM B117, a salt spray test on the specimen was carried out for 500 hours.
[0057] (5) Self-cleaning property: According to the detection method specified in ASTM D5946, the contact angle of the specimen surface was detected.
[0058] The detection results are shown in Table 2.
[0059] Table 2 Performance detection results of the high temperature ablation resistant carbon fiber composites in the examples and comparative examples From the detection results in the above table, it can be seen that by using the technical solution provided in this application, the bonding strength at the interface between carbon fiber and resin in the prepared carbon fiber composite is high, and it has excellent high temperature resistance, heat aging resistance, corrosion resistance, and self-cleaning property.
[0060] By comparing the test results of Examples 1-5 and Comparative Examples 1-2, it can be seen that the dosages of the raw material components in the high-temperature resistant resin coating have a great influence on the performance of the product. In this application, by screening the dosages of the raw material components in the high-temperature resistant resin coating, the performance of the carbon fiber composite material is effectively improved.
[0061] By comparing the test results of Example 3, Examples 6-9 and Comparative Examples 3-4, it can be seen that in Comparative Example 3, an equal amount of styrene-butadiene copolymer is used instead of poly(ethylene maleic anhydride) copolymer in the preparation method of the modified silicate resin, and in Comparative Example 4, the weight ratio of ethanol, tetraethyl orthosilicate, silane coupling agent and poly(ethylene maleic anhydride) copolymer is 100:9:25:1, and the performance of the prepared carbon fiber composite material is poor. In contrast, in the examples of this application, by using ethanol, tetraethyl orthosilicate, silane coupling agent and poly(ethylene maleic anhydride) copolymer with a weight ratio of 100:20-30:7-11:3-5 to prepare the modified silicate resin, the performance of the carbon fiber composite material is effectively improved.
[0062] By comparing the test results of Example 3, Examples 10-13 and Comparative Examples 5-6, it can be seen that in Comparative Example 5, no polyethylene wax is added in the preparation method of the modified filler, and in Comparative Example 6, the preparation method of the modified filler is to use an equal amount of sodium lactate instead of sodium gluconate, and the performance of the prepared carbon fiber composite material is poor. In contrast, in the examples of this application, by using mica powder, zirconia, sodium gluconate, polyethylene wax and water with a weight ratio of 40-50:15-20:1-7:1-7:100 to prepare the modified filler, the performance of the carbon fiber composite material is effectively improved.
[0063] Although the present invention has been described in detail above with general descriptions and specific embodiments, based on the present invention, some modifications or improvements can be made, which are obvious to those skilled in the art. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of the present invention claimed.
Claims
1. A high-temperature ablation-resistant carbon fiber composite material, characterized in that, Prepared by brushing a high-temperature resistant resin coating on a carbon fiber substrate; The high-temperature resistant resin coating specifically comprises the following components in parts by weight: 40-50 parts of modified silicate resin, 20-30 parts of modified filler, 8-15 parts of solvent, 0.4-0.9 part of dispersant, 0.1-0.5 part of defoamer, 0.2-0.6 part of leveling agent; The preparation method of the modified silicate resin is as follows: Disperse tetraethyl orthosilicate in ethanol, perform ultrasonic treatment for 30-50 min under the condition of a power of 200-400 W, add a silane coupling agent, adjust the pH to 3-4, and perform a reflux reaction at 55-65 °C for 4-8 h; Then add a polyethylene maleic anhydride copolymer and react at 55-65 °C for 8-16 h, and distill off the solvent to obtain it; The weight ratio of ethanol, tetraethyl orthosilicate, silane coupling agent, and polyethylene maleic anhydride copolymer is 100:20-30:7-11:3-5; The preparation method of the modified filler is as follows: Add mica powder, zirconia, sodium gluconate, and polyethylene wax to water, mix evenly, heat to 70-90 °C in a water bath environment, and stir for 6-10 h; Then perform centrifugation, drying, and grinding to a fineness of ≤10 μm to obtain the modified filler; The weight ratio of mica powder, zirconia, sodium gluconate, polyethylene wax, and water is 40-50:15-20:1-7:1-7:100; The solvent consists of ethanol and butanol.
2. The high-temperature ablation-resistant carbon fiber composite material according to claim 1, wherein The high-temperature resistant resin coating specifically comprises the following components in parts by weight: 42-48 parts of modified silicate resin, 23-17 parts of modified filler, 10-13 parts of solvent, 0.5-0.8 part of dispersant, 0.2-0.4 part of defoamer, 0.3-0.5 part of leveling agent.
3. The high-temperature ablation-resistant carbon fiber composite material according to claim 1, wherein The weight ratio of ethanol, tetraethyl orthosilicate, silane coupling agent, and polyethylene maleic anhydride copolymer is 100:22-28:8-10:3.5-4.
5.
4. The high-temperature ablation-resistant carbon fiber composite material according to claim 1, wherein The silane coupling agent is selected from one or more of γ-aminopropyltriethoxysilane KH-550, γ-methacryloxypropyltrimethoxysilane KH-570, and γ-mercaptopropyltrimethoxysilane KH-592.
5. The high-temperature ablation-resistant carbon fiber composite material according to claim 1, wherein The weight ratio of mica powder, zirconia, sodium gluconate, polyethylene wax, and water is 42-48:16-19:2-6:2-6:
100.
6. The high-temperature ablation-resistant carbon fiber composite material according to claim 1, wherein In the preparation method of the modified filler, the particle size of the mica powder is 400-500 mesh; The polyethylene wax is Licowax PE 520 with a molecular weight of 2000-2500.
7. The high-temperature ablation-resistant carbon fiber composite material according to claim 1, wherein The solvent consists of ethanol and butanol in a weight ratio of 0.5-1.5:3-10.
8. The high-temperature ablation-resistant carbon fiber composite material according to claim 1, wherein The dispersant is selected from one or more of BYK-110, BYK-W 692, and SOLSPERSE 32000; The defoamer is selected from one or more of BYK-066N, TEGO-932, and BYK141; The leveling agent is selected from one or more of TEGO Glide 410, BYK349, and TEGO 2700.
9. A method for preparing a high-temperature ablation-resistant carbon fiber composite material according to any one of claims 1-8, characterized in that, Specifically includes the following steps carried out in sequence: Weigh the respective raw material components according to the formula dosage; add the modified silicate resin and modified filler to the solvent, stir evenly at 70-90°C and 300-500 rpm, and then cool to room temperature for standby; under stirring conditions, add a dispersant, an antifoaming agent, and a leveling agent, and mix evenly to obtain the high-temperature resistant resin coating; Brush the high-temperature resistant resin coating on both the front and back sides of the carbon fiber substrate, first bake at 110-130°C for 2-3 minutes; then keep warm at 150-180°C for 3-6 hours to obtain.
10. The preparation method of the high-temperature resistant ablation carbon fiber composite material according to claim 9, characterized in that The coating amount of the high-temperature resistant resin coating is 140-160 g / m 2 .