High-temperature-resistant ceramic-based resin composite material, preparation method and application thereof

Abstract

This application discloses a high-temperature resistant ceramic-based resin composite material, its preparation method, and its application, belonging to the field of silicon carbide ceramic preparation technology. The high-temperature resistant ceramic-based resin composite material provided in this application includes a fiber material matrix, a modified phenolic resin, and a ceramic reinforcing slurry composited on the fiber material matrix; the fiber material matrix includes one of carbon fiber cloth, quartz cloth, or silicon carbide fiber cloth; the modified phenolic resin is POSS-modified phenolic resin; the raw materials for preparing the ceramic reinforcing slurry include, by weight: 5-10 parts silicon carbide powder, 15-45 parts tantalum nitride powder, 1-10 parts nickel powder, 10-25 parts pitch, and 35-50 parts modified phenolic resin. The high-temperature resistant ceramic-based resin composite material prepared in this application exhibits a dense microstructure and intact overall structure after treatment at ultra-high temperatures of 2000℃, with minimal expansion and high mass retention, maintaining excellent mechanical properties after ultra-high temperature treatment, meeting the application requirements of composite materials at high temperatures.

Description

Technical Field

[0001] This application belongs to the field of silicon carbide ceramic preparation technology, and particularly relates to a high-temperature resistant ceramic matrix resin composite material, its preparation method and application. Background Technology

[0002] Silicon carbide fiber composites, due to their high strength, low density, and high-temperature resistance, can withstand even higher-temperature thermal oxidation environments and maintain material stability at high temperatures, making them considered ideal alternatives to high-temperature alloys. However, existing high-temperature composites prepared by blending inorganic fillers with ablation-resistant resins as the matrix resin and reinforcing with carbon or quartz fibers, involving chemical reactions during curing, are only suitable for high-temperature applications. Therefore, their properties need to be modified to improve their application in ultra-high-temperature fields.

[0003] The prior art with application publication number CN 110194609 A discloses a high-temperature resistant, oxidation-resistant, ceramizable resin composite material. The resin composite material is made by mixing a carbon-based resin as a matrix and ceramic powder, which is a mixture of supporting filler, molten filler and reactive filler, as a filler. It can be used for a long time (>1000s) in an oxidizing atmosphere at 1400℃-1700℃ without significant ablation.

[0004] However, existing silicon carbide fiber composite materials are mainly designed for long-term use in atmospheric or oxygen-rich environments at 1400℃-1700℃. They cannot meet the requirements for long-term use in ultra-high temperature thermal environments above 2000℃, thus hindering their development and application in the ultra-high temperature field. Summary of the Invention

[0005] This application discloses a high-temperature resistant ceramic matrix resin composite material, its preparation method and application, aiming to solve the technical problem that existing resin composite materials cannot meet the requirements for long-term use in ultra-high temperature thermal environments.

[0006] To achieve the above objectives, the technical solution of this application is:

[0007] The first aspect of this application provides a high-temperature resistant ceramic-based resin composite material, the composite material comprising a fiber material matrix and a modified phenolic resin and a ceramic-reinforced slurry compounded on the fiber material matrix.

[0008] The fiber material matrix includes one of carbon fiber cloth, quartz cloth or silicon carbide fiber cloth.

[0009] The modified phenolic resin is a POSS-modified phenolic resin.

[0010] The raw materials for preparing the ceramic reinforced slurry include, by weight: 5-10 parts silicon carbide powder, 15-45 parts tantalum nitride powder, 1-10 parts nickel powder, 10-25 parts asphalt, and 35-50 parts modified phenolic resin.

[0011] Preferably, in conjunction with the first aspect, the raw materials for preparing the ceramic reinforced slurry include, by weight: 6-8 parts silicon carbide powder, 25-35 parts tantalum nitride powder, 4-8 parts nickel powder, 15-20 parts asphalt, and 40-45 parts modified phenolic resin.

[0012] Preferably, in conjunction with the first aspect, the silicon carbide powder has a diameter of 200-400 nm;

[0013] And / or, the tantalum nitride powder has a diameter of 200-400 nm;

[0014] And / or, the nickel powder has a diameter of 10-40 μm.

[0015] Preferably, in conjunction with the first aspect, the amount of modified phenolic resin added is 0.3-0.7 times that of the resin composite material.

[0016] The second aspect of this application provides a method for preparing the high-temperature resistant ceramic-based resin composite material described in the first aspect, the method comprising:

[0017] The fiber material matrix is ​​impregnated with a modified phenolic resin solution and then dried to obtain a primary modified material;

[0018] The ceramic-reinforced slurry is applied to the surface of the primary modified material to obtain the secondary modified material;

[0019] The secondary modified material is calcined to obtain the tertiary modified material;

[0020] The ceramic-reinforced slurry is applied to the surface of the tertiary modified material to obtain a quaternary modified material;

[0021] The four modified materials are stacked and then hot-pressed to obtain the high-temperature resistant ceramic-based resin composite material.

[0022] Preferably, in conjunction with the second aspect, the concentration of the modified phenolic resin solution is 5-20%;

[0023] And / or, the fiber material matrix is ​​impregnated in a solution of modified phenolic resin for 24-48 hours;

[0024] And / or, the drying temperature is 60-80℃.

[0025] Preferably, in conjunction with the second aspect, the concentration of the ceramic-reinforced slurry is 10-20%.

[0026] In conjunction with the second aspect, preferably, the calcination temperature of the secondary modified material is 400-600℃ and the time is 0.5-2h.

[0027] In conjunction with the second aspect, preferably, the temperature for hot pressing after the four modified materials are stacked is 150-200℃, and the time is 1.5-3h.

[0028] The third aspect of this application provides the application of high-temperature resistant ceramic matrix resin composite materials prepared by the preparation method described in the second aspect in the preparation of turbine rotors.

[0029] Compared with the prior art, the advantages or beneficial effects of the embodiments of this application include at least the following:

[0030] The high-temperature resistant ceramic-based resin composite material provided in this application combines POSS-modified phenolic resin and ceramic-reinforced slurry onto a fiber matrix. On the one hand, it endows the resin composite material with excellent high-temperature resistance. After treatment at 2000℃ for 10 min, the material's microstructure is dense and the overall structure is intact, which can meet the requirements for continuous use in ultra-high temperature environments. On the other hand, it endows the resin composite material with excellent mechanical properties and minimal expansion under continuous ultra-high temperature environments, maintaining excellent mechanical properties after ultra-high temperature treatment. Finally, it can maintain its quality for a long time in ultra-high temperature environments with a high quality retention rate, meeting the application requirements of composite materials at high temperatures. Attached Figure Description

[0031] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0032] Figure 1 Scanning electron microscope (SEM) images of the primary and tertiary modified materials in the Al-high temperature resistant ceramic matrix resin composite material prepared in the embodiments of this application;

[0033] Figure 2 Scanning electron microscope images of the Al-high temperature resistant ceramic matrix resin composite material prepared for the embodiments of this application before and after treatment at 2000°C;

[0034] Figure 3 The images show the Al-high temperature resistant ceramic matrix resin composite material prepared for the embodiments of this application before and after treatment at 2000℃. Detailed Implementation

[0035] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0036] In the following description of this embodiment, the term "and / or" is used to describe the association relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, B existing alone, and A and B existing simultaneously. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0037] In the following description of this embodiment, the term "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0038] Those skilled in the art should understand that, in the following description of the embodiments of this application, the sequence of numbers does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0039] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms "a" and "the" as used in the embodiments of this application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0040] It should be noted that all raw materials and reagents in the embodiments of this application were purchased from the market or prepared according to conventional methods known to those skilled in the art.

[0041] In a first aspect, embodiments of this application provide a high-temperature resistant ceramic-based resin composite material, the composite material comprising a fiber material matrix and a modified phenolic resin and a ceramic-reinforced slurry composited on the fiber material matrix;

[0042] The fiber material matrix includes one of carbon fiber cloth, quartz cloth or silicon carbide fiber cloth.

[0043] The modified phenolic resin is a POSS-modified phenolic resin.

[0044] The raw materials for preparing the ceramic reinforced slurry include, by weight: 5-10 parts silicon carbide powder, 15-45 parts tantalum nitride powder, 1-10 parts nickel powder, 10-25 parts asphalt, and 35-50 parts modified phenolic resin.

[0045] In one aspect, it can endow resin composites with excellent high-temperature resistance. After treatment at 2000℃ for 10 min, the microstructure of the material is dense and the overall structure is intact, which can meet the requirements for continuous use in ultra-high temperature environments. In another aspect, it can endow resin composites with excellent mechanical properties and have small expansion under continuous ultra-high temperature environments, and can maintain excellent mechanical properties after ultra-high temperature treatment. Finally, it can maintain its quality for a long time in ultra-high temperature environments with a high quality retention rate, which meets the application requirements of composite materials at high temperatures.

[0046] It should be noted that the modified phenolic resin used in this application is a POSS-modified phenolic resin. Specifically, a +8 valent metal oxide and POSS are used to modify ordinary phenolic resin. The +8 valent metal oxide is preferably osmium tetroxide. In an acidic aqueous solution of a phenol-formaldehyde mixture, the amine-terminated POSS can chemically react with the hydroxymethyl group of the thermosetting phenolic resin generated by the condensation reaction, resulting in a +8 valent osmium metal and POSS structure within the resin structure. This imparts excellent adhesion to the composite material, providing a foundation for subsequent ceramic-reinforced slurry lamination.

[0047] It should be noted that the phenolic resin used in this application is an ideal flame-retardant adhesive due to its excellent bonding performance, superior ablation resistance, excellent flame retardancy, good stability, heat resistance and good mechanical properties. The phenolic resin modified by POSS has a greater improvement in all properties than the original, especially the mechanical properties, and it also gives the ceramic matrix resin composite material excellent high-temperature resistance.

[0048] In this embodiment, the raw materials used to prepare the ceramic reinforcing slurry include, by weight: silicon carbide powder preferably 5-10 parts, more preferably 6-8 parts; tantalum nitride powder preferably 15-45 parts, more preferably 25-35 parts; nickel powder preferably 1-10 parts, more preferably 4-8 parts; bitumen preferably 10-25 parts, more preferably 15-20 parts; and modified phenolic resin preferably 35-50 parts, more preferably 40-45 parts. By selecting and controlling the content of silicon carbide powder, tantalum nitride powder, nickel powder, bitumen, and modified phenolic resin, a chemically enriched inorganic filler is formed, containing active hydroxyl or carboxyl groups in its structure. This facilitates reaction and rearrangement with phenolic resin at high temperatures, resulting in carbon bonds that combine to form an ultra-high temperature ceramic. After ultra-high temperature treatment at 2000℃, the composite material becomes more dense.

[0049] It should be noted that the ceramic reinforcing slurry used in this application can be pretreated by adding sodium hydroxide, coupling agent and organic solvent containing carboxyl and hydroxyl groups, so that its structure contains active hydroxyl or carboxyl groups, which is beneficial to react and rearrange with phenolic resin at high temperature, and form an ultra-high temperature ceramic structure through carbon bonding.

[0050] In this embodiment, the silicon carbide powder is preferably 200-400 nm in diameter, more preferably 300-350 nm; the tantalum nitride powder is preferably 200-400 nm in diameter, more preferably 300-350 nm; and the nickel powder is preferably 10-40 μm in diameter, more preferably 10-20 μm. By controlling the particle size of the silicon carbide, tantalum nitride, and nickel powders, the performance stability of the ceramic reinforcing slurry can be controlled, ensuring that the slurry is uniformly dispersed on the material matrix. During calcination, a dense ceramic structure can be formed, thereby improving the material's mechanical strength, high-temperature resistance, and chemical stability.

[0051] In this embodiment, the amount of modified phenolic resin added is preferably 0.3-0.7 times that of the composite material, more preferably 0.42 times. The amount of modified phenolic resin added has a significant impact on the performance of the composite material. Too little resin will result in uneven dispersion of the slurry and poor adhesion between the silicon carbide fiber cloths, making hot pressing impossible. Too much resin, on the other hand, will lead to excessive residual carbon in the composite material during high-temperature processes, causing severe overall expansion and deformation, and a significant decrease in mechanical properties.

[0052] Secondly, embodiments of this application also provide a method for preparing the high-temperature resistant ceramic-based resin composite material described in the first aspect, the method comprising:

[0053] The fiber material matrix is ​​impregnated with a solution of modified phenolic resin and then dried to obtain a primary modified material.

[0054] The ceramic-reinforced slurry is applied to the surface of the primary modified material to obtain the secondary modified material;

[0055] The secondary modified material is calcined to obtain the tertiary modified material;

[0056] The ceramic-reinforced slurry is applied to the surface of the tertiary modified material to obtain a quaternary modified material;

[0057] The four modified materials are stacked and then hot-pressed to obtain the high-temperature resistant ceramic-based resin composite material.

[0058] It should be noted that the preparation method provided in this application involves impregnating the fiber material matrix with a modified phenolic resin solution and then drying and curing it, resulting in higher mechanical properties and significantly improved high-temperature resistance. The ceramic-reinforced slurry is then applied to the surface of the primary modified material, and chemically enriched inorganic fillers are added to form a slurry resistant to high-temperature ablation. Silicon carbide fiber cloth itself has advantages such as high tensile strength and tensile modulus, and good heat resistance. After prolonged impregnation with the modified phenolic resin solution, the fiber voids are filled with modified phenolic resin, further enhancing its high-temperature resistance. Furthermore, the impregnated silicon carbide fiber cloth exhibits better fusion with the slurry. The coated single-layer silicon carbide fiber cloth is calcined in a muffle furnace at 400-600℃ for 0.5-2 hours, consuming most of the organic components, which effectively reduces the expansion rate of the composite material during the subsequent high-temperature calcination. The calcined silicon carbide fiber cloth is then impregnated separately into the ceramic-reinforced slurry solution to increase the adhesion between the silicon carbide fibers. The impregnated single-layer silicon carbide fiber cloth is stacked and placed in a hot press instrument and hot-pressed at 150-200℃ for 1.5-3 hours to prepare a high-temperature resistant ceramic matrix resin composite material.

[0059] It should be noted that the fiber material matrix is ​​selected as a single-layer fiber cloth, preferably 10-20 sheets, and more preferably 12-18 sheets. By controlling the number of single-layer fiber cloth sheets as the fiber material matrix and performing hot pressing, a composite material with a uniform and stable thickness can be formed, meeting the requirements in applications.

[0060] In this embodiment, the concentration of the modified phenolic resin solution is preferably 5-20%, more preferably 10-15%; the time for impregnating the fiber matrix in the modified phenolic resin solution is preferably 24-48 hours; and the drying temperature is preferably 60-80°C. By controlling the concentration of the modified phenolic resin solution and the impregnation time of the fiber matrix in the solution, the modified phenolic resin can be uniformly dispersed on the fiber material, thereby improving the adhesion of the fiber matrix and providing a foundation for subsequent composite of ceramic reinforcing slurry.

[0061] In this embodiment, the concentration of the ceramic reinforcing slurry is preferably 10-20%, more preferably 12-17%. By controlling the concentration of the ceramic reinforcing slurry, it can be uniformly bonded to the fiber surface, providing a foundation for further formation of a dense ceramic structure.

[0062] In this embodiment, the preferred calcination temperature for the secondary modified material is 400-600℃, and the preferred calcination time is 0.5-2 hours. By controlling the calcination temperature and time, a dense carbon layer structure can be formed on the surface of the fiber matrix, resulting in a significant ceramic structure in the composite material and thus endowing it with excellent mechanical properties. Furthermore, this process facilitates the removal of most organic components from the slurry while maintaining the original morphology of the silicon carbide fiber cloth. It is particularly beneficial for ceramicizing the slurry portion of the silicon carbide fiber cloth, ensuring a significant reduction in residual carbon in the phenolic resin during the subsequent high-temperature calcination and increasing the ablation resistance of the silicon carbide fiber cloth, thereby improving the high-temperature ablation resistance of the composite material.

[0063] In this embodiment, the temperature for hot pressing after laminating the four modified materials is preferably 150-200℃, more preferably 180℃, and the time is preferably 1.5-3h, more preferably 2.2h. The heating rate is 1-5℃ / min. By controlling the temperature and time of hot pressing, a composite material of a certain thickness can be produced to meet application requirements. Furthermore, the coefficient of thermal expansion of the material can be reduced, thereby endowing the resulting resin composite material with excellent mechanical properties.

[0064] It should be noted that in this application, the ceramic reinforcing slurry is coated and then calcined. This two-coating process, followed by hot pressing, yields a composite material. This double-coating technique imparts excellent high-temperature resistance and mechanical properties to the resin composite. A single coating cannot achieve the desired beneficial effects; multiple coatings not only waste resources but also significantly reduce the material's mechanical properties due to repeated calcination. Therefore, only the preparation process described in this application can produce a high-temperature resistant ceramic-based resin composite material with beneficial comprehensive properties.

[0065] The third aspect of this application provides the application of the high-temperature resistant ceramic-based resin composite material prepared by the method described in the second aspect in a turbine rotor. The high-temperature resistant ceramic-based resin composite material prepared as described above exhibits excellent ultra-high temperature resistance, and after ultra-high temperature treatment at 2000℃, it possesses excellent mechanical properties and mass retention, giving the manufactured turbine rotor superior product competitiveness and broad application prospects.

[0066] The technical solution of this application will be further described below with reference to specific embodiments.

[0067] Example 1

[0068] This embodiment provides a method for preparing A1-high temperature resistant ceramic matrix resin composite material, specifically including:

[0069] S101: Fifteen single-layer silicon carbide fiber cloths were immersed in a 12% concentration modified phenolic resin solution for 32 hours and then dried in an oven at 80°C to obtain a primary modified material.

[0070] S102: Prepare a ceramic reinforcing slurry by mixing 6 parts silicon carbide powder, 30 parts tantalum nitride powder, 5 parts nickel powder, 18 parts asphalt and 40 parts modified phenolic resin. Apply the slurry evenly to the above 15 sheets of secondary modified material using a coating machine.

[0071] S103: Fifteen sheets of secondary modified material were placed in a muffle furnace and calcined for 1.5 hours at a temperature of 550°C and a heating rate of 5°C / min to obtain tertiary modified material.

[0072] S104: The ceramic reinforcing slurry is uniformly coated onto the three-stage modified material using a coating machine to obtain the four-stage modified material;

[0073] S105: The prepared single-layer four-modified material is stacked and placed in a hot press at 180℃ for 2.2h with a heating rate of 5℃ / min to obtain A1-high temperature resistant ceramic matrix resin composite material.

[0074] Example 2

[0075] This embodiment provides a method for preparing A2-high temperature resistant ceramic matrix resin composite material, specifically including:

[0076] S201: Fifteen single-layer silicon carbide fiber cloths were immersed in a 12% concentration modified phenolic resin solution for 32 hours and then dried in an oven at 80°C to obtain a primary modified material.

[0077] S202: Prepare a ceramic reinforcing slurry by mixing 5 parts silicon carbide powder, 45 parts tantalum nitride powder, 1 part nickel powder, 12 parts asphalt and 50 parts modified phenolic resin. Apply the slurry evenly to the above 15 sheets of secondary modified material using a coating machine.

[0078] S203: Fifteen sheets of secondary modified material were placed in a muffle furnace and calcined for 1.5 hours at a temperature of 600°C and a heating rate of 5°C / min to obtain tertiary modified material.

[0079] S204: The ceramic reinforcing slurry is uniformly coated onto the three-stage modified material using a coating machine to obtain the four-stage modified material;

[0080] S205: The single-layer four-modified material is stacked and placed in a hot press at 180℃ for 2.2h with a heating rate of 5℃ / min to obtain A2-high temperature resistant ceramic matrix resin composite material.

[0081] Example 3

[0082] This embodiment provides a method for preparing A3-high temperature resistant ceramic matrix resin composite material, specifically including:

[0083] S301: 18 single-layer silicon carbide fiber cloths were immersed in a 12% concentration modified phenolic resin solution for 32 hours and then dried in an oven at 80°C to obtain a primary modified material.

[0084] S302: Prepare a ceramic reinforcing slurry by mixing 10 parts silicon carbide powder, 15 parts tantalum nitride powder, 1 part nickel powder, 25 parts asphalt and 35 parts modified phenolic resin. Apply the slurry evenly to the above 18 secondary modified materials using a coating machine.

[0085] S303: 18 sheets of secondary modified material were placed in a muffle furnace for calcination. The calcination time was 1.5 h, the calcination temperature was 550 ℃, and the heating rate was 5 ℃ / min to obtain tertiary modified material.

[0086] S304: The ceramic reinforcing slurry is uniformly coated onto the three-stage modified material using a coating machine to obtain the four-stage modified material;

[0087] S305: The single-layer four-modified material is stacked and placed in a hot press at 180℃ for 2.2h with a heating rate of 5℃ / min to obtain A3-high temperature resistant ceramic matrix resin composite material.

[0088] Embodiments 1, 2, and 3 of this application have essentially similar overall performance.

[0089] Meanwhile, to verify the comprehensive performance of the high-temperature resistant ceramic-based resin composite materials prepared in the above embodiments, this application provides the following comparative examples for detailed illustration.

[0090] Comparative Example 1

[0091] This comparative example provides a method for preparing B1-resin composite materials, specifically including:

[0092] S401: Fifteen single-layer silicon carbide fiber cloths were immersed in a 12% concentration modified phenolic resin solution for 32 hours and then dried in an oven at 80°C to obtain a primary modified material.

[0093] S402: Prepare a ceramic reinforcing slurry by mixing 6 parts silicon carbide powder, 30 parts tantalum nitride powder, 5 parts nickel powder, 18 parts asphalt and 40 parts modified phenolic resin. Apply the slurry evenly to the above 15 sheets of secondary modified material using a coating machine.

[0094] S403: Fifteen sheets of secondary modified material were placed in a muffle furnace and calcined for 1.5 hours at a temperature of 550°C and a heating rate of 5°C / min to obtain the secondary modified material.

[0095] S404: The prepared single-layer tertiary modified material is laminated and placed in a hot press at 180℃ for 2.2h with a heating rate of 5℃ / min to obtain B1-resin composite material.

[0096] The difference between Comparative Example 1 and Example 1 is that only one layer of ceramic reinforcing slurry is applied. Because only one application is performed, it cannot meet the requirements for continuous use in ultra-high temperature environments.

[0097] Comparative Example 2

[0098] The composition ratio, preparation operation, and process parameters of the B2-resin composite material prepared in this application are basically the same as those in Example 1. The difference is that after coating a layer of ceramic reinforcing slurry, the material is calcined, then coated with slurry a second time, calcined again, and coated with ceramic reinforcing slurry a third time, and then hot-pressed to obtain the B2-resin composite material.

[0099] The difference between Comparative Example 2 and Example 1 is that the three-layer ceramic reinforcing slurry is applied, and the mechanical properties of the resin composite material are significantly reduced due to the two calcination treatments.

[0100] Comparative Example 3

[0101] The composition ratio, preparation operation, and process parameters of the B3-resin composite material prepared in this application are basically the same as those in Example 1. The difference is that the modified phenolic resin is not coated, and ceramic reinforcing slurry is used for direct treatment to obtain the B3-resin composite material.

[0102] The B3-resin composite material prepared in this application cannot meet the requirements for continuous use in ultra-high temperature environments because it does not have a modified phenolic resin coating and the ceramic reinforcing slurry cannot be effectively bonded to the surface of the fiber material.

[0103] Comparative Example 4

[0104] The composition ratio, preparation operation, and process parameters of the B4-resin composite material prepared in this application are basically the same as those in Example 1. The difference is that only the modified phenolic resin is coated to obtain the B4-resin composite material.

[0105] The B4-resin composite material prepared in this application does not have high-temperature resistance because it is only coated with modified phenolic resin and does not contain ceramic reinforcing slurry. Therefore, it cannot be used in high-temperature environments.

[0106] To verify the morphology and structure of the high-temperature resistant ceramic-based resin composite material prepared in the embodiments of this application, scanning electron microscopy (SEM) was performed on the high-temperature resistant ceramic-based resin composite material prepared in the embodiments. The results are as follows: Figures 1-2 As shown; where, Figure 1Scanning electron microscope (SEM) images of primary and tertiary modified materials in A1-high temperature resistant ceramic matrix resin composites; Figure 2 Scanning electron microscope (SEM) images of A1-high temperature resistant ceramic matrix resin composite material before and after treatment at 2000℃.

[0107] according to Figure 1 Scanning electron microscope images of the primary and tertiary modified materials in the Al-high temperature resistant ceramic matrix resin composite material prepared in this application, where a) is the primary modified material and b) is the tertiary modified material. After high-temperature calcination, the carbon layer formed by the ceramic reinforcing slurry is more dense and more uniform.

[0108] according to Figure 2 The scanning electron microscope (SEM) images of the Al-high temperature resistant ceramic matrix resin composite material prepared in this application before and after treatment at 2000℃ are shown. The Al-high temperature resistant ceramic matrix resin composite material was tested at 2000℃. In the image, a) is before treatment and b) is after treatment. Before treatment, the microstructure of the material is dense. After treatment at 2000℃ for 10 min, although the phenolic resin in the resin composite material decomposes at high temperature, only a small amount of small molecules volatilize, and the overall structure remains intact. This further verifies that this formulation has good heat resistance.

[0109] To verify the high-temperature resistance of the high-temperature resistant ceramic-based resin composite material prepared in the embodiments of this application, DSC / TG tests were performed on the high-temperature resistant ceramic-based resin composite material prepared in the embodiments. After DSC / TG testing of the sample prepared in Example 1 of this application, the maximum exothermic peak was found at 757.6℃; the material experienced the largest weight loss at around 700℃, with a weight loss of 8.68%, mainly due to the volatilization of small molecules generated by the high-temperature decomposition of phenolic resin. When the temperature was further increased, some fillers were oxidized, resulting in an increase in weight, with a thermal weight loss of only 0.5% at 1600℃.

[0110] To verify the mechanical properties of the high-temperature resistant ceramic-based resin composite material prepared in the embodiments of this application, the flexural strength of the high-temperature resistant ceramic-based resin composite material prepared in the embodiments was tested, and the results are shown in Table 1. All mechanical property tests in this application were conducted according to relevant national standards, with flexural strength: GB / T 6569-86. The testing requirements were based on those in the literature "Duan Liuyang; Preparation and Ablation Properties of Ceramizable Resin-Based Composite Materials [D]; Northwestern Polytechnical University; 2020".

[0111] The Al-high temperature resistant ceramic matrix resin composite material prepared in this application was calcined at 1000℃, 1600℃, and 2000℃ for 10 minutes, and then its flexural strength was tested and compared with that of the uncalcined resin composite material at room temperature. The test results are shown in Table 1.

[0112] Table 1. Flexural strength test results of high-temperature resistant ceramic matrix resin composites

[0113]

[0114] As shown in Table 1, the flexural strength of the composite material decreases with increasing treatment temperature, especially when the temperature rises from room temperature to 1000℃. This is partly due to the thermal decomposition of the phenolic resin during the heating process, leading to structural damage; another reason is the oxidation of some high-temperature fillers during heating, forming low-boiling-point oxides that volatilize, resulting in reduced strength. Based on the overall analysis of the mechanical properties after treatment at different temperatures, the high-temperature resistant ceramic-based resin composite material prepared in Example 1 of this application exhibits optimal mechanical properties, meeting the application requirements.

[0115] To verify the morphology and structure of the high-temperature resistant ceramic-based resin composite material prepared in the embodiments of this application after high-temperature treatment, comparative photographs were taken of the actual samples of the high-temperature resistant ceramic-based resin composite material prepared in the embodiments after high-temperature treatment. The results are as follows: Figure 3 As shown; where, Figure 3 These are photos of the A1-high temperature resistant ceramic matrix resin composite material before and after treatment at 2000℃.

[0116] according to Figure 3 As is known, when Al-high temperature resistant ceramic matrix resin composite material is treated at 2000℃ for 10 min, the upper sample is before calcination and the lower sample is after calcination. A comparison of the two samples clearly shows that the composite material after calcination does not show significant expansion, with an expansion rate of 7%. Therefore, the resin composite material prepared in this application can maintain good mechanical properties.

[0117] Therefore, the high-temperature resistant ceramic-based resin composite material provided in this application includes a fiber material matrix and a modified phenolic resin and a ceramic reinforcing slurry composited on the fiber material matrix; the fiber material matrix includes one of carbon fiber cloth, quartz cloth, or silicon carbide fiber cloth; the modified phenolic resin is POSS-modified phenolic resin; the raw materials for preparing the ceramic reinforcing slurry include, by weight: 5-10 parts silicon carbide powder, 15-45 parts tantalum nitride powder, 1-10 parts nickel powder, 10-25 parts pitch, and 35-50 parts modified phenolic resin. After treatment at an ultra-high temperature of 2000℃, the material exhibits a dense microstructure and intact overall structure. Under continuous use in an ultra-high temperature environment, it shows minimal expansion and high mass retention, maintaining excellent mechanical properties after ultra-high temperature treatment, thus meeting the application requirements of composite materials at high temperatures.

[0118] The various embodiments in this specification are described in a progressive manner. The same or similar parts between the various embodiments can be referred to each other. Each embodiment focuses on describing the differences from other embodiments.

[0119] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit this application. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of this application.

Claims

1. A high-temperature resistant ceramic-based resin composite material, characterized in that, The composite material includes a fiber material matrix and a modified phenolic resin and a ceramic reinforcing slurry compounded on the fiber material matrix; The fiber material matrix includes one of carbon fiber cloth, quartz cloth or silicon carbide fiber cloth. The modified phenolic resin is a POSS-modified phenolic resin. The raw materials for preparing the ceramic reinforced slurry include, by weight: 5-10 parts silicon carbide powder, 15-45 parts tantalum nitride powder, 1-10 parts nickel powder, 10-25 parts asphalt, and 35-50 parts modified phenolic resin. The high-temperature resistant ceramic-based resin composite material is obtained by a preparation method including the following process: The fiber material matrix is ​​impregnated with a modified phenolic resin solution and then dried to obtain a primary modified material; The ceramic-reinforced slurry is applied to the surface of the primary modified material to obtain the secondary modified material; The secondary modified material is calcined to obtain the tertiary modified material; The ceramic-reinforced slurry is applied to the surface of the tertiary modified material to obtain a quaternary modified material; The four modified materials are stacked and then hot-pressed to obtain the high-temperature resistant ceramic-based resin composite material.

2. The high-temperature resistant ceramic-based resin composite material according to claim 1, characterized in that, The raw materials for preparing the ceramic reinforced slurry include, by weight: 6-8 parts silicon carbide powder, 25-35 parts tantalum nitride powder, 4-8 parts nickel powder, 15-20 parts asphalt, and 40-45 parts modified phenolic resin.

3. The high-temperature resistant ceramic-based resin composite material according to claim 1, characterized in that, The silicon carbide powder has a diameter of 200-400 nm. And / or, the tantalum nitride powder has a diameter of 200-400 nm; And / or, the nickel powder has a diameter of 10-40 μm.

4. The high-temperature resistant ceramic-based resin composite material according to claim 1, characterized in that, The concentration of the modified phenolic resin solution is 5-20%; And / or, the fiber material matrix is ​​impregnated in the modified phenolic resin solution for 24-48 hours; And / or, the drying temperature is 60-80℃.

5. The high-temperature resistant ceramic-based resin composite material according to claim 1, characterized in that, The concentration of the ceramic-reinforced slurry is 10-20%.

6. The high-temperature resistant ceramic-based resin composite material according to claim 1, characterized in that, The secondary modified material is calcined at a temperature of 400-600℃ for 0.5-2 hours.

7. The high-temperature resistant ceramic-based resin composite material according to claim 1, characterized in that, The temperature for hot pressing after the four modified materials are stacked is 150-200℃, and the time is 1.5-3h.

8. The application of a high-temperature resistant ceramic matrix resin composite material according to any one of claims 1-7 in the preparation of a turbine rotor.

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