Reusable high-toughness in-situ ceramic composite material as well as preparation method and application thereof

Abstract

The invention discloses a reusable high-toughness in-situ ceramic composite material as well as a preparation method and application thereof, and belongs to the technical field of thermal protection materials. The composite material is prepared by sewing a plurality of layers of in-situ ceramic prepregs by adopting ceramic fiber stitches and then curing and forming; wherein the multi-layer in-situ ceramic prepreg is prepared by impregnating ceramic fiber cloth with in-situ ceramic resin; the in-situ ceramic resin comprises heat-resistant phenolic resin and an in-situ ceramic functional component; the in-situ ceramic functional component comprises MAX phase ceramic micro powder and ceramic whiskers. According to the invention, the ceramic fiber cloth is used as a reinforcing body, is cooperated with the MAX-phase ceramic micro powder and the ceramic whiskers, and is matched with a sewing integration and curing molding process, so that the toughening effect and the shape maintaining property are obviously enhanced; the obtained composite material has the capability of being repeatedly used for 20-50 times under severe working conditions of high temperature of 1200 DEG C and long-term service for 30 minutes, and has important application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical field of thermal protection materials, and particularly relates to a reusable, high-strength and tough in-situ ceramized composite material, a preparation method thereof and an application thereof. Background Art

[0002] Hypersonic aircraft are a type of reusable hypersonic vehicle with a speed greater than 5 Mach (Ma) that can maneuver in the near space. When the flight speed reaches 6 Ma, the temperature of large areas such as the windward surface can reach 1200 °C. Without appropriate thermal protection measures, excessive aerodynamic heating will endanger the normal operation of the internal components of the hypersonic aircraft and seriously affect the flight service safety. Thermal protection materials are a key type of material used to cope with aerodynamic heating. Hypersonic aircraft require thermal protection materials to meet requirements such as high temperature resistance, ablation resistance, reusability, high-efficiency heat insulation, high reliability, easy replacement / repair, and low cost.

[0003] Traditional reusable large-area thermal protection materials mainly include rigid ceramic heat shields, metal cover plate thermal protection systems, and ceramic cover plate thermal protection systems. Rigid ceramic heat shields are a typical representative of the first-generation reusable large-area thermal protection materials, having advantages such as low density, good temperature resistance and heat insulation properties. However, they have disadvantages such as brittleness, poor damage resistance, high-temperature shrinkage, easy moisture absorption, and difficult repair. After one service, a large number of replacements are required, resulting in high maintenance costs, large assembly workloads, and long replacement cycles. Metal cover plate thermal protection systems are representatives of the second-generation reusable large-area thermal protection materials. Patent CN

[0004] 101722687A discloses a metal alloy cover plate for a hypersonic vehicle thermal protection system, and its structure includes a honeycomb body, an upper plate, a lower plate, a phase change material, and a housing. However, the use temperature of the metal alloy cover plate is only 600 - 1000 °C. At higher temperatures, the metal alloy cover plate will gradually oxidize and produce irreversible deformation. Therefore, it cannot meet the large-area thermal protection requirements of hypersonic aircraft at 1200 °C. Ceramic cover plate thermal protection systems are representatives of the third-generation reusable large-area thermal protection materials. Patent CN 109367758 B discloses a thermal protection component and a thermal protection system, and its structure includes a ceramic matrix composite material cover plate with an antioxidant coating on the surface, a cover plate support, and a heat insulation layer, which can withstand a high temperature of 1700 °C. However, the preparation cycle of its ceramic matrix composite material cover plate is long and the cost is high. Moreover, the overall structure is complex and the assembly difficulty is large. Therefore, the ceramic cover plate thermal protection system is not suitable for use as a reusable thermal protection material for large areas such as the windward surface of hypersonic aircraft.

[0005] Fiber-reinforced phenolic resin composites have significant advantages such as simple molding process, short preparation cycle, and low cost. They are typical representatives of disposable large-area thermal protection materials and can also be reused a limited number of times at relatively low temperatures. Patent CN117866440A discloses a nano-porous hybrid resin-based thermal insulation and protection material that can be reused a limited number of times and its preparation method. It prepares the nano-porous hybrid resin-based thermal insulation and protection material through a combined process of sol preparation, sol perfusion, reaction gelation, aging, and drying. However, due to the severe oxidation of the pyrolytic carbon of phenolic resin at high temperatures, it can only meet the thermal protection requirements of being reused 10 times at 1000 °C for 1000 s. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a reusable, high-strength and tough in-situ ceramized composite material, its preparation method and application. The obtained composite material can achieve the ability to be reused 20 - 50 times under the harsh working conditions of serving at a high temperature of 1200 °C for 30 min, and has important application prospects.

[0007] To solve the above technical problems, the present invention provides the following technical solutions:

[0008] Provide a reusable, high-strength and tough in-situ ceramized composite material, which is prepared by stitching multiple layers of in-situ ceramized prepregs with ceramic fiber sutures and then curing and molding; wherein:

[0009] The multiple layers of in-situ ceramized prepregs are obtained by impregnating ceramic fiber cloth with in-situ ceramizing resin;

[0010] The in-situ ceramizing resin includes heat-resistant phenolic resin and in-situ ceramizing functional components;

[0011] The in-situ ceramizing functional components include MAX-phase ceramic micro-powders and ceramic whiskers, and the mass ratio of MAX-phase ceramic micro-powders to ceramic whiskers is 3 - 6:1.

[0012] According to the above scheme, the MAX-phase ceramic micro-powder is a self-healing functional element, which is Ta 3 AlC 2 、Ti 3 AlC 2 、Cr 2 TiAlC 2 、Ti 2 AlC、Cr 2 AlC、Ta 2 AlC、Nb 2 AlC、V 2 AlC and Ti 2A combination of one or more of AlN; the ceramic whiskers are toughening functional elements, which are a combination of one or more of silicon carbide, potassium titanate, alumina, and aluminum borate.

[0013] According to the above solution, the heat-resistant phenolic resin is a combination of one or more of boron-modified phenolic resin, silicon-modified phenolic resin, titanium-modified phenolic resin, zirconium-modified phenolic resin, and molybdenum-modified phenolic resin.

[0014] According to the above solution, in the in-situ ceramized resin, by mass, it is: 100 parts of heat-resistant phenolic resin and 50 - 200 parts of in-situ ceramization functional components.

[0015] According to the above solution, the ceramic fiber cloth is a combination of one or more of mullite fiber, alumina fiber, silicon carbide fiber, and silicon nitride fiber.

[0016] According to the above solution, the ceramic fiber suture is a combination of one or more of quartz fiber suture, mullite fiber suture, alumina fiber suture, silicon carbide fiber suture, and silicon nitride fiber suture.

[0017] According to the above solution, the number of layers is 5 - 50 layers.

[0018] According to the above solution, the reusable in-situ ceramized thermal protection composite material can be reused 20 - 50 times under the harsh working conditions of high temperature of 1200 °C and long-term service of 30 min.

[0019] Provide a preparation method of the above reusable and high-strength and tough in-situ ceramized composite material, including the following steps:

[0020] 1) Disperse the in-situ ceramization functional components in the heat-resistant phenolic resin to obtain in-situ ceramized resin; wherein, the in-situ ceramization functional components include MAX phase ceramic micropowder and ceramic whiskers;

[0021] 2) Impregnate the ceramic fiber cloth with the in-situ ceramized resin obtained in step 1), and obtain in-situ ceramized prepreg after drying;

[0022] 3) Sew multiple layers of the in-situ ceramized prepreg obtained in step 2) with ceramic fiber sutures into an integrated in-situ ceramized prepreg, and cure and mold to obtain a reusable and high-strength and tough in-situ ceramized composite material.

[0023] The in-situ ceramization functional components are a composite of self-healing functional elements and toughening functional elements. These components can undergo a ceramization reaction with oxygen and pyrolytic carbon at high temperature, playing the roles of consuming oxygen, isolating oxygen, self-healing, reaction carbon fixation, and synergistic strengthening and toughening.

[0024] According to the above solution, in step 2), the drying process is as follows: drying at 70 - 90 °C for 3 - 5 h to remove the solvent.

[0025] According to the above solution, in step 3), the number of layers is 5 - 50 layers.

[0026] According to the above solution, in step 3), gradient thermal curing process is adopted for curing. Preferably, the gradient thermal curing process is specifically: pre - curing at 100 - 130 °C for 0.5 - 1 h, curing at 150 - 170 °C for 2 - 5 h, and post - curing at 180 - 220 °C for 0.5 - 1.5 h.

[0027] Provide an application of the above reusable, high - strength and tough in - situ ceramized composite material as a thermal protection material in hypersonic aircraft.

[0028] The present invention provides a preparation method of a reusable, high - strength and tough in - situ ceramized composite material, using ceramic fiber cloth with excellent heat resistance as the reinforcement, MAX - phase ceramic micro - powder as the self - healing functional element, and ceramic whiskers as the toughening functional element. It can not only play their respective roles of reinforcement, in - situ oxidation - induced self - healing, and toughening, but also achieve multi - scale synergistic reinforcement and toughening effects. On the one hand, MAX - phase ceramic micro - powder can undergo in - situ ceramization reactions such as oxidation and carbothermal reduction with oxygen and pyrolytic carbon, playing the role of in - situ oxidation - induced self - healing and protecting pyrolytic carbon from being severely oxidized. In addition, because ceramic whiskers can bridge defects, MAX - phase ceramic micro - powder can disperse macroscopic stress, and ceramic fiber cloth can bear the main stress, the three composites can construct a "sub - micron → micron → macroscopic" cascade load transfer chain to achieve cross - scale stress transfer effect. And, ceramic whiskers can absorb energy through pulling out and fracture, MAX - phase ceramic micro - powder can dissipate energy through interface slip, and ceramic fiber cloth can delay failure through delamination and fracture. The three composites can achieve multi - level energy dissipation from the molecular level to the macroscopic level to achieve multi - level toughening effect. And, ceramic whiskers can anchor the self - healing functional element and its oxidation products, and the oxidation products of the self - healing functional element can bond ceramic whiskers and pyrolytic carbon, thereby in - situ constructing a thermal protection barrier integrating ceramic whiskers, pyrolytic carbon, self - healing functional element and its oxidation products, greatly improving the shape - holding property of the material. Moreover, by stitching multiple layers of in - situ ceramized prepregs into an integrated in - situ ceramized prepreg and then curing and molding, the stitching reinforcement effect can be exerted to further improve the strength and shape - holding property of the material. Therefore, this material can be reused 20 - 50 times under the harsh working conditions of 1200 °C high temperature and 30 min long - term service. In addition, this material has a simpler forming process, shorter preparation cycle and lower cost than the ceramic cover - type thermal protection system, and is suitable for use as a reusable thermal protection material for large - area regions such as the windward side of hypersonic aircraft.

[0029] The beneficial effects of the present invention are as follows:

[0030] 1. The present invention provides a reusable, high-strength and tough in-situ ceramized composite material, which uses a ceramic fiber cloth with excellent heat resistance as the reinforcement, MAX-phase ceramic micropowder as the self-healing functional element, and ceramic whiskers as the toughening functional element. The synergistic combination of the three plays a multi-scale synergistic strengthening and toughening role, and also greatly improves the formability of the material. Then, the multi-layer in-situ ceramized prepregs are stitched into an integral body by ceramic fiber sutures and then cured and formed, which can exert the suture reinforcement effect and further improve the strength and formability of the material. The obtained composite material can be reused 20 - 50 times under the harsh working conditions of 1200 °C high temperature and 30 min long-term service, and has important application prospects.

[0031] 2. The preparation method of the present invention has simple process, mild conditions and good repeatability, which is beneficial to industrial application. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 It is a physical picture of the reusable, high-strength and tough in-situ ceramized composite material described in Example 1 after thermal oxidation treatment at 1200 °C for 30 min and repeated accumulation for 20 times.

[0033] Figure 2 It is a surface microtopography picture of the reusable, high-strength and tough in-situ ceramized composite material described in Example 2 after thermal oxidation treatment at 1200 °C for 30 min and repeated accumulation for 30 times. DETAILED DESCRIPTION OF THE INVENTION

[0034] In order to make the technical means, creative features, achieved purposes and effects of the present invention simple and clear, the present invention will be further elaborated below in conjunction with specific embodiments. It should be noted that the present invention includes but is not limited to the following embodiments, and the embodiments and their features in the present invention can be combined with each other without conflict.

[0035] The present invention will be further described below in conjunction with the drawings and embodiments.

[0036] Example 1

[0037] A reusable, high-strength and tough in-situ ceramized composite material and its preparation method, including the following steps:

[0038] 1) Disperse 75 parts of Ti 3 AlC 2 micropowder and 15 parts of potassium titanate whiskers in 100 parts of boron-modified phenolic resin to obtain an in-situ ceramized resin;

[0039] 2) Impregnate the alumina fiber cloth with the in-situ ceramized resin obtained in step 1), and dry it at 80 °C for 4 h to remove the solvent to obtain an in-situ ceramized prepreg;

[0040] 3) Use quartz fiber sutures to stitch the 10 layers of in-situ ceramized prepregs obtained in step 2) into an integrated in-situ ceramized prepreg, pre-cure at 120 °C for 0.5 h, cure at 160 °C for 4 h, and post-cure at 180 °C for 1 h to obtain a reusable, high-strength and tough in-situ ceramized composite material.

[0041] The reusable, high-strength and tough in-situ ceramized composite material prepared in this example was thermally oxidized at 1200 °C for 30 min in an air atmosphere and repeated 20 times cumulatively. The physical picture is as Figure 1 shown. The figure shows that the surface of the sample is flat, without obvious macroscopic defects such as deformation, delamination, cracking, and holes. It shows that the material has excellent high-temperature shape retention. And the flexural strength of the material after thermal oxidation treatment was tested, and the test result was 71 MPa.

[0042] It shows that the reusable, high-strength and tough in-situ ceramized composite material prepared in this example still has a very high flexural strength after being thermally oxidized at 1200 °C for 30 min and repeated 20 times cumulatively.

[0043] Example 2

[0044] A reusable, high-strength and tough in-situ ceramized composite material and its preparation method, including the following steps:

[0045] 1) Disperse 100 parts of Ti 2 AlC micropowder and 30 parts of aluminum borate whiskers in 100 parts of boron-modified phenolic resin to obtain an in-situ ceramized resin;

[0046] 2) Impregnate mullite fiber cloth with the in-situ ceramized resin obtained in step 1), and dry at 80 °C for 4 h to remove the solvent to obtain an in-situ ceramized prepreg;

[0047] 3) Use silicon carbide fiber sutures to stitch the 10 layers of in-situ ceramized prepregs obtained in step 2) into an integrated in-situ ceramized prepreg, pre-cure at 120 °C for 0.5 h, cure at 160 °C for 4 h, and post-cure at 180 °C for 1 h to obtain a reusable, high-strength and tough in-situ ceramized composite material.

[0048] The reusable, high-strength and tough in-situ ceramized composite material prepared in this example was thermally oxidized at 1200 °C for 30 min in an air atmosphere and repeated 30 times cumulatively. The surface microtopography is as Figure 2 shown. The figure shows that the microstructure of the sample is dense and no microcracks are seen. It shows that the material has not been severely damaged; and the flexural strength of the material after thermal oxidation treatment was tested, and the test result was 52 MPa, indicating that the reusable, high-strength and tough in-situ ceramized composite material prepared in this example still has a very high flexural strength after being thermally oxidized at 1200 °C for 30 min and repeated 30 times cumulatively.

[0049] Example 3

[0050] A reusable, high-strength and tough in-situ ceramized composite material and a preparation method thereof, comprising the following steps:

[0051] 1) Disperse 125 parts of Ti 2 AlC micropowder, 30 parts of aluminum borate whiskers and 10 parts of silicon carbide whiskers in 100 parts of boron-modified phenolic resin to obtain an in-situ ceramized resin;

[0052] 2) Impregnate the in-situ ceramized resin obtained in step 1) into a silicon carbide fiber cloth, and dry it at 80 °C for 4 h to remove the solvent to obtain an in-situ ceramized prepreg;

[0053] 3) Sew 10 layers of the in-situ ceramized prepreg obtained in step 2) into an integrated in-situ ceramized prepreg with silicon carbide fiber sutures, and pre-cure it at 120 °C for 0.5 h, cure it at 160 °C for 4 h and post-cure it at 180 °C for 1 h to obtain a reusable, high-strength and tough in-situ ceramized composite material.

[0054] The reusable, high-strength and tough in-situ ceramized composite material prepared in this example was subjected to thermal oxidation treatment at 1200 °C for 30 min in an air atmosphere and repeated 50 times, and the flexural strength of the material after thermal oxidation treatment was tested. The test result was 55 MPa, indicating that the reusable, high-strength and tough in-situ ceramized composite material prepared in this example still had a very high flexural strength after being subjected to thermal oxidation treatment at 1200 °C for 30 min and repeated 50 times.

[0055] Comparative Example 1

[0056] Comparative Example 1 lacks Ti3AlC 2 micropowder compared with Example 1, specifically as follows:

[0057] 1) Disperse 15 parts of potassium titanate whiskers in 100 parts of boron-modified phenolic resin to obtain an in-situ ceramized resin;

[0058] 2) Impregnate the in-situ ceramized resin obtained in step 1) into an alumina fiber cloth, and dry it at 80 °C for 4 h to remove the solvent to obtain an in-situ ceramized prepreg;

[0059] 3) Sew 10 layers of the in-situ ceramized prepreg obtained in step 2) into an integrated in-situ ceramized prepreg with quartz fiber sutures, and pre-cure it at 120 °C for 0.5 h, cure it at 160 °C for 4 h and post-cure it at 180 °C for 1 h to obtain a reusable, high-strength and tough in-situ ceramized composite material.

[0060] The reusable, high-strength and tough in-situ ceramized composite material prepared in this comparative example was subjected to thermal oxidation treatment in an air atmosphere at 1200 °C for 30 min and repeated 20 times in total. After the thermal oxidation treatment, the pyrolytic carbon was severely oxidized and a large number of cracks appeared on the surface of the sample. Then, the flexural strength of the material after the thermal oxidation treatment was tested, and the test result was 8 MPa, indicating that the reusable, high-strength and tough in-situ ceramized composite material prepared in this example basically lost its load-bearing capacity after being thermally oxidized at 1200 °C for 30 min and repeated 20 times in total.

[0061] Comparative Example 2

[0062] Comparative Example 2 lacks potassium titanate whiskers compared with Example 1, as follows:

[0063] 1) Disperse 75 parts of Ti3AlC2 micropowder in 100 parts of boron-modified phenolic resin to obtain an in-situ ceramized resin;

[0064] 2) Impregnate the alumina fiber cloth with the in-situ ceramized resin obtained in step 1), and dry it at 80 °C for 4 h to remove the solvent to obtain an in-situ ceramized prepreg;

[0065] 3) Stitch 10 layers of the in-situ ceramized prepreg obtained in step 2) into an integrated in-situ ceramized prepreg with quartz fiber sutures, and pre-cure it at 120 °C for 0.5 h, cure it at 160 °C for 4 h, and post-cure it at 180 °C for 1 h to obtain a reusable, high-strength and tough in-situ ceramized composite material.

[0066] The reusable, high-strength and tough in-situ ceramized composite material prepared in this comparative example was subjected to thermal oxidation treatment in an air atmosphere at 1200 °C for 30 min and repeated 20 times in total. Then, the flexural strength of the material after the thermal oxidation treatment was tested, and the test result was 28 MPa, indicating that the strength of the reusable, high-strength and tough in-situ ceramized composite material prepared in this example was very low after being thermally oxidized at 1200 °C for 30 min and repeated 20 times in total.

[0067] Comparative Example 3

[0068] Comparative Example 3 lacks the stitching process compared with Example 1, as follows:

[0069] 1) Disperse 75 parts of Ti3AlC2 micropowder and 15 parts of potassium titanate whiskers in 100 parts of boron-modified phenolic resin to obtain an in-situ ceramized resin;

[0070] 2) Impregnate the alumina fiber cloth with the in-situ ceramized resin obtained in step 1), and dry it at 80 °C for 4 h to remove the solvent to obtain an in-situ ceramized prepreg;

[0071] 3) Cure the in-situ ceramized prepreg obtained in step 2) for 0.5 h at 120 °C, 4 h at 160 °C, and post-cure for 1 h at 180 °C to obtain a reusable, high-strength and tough in-situ ceramized composite material.

[0072] The reusable, high-strength and tough in-situ ceramized composite material prepared in this comparative example was heat-oxidized in an air atmosphere at 1200 °C for 30 min and repeated 20 times. After the heat-oxidation treatment, obvious delamination occurred in the sample. And the flexural strength of the material after the heat-oxidation treatment was tested, and the test result was 21 MPa, indicating that the reusable, high-strength and tough in-situ ceramized composite material prepared in this example had very low strength and poor formability after being heat-oxidized at 1200 °C for 30 min and repeated 20 times.

[0073] Comparative Example 4

[0074] Compared with Example 1, the ratio of the self-healing functional elements to the strengthening and toughening functional elements in Comparative Example 4 was less than 3, specifically as follows:

[0075] 1) Disperse 75 parts of Ti3AlC 2 micropowder and 30 parts of potassium titanate whiskers in 100 parts of boron-modified phenolic resin to obtain an in-situ ceramized resin;

[0076] 2) Impregnate the alumina fiber cloth with the in-situ ceramized resin obtained in step 1), and dry it at 80 °C for 4 h to remove the solvent to obtain an in-situ ceramized prepreg;

[0077] 3) Stitch 10 layers of the in-situ ceramized prepreg obtained in step 2) into an integrated in-situ ceramized prepreg, cure it for 0.5 h at 120 °C, 4 h at 160 °C, and post-cure for 1 h at 180 °C to obtain a reusable, high-strength and tough in-situ ceramized composite material.

[0078] The reusable, high-strength and tough in-situ ceramized composite material prepared in this comparative example was heat-oxidized in an air atmosphere at 1200 °C for 30 min and repeated 20 times. After the heat-oxidation treatment, obvious warping occurred in the sample. And the flexural strength of the material after the heat-oxidation treatment was tested, and the test result was 29 MPa, indicating that the reusable, high-strength and tough in-situ ceramized composite material prepared in this example had very low strength and poor formability after being heat-oxidized at 1200 °C for 30 min and repeated 20 times.

[0079] Comparative Example 5

[0080] Compared with Example 1, the ratio of the self-healing functional elements to the strengthening and toughening functional elements in Comparative Example 5 was greater than 6, specifically as follows:

[0081] 1) Dispersed 75 parts of Ti3AlC2 micropowder and 7.5 parts of potassium titanate whiskers in 100 parts of boron-modified phenolic resin to obtain an in-situ ceramized resin;

[0082] 2) Impregnated alumina fiber cloth with the in-situ ceramized resin obtained in step 1), and dried it at 80 °C for 4 h to remove the solvent to obtain an in-situ ceramized prepreg;

[0083] 3) Sewed 10 layers of the in-situ ceramized prepreg obtained in step 2) into an integrated in-situ ceramized prepreg, pre-cured it at 120 °C for 0.5 h, cured it at 160 °C for 4 h, and post-cured it at 180 °C for 1 h to obtain a reusable, high-strength and tough in-situ ceramized composite material.

[0084] The reusable, high-strength and tough in-situ ceramized composite material prepared in this comparative example was subjected to thermal oxidation treatment at 1200 °C for 30 min in an air atmosphere and repeated 20 times. And the flexural strength of the material after thermal oxidation treatment was tested, and the test result was 26 MPa, indicating that the reusable, high-strength and tough in-situ ceramized composite material prepared in this example had very low strength after thermal oxidation treatment at 1200 °C for 30 min and repeated 20 times.

[0085] It should be understood that for those of ordinary skill in the art, improvements or transformations can be made according to the above description, and all such improvements and transformations should fall within the protection scope of the appended claims of the present invention.

Claims

1. A reusable, high-strength and high-toughness in-situ ceramic composite material, characterized in that: The prepreg is prepared by stitching multiple layers of in-situ ceramic prepreg with ceramic fiber stitching and then curing and molding; wherein: The multi-layer in-situ ceramic prepreg is prepared by impregnating ceramic fiber cloth with in-situ ceramic resin; The in-situ ceramic resin comprises a heat-resistant phenolic resin and an in-situ ceramic functional component; The in-situ ceramic functional component comprises MAX phase ceramic micropowder and ceramic whisker, and the mass ratio of MAX phase ceramic micropowder to ceramic whisker is 3-6:

1.

2. The composite material according to claim 1, characterized in that The MAX phase ceramic powder is a combination of one or more of Ta3AlC2, Ti3AlC2, Cr2TiAlC2, Ti2AlC, Cr2AlC, Ta2AlC, Nb2AlC, V2AlC and Ti2AlN; the ceramic whiskers are a combination of one or more of silicon carbide, potassium titanate, aluminum oxide and aluminum borate.

3. The composite material according to claim 1, characterized in that The heat-resistant phenolic resin is a combination of one or more of boron-modified phenolic resin, silicon-modified phenolic resin, titanium-modified phenolic resin, zirconium-modified phenolic resin and molybdenum-modified phenolic resin.

4. The composite material according to claim 1, characterized in that The in-situ ceramic resin comprises, by weight: 100 parts of heat-resistant phenolic resin and 50-200 parts of in-situ ceramic functional components.

5. The composite material according to claim 1, characterized in that The ceramic fiber cloth is a combination of one or more of mullite fiber, alumina fiber, silicon carbide fiber and silicon nitride fiber; the ceramic fiber suture is a combination of one or more of quartz fiber suture, mullite fiber suture, alumina fiber suture, silicon carbide fiber suture and silicon nitride fiber suture.

6. The composite material according to claim 1, characterized in that Multi-layer has 5-50 layers.

7. The composite material according to claim 1, characterized in that The composite material can be reused 20-50 times under the harsh working conditions of high temperature of 1200° C. and long service time of 30 minutes.

8. A method for preparing a reusable, high-strength and high-toughness in-situ ceramic composite material according to any one of claims 1 to 7, characterized in that: The following steps are involved: 1) dispersing an in-situ ceramic functional component in a heat-resistant phenolic resin to obtain an in-situ ceramic resin; wherein the in-situ ceramic functional component comprises MAX phase ceramic powder and ceramic whiskers; 2) impregnating ceramic fiber cloth with the in-situ ceramic resin obtained in step 1), and obtaining an in-situ ceramic prepreg after drying; 3) Using ceramic fiber stitches to stitch the multiple layers of in-situ ceramic prepreg obtained in step 2) into an integrated in-situ ceramic prepreg, and curing and molding to obtain a reusable, high-strength and high-toughness in-situ ceramic composite material.

9. The preparation method according to claim 8, characterized in that: In the step 3), the curing adopts a gradient thermal curing process, specifically: pre-curing at 100-130° C. for 0.5-1 h, curing at 150-170° C. for 2-5 h, and post-curing at 180-220° C. for 0.5-1.5 h.

10. Use of the reusable, high-strength and high-toughness in-situ ceramic composite material according to any one of claims 1 to 7 as a thermal protection material in hypersonic aircraft.

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