A heat-conducting ceramic-based composite material and a preparation method thereof

Abstract

The present invention relates to a thermally conductive ceramic-based composite material and a preparation method thereof. The method comprises the following steps: weaving thin-diameter mesophase pitch-based carbon fibers into a high thermal conductivity fiber preform; preparing an interface layer on the fiber surface of the high thermal conductivity fiber preform by chemical vapor deposition to obtain a porous carbon / carbon matrix; and reacting a hafnium-zirconium composite ceramic precursor solution with the porous carbon / carbon matrix by a precursor impregnation and cracking process to obtain a thermally conductive ceramic-based composite material. The method of the present invention adopts thin-diameter mesophase pitch-based carbon fibers to weave a preform, which greatly reduces the fiber breakage rate in the preform, thereby improving the thermal conductivity of the final composite material; at the same time, a hafnium-zirconium composite ceramic precursor is used as a reactant, and high-temperature cracking is performed to obtain a hafnium-zirconium-carbon solid solution as the matrix of the composite material, which can improve the thermal conductivity and mechanical properties of the composite material, and enhance the ablation resistance of the composite material.

Description

Technical Field

[0001] The present invention belongs to the technical field of ceramic-based composite material preparation, and in particular relates to a heat-conducting ceramic-based composite material and a preparation method thereof. Background Art

[0002] PAN-based carbon fibers and mesophase pitch-based carbon fibers are the two most common types of carbon fibers in this field, and both have been mass-produced. Compared with PAN-based carbon fibers, mesophase pitch-based carbon fibers have the characteristics of high thermal conductivity and can achieve an ultra-high thermal conductivity of 800W / m·K. However, the diameter of general mesophase pitch-based carbon fibers can reach 14μm. Due to the limitation of the diameter of the fiber monofilament, the flexibility is poor. During the weaving process of the preform, the monofilament is more likely to break, which leads to a significant impact on the thermal conductivity and mechanical properties of the final ceramic matrix composite material. In addition, zirconium carbide and hafnium carbide are two common high-performance ceramics with extremely high melting points. They can be used as ceramic matrices resistant to ultra-high temperatures. In comparison, hafnium carbide has better ablation resistance than zirconium carbide, but its density is also higher, which is not conducive to achieving lightweight materials. Therefore, how to further improve the comprehensive performance of ceramic matrix composites, ensure their thermal conductivity, mechanical and ablation resistance in extreme environments, and take lightweighting into account, has become a key research issue in this technical field.

[0003] In summary, it is very necessary to provide a thermally conductive ceramic-based composite material and a preparation method thereof. Summary of the Invention

[0004] In order to solve one or more technical problems existing in the prior art, the present invention provides a thermally conductive ceramic-based composite material and a preparation method thereof. The method of the present invention uses a thinned mesophase pitch-based carbon fiber to weave a high-thermal conductivity fiber preform, significantly reducing the fiber breakage rate in the preform, thereby improving the thermal conductivity of the final composite material; at the same time, a new hafnium-zirconium composite ceramic precursor is used as a reactant, and high-temperature pyrolysis can obtain a high-performance hafnium-zirconium-carbon solid solution as the matrix of the composite material; the method of the present invention can significantly improve the thermal conductivity and mechanical properties of the composite material, and enhance the ablation resistance of the composite material, thereby solving the problem of low thermal conductivity, mechanical properties and / or ablation resistance of ceramic-based composite materials prepared by traditional technologies.

[0005] In a first aspect, the present invention provides a method for preparing a heat-conducting ceramic-based composite material, the method comprising the following steps:

[0006] (1) Weaving thinned mesophase pitch-based carbon fibers into a high thermal conductivity fiber preform;

[0007] (2) preparing an interface layer on the fiber surface of the high thermal conductivity fiber preform by chemical vapor deposition to obtain a porous carbon / carbon matrix;

[0008] (3) The hafnium-zirconium composite ceramic precursor solution is reacted with the porous carbon / carbon matrix through a precursor impregnation and cracking process to obtain a heat-conducting ceramic-based composite material.

[0009] In a second aspect, the present invention provides a thermally conductive ceramic-based composite material prepared by the preparation method described in the first aspect of the present invention.

[0010] Compared with the prior art, the present invention has at least the following beneficial effects:

[0011] (1) The present invention adopts thinned mesophase pitch-based carbon fibers with a diameter of 7-9 μm, which greatly improves their flexibility and makes them more braidable without reducing thermal conductivity and mechanical strength. Weaving them into high thermal conductivity fiber preforms can significantly reduce the fiber breakage rate in the preforms, which is manifested as a significant improvement in the thermal conductivity and mechanical properties of the heat-conducting ceramic-based composite material.

[0012] (2) The present invention adopts a new type of hafnium-zirconium composite ceramic precursor, and on the premise of achieving atomic-level mixing of hafnium and zirconium, a hafnium-zirconium-carbon solid solution with an adjustable ratio of hafnium and zirconium atoms can be prepared; the present invention finds that the hafnium-zirconium-carbon solid solution has excellent anti-ablation performance, which can greatly improve the anti-ablation performance of the composite material in an oxyacetylene ablation environment; the present invention finds that the hafnium-zirconium-carbon solid solution ceramic matrix obtained by using the hafnium-zirconium composite ceramic precursor solution in a ceramic-based composite material has an ultra-high melting point and better anti-ablation performance than a mixed matrix of hafnium carbide and zirconium carbide obtained by using other hafnium-zirconium precursor solutions as reactants, which can greatly improve the temperature resistance and anti-ablation performance of the ceramic-based composite material, and is also more conducive to improving the mechanical properties of the ceramic-based composite material.

[0013] (3) In some preferred embodiments of the present invention, after the precursor impregnation and cracking process, the process further includes a step of performing multiple annealing treatments using a Joule heat ultrafast synthesis process. The present invention has found that performing multiple rapid annealing treatments using a Joule heat ultrafast synthesis process can promote matrix recrystallization and densification through uniform high-temperature rapid heat treatment, and can induce the ceramic grain boundaries of the ceramic-based composite material to be redistributed, forming a grain boundary structure that is more conducive to toughness. In addition, Joule heat rapid annealing is beneficial to retaining the fine grain structure of the material and is more conducive to promoting the formation of a high-temperature stable phase, thereby improving the mechanical properties, temperature resistance and ablation resistance of the finally prepared ceramic-based composite material. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 This is a microstructure diagram (SEM diagram) of the thermal conductivity ceramic-based composite material prepared in Example 1 of the present invention; Figure 1 It can be seen that a hafnium-zirconium-carbon solid solution is formed in the thermal conductivity ceramic matrix composite;

[0015] Figure 2 Schematic diagram of a wedge-shaped high thermal conductivity fiber preform produced according to some specific embodiments of the present invention. DETAILED DESCRIPTION

[0016] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the embodiments described are part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0017] In a first aspect, the present invention provides a method for preparing a heat-conducting ceramic-based composite material, the method comprising the following steps:

[0018] (1) Weaving the thin-diameter mesophase pitch-based carbon fibers into a high thermal conductivity fiber preform; in the present invention, for example, a fine weaving and puncturing process is adopted to obtain a high thermal conductivity fiber preform using the thin-diameter mesophase pitch-based carbon fibers as raw materials;

[0019] (2) preparing an interface layer on the fiber surface of the high thermal conductivity fiber preform by chemical vapor deposition to obtain a porous carbon / carbon matrix; the present invention does not specifically limit the process conditions of the chemical vapor deposition method, and those skilled in the art can routinely select;

[0020] (3) reacting the hafnium-zirconium composite ceramic precursor solution with the porous carbon / carbon matrix through a precursor impregnation and pyrolysis process to obtain a heat-conducting ceramic-based composite material; that is, in step (3), the hafnium-zirconium composite ceramic precursor solution is used as a reactant to compound the porous carbon / carbon matrix, and the heat-conducting ceramic-based composite material is prepared by a precursor impregnation and pyrolysis method.

[0021] The present invention adopts a thinned mesophase asphalt-based carbon fiber with a diameter of 7-9 μm, which greatly improves its flexibility and makes it more braidable without reducing the thermal conductivity and mechanical strength. Weaving it into a high-thermal-conductivity fiber preform can significantly reduce the fiber breakage rate in the preform, which is manifested as a significant improvement in the thermal conductivity and mechanical properties of the heat-conducting ceramic-based composite material. The present invention adopts a novel hafnium-zirconium composite ceramic precursor to achieve atomic-level mixing of hafnium and zirconium, thereby preparing a hafnium-zirconium-carbon solid solution with an adjustable hafnium-zirconium atomic ratio. The present invention finds that the hafnium-zirconium-carbon solid solution has excellent ablation resistance and can significantly improve the ablation resistance of the composite material in an oxyacetylene ablation environment. The present invention finds that the hafnium-zirconium-carbon solid solution ceramic matrix obtained by using the hafnium-zirconium composite ceramic precursor solution in a ceramic-based composite material has an ultra-high melting point and better ablation resistance than a mixed matrix of hafnium carbide and zirconium carbide obtained by using other hafnium-zirconium precursor solutions as reactants, can significantly improve the temperature resistance and ablation resistance of the ceramic-based composite material, and is also more conducive to improving the mechanical properties of the ceramic-based composite material.

[0022] According to some preferred embodiments, in step (1): the diameter of the thinned mesophase pitch-based carbon fiber is 7-9 μm, the tensile strength is 2-3 GPa, and the thermal conductivity is 600-800 W / m·K; the fiber diameter of general mesophase pitch-based carbon fibers can reach 14 μm, which shows poor flexibility. In the subsequent weaving process, the broken wire ratio is high, resulting in a decrease in the mechanical properties and thermal conductivity of the final ceramic-based composite material; generally speaking, the smaller the fiber diameter, the better its flexibility and the higher its weavability; but when the diameter of the mesophase pitch-based carbon fiber is lower than 7 μm, its tensile strength is difficult to meet the weaving requirements, which easily leads to a high broken wire rate in the high thermal conductivity fiber preform; and when the diameter is higher than 9 μm, the fiber flexibility is poor, which also makes the broken wire rate in the high thermal conductivity fiber preform high; the present invention adopts a fiber with a diameter of 7-9 μm, a tensile strength of 2-3 GPa, and a thermal conductivity of 600-800 W / m·K thin-diameter mesophase asphalt-based carbon fibers have high flexibility and high weavability, which are helpful to improve the mechanical properties and thermal conductivity of ceramic-based composite materials; the present invention preferably adopts thin-diameter mesophase asphalt-based carbon fibers with a diameter of 7-9 μm, a tensile strength of 2-3 GPa, and a thermal conductivity of 600-800 W / m·K to obtain the high thermal conductivity fiber preform. The present invention does not make specific restrictions on the source of the thin-diameter mesophase asphalt-based carbon fibers, which are existing known materials. In the present invention, the thin-diameter mesophase asphalt-based carbon fibers can be from Shaanxi Tiance New Materials Technology Co., Ltd.; in the present invention, for example, a fine-weaving puncture process is used to weave the thin-diameter mesophase asphalt-based carbon fibers into a high thermal conductivity fiber preform; the present invention does not make specific restrictions on the fine-weaving puncture process, which can be conventionally selected by those skilled in the art; and / or the density of the high thermal conductivity fiber preform is 0.7-1.0 g / cm3 The present invention adjusts the volume percentage of the thin-diameter mesophase pitch-based carbon fiber to obtain a density of 0.7-1.0g / cm 3 High thermal conductivity fiber preform.

[0023] According to some preferred embodiments, in step (2): the density of the porous carbon / carbon matrix is ​​0.9 to 1.2 g / cm 3 ; and / or the interface layer is one or more of a pyrolytic carbon interface layer, a boron nitride interface layer, and a silicon carbide interface layer; the present invention does not specifically limit the process conditions for depositing the interface layer, which is a conventional technique in the art. The density of the porous carbon / carbon matrix after depositing the interface layer can be 0.9 to 1.2 g / cm by adjusting the volume percentage and / or thickness of the interface layer, which is preferably a pyrolytic carbon interface layer, by using chemical vapor deposition technology. 3 .

[0024] According to some preferred embodiments, in step (3): the hafnium-zirconium composite ceramic precursor solution is prepared by: using xylene to mix propyl hafnate (i.e., tetrapropyl hafnate) and propyl zirconate (i.e., n-propyl zirconate) evenly, then adding ninhydrin as a ligand and adding phenolic epoxy vinyl ester resin and mixing evenly to obtain a mixed solution, and reacting the mixed solution in an argon atmosphere at 5°C to 10°C for 100 to 150 minutes to obtain the hafnium-zirconium composite ceramic precursor solution; the present invention does not specifically limit the phenolic epoxy vinyl ester resin, and a directly purchased product or The products synthesized by the existing methods are all available; the present invention obtains a novel hafnium-zirconium composite ceramic precursor solution in which hafnium and zirconium are mixed at the atomic level by mixing hafnium propyl ester and zirconate and then undergoing coordination reaction and co-hydrolysis reaction; the polyhafnium zirconoxane in the hafnium-zirconium composite ceramic precursor solution has hafnium and zirconium on the same main chain, thus achieving atomic-level mixing; in the present invention, since hafnium and zirconium are associated elements, their properties are similar and their atomic diffusion coefficient is relatively large, thus achieving crystal atomic replacement; and the present invention uses ninhydrin as a ligand, which has three binding sites, compared with ligands such as acetylacetone , which can ensure a more uniform distribution of hafnium propyl ester and zirconate propyl ester, making the ratio of hafnium to zirconium in the polyhafnium zirconoxane main chain more accurate, effectively avoiding excessive aggregation of a certain component resulting in large differences in the atomic composition of the hafnium zirconium carbon solid solution in different regions, and the present invention takes into account the molar mass difference between hafnium and zirconium, and by extending the reaction time in the low-temperature argon environment, it can ensure that the reaction is sufficiently sufficient and uniform, and also ensures a more accurate ratio of hafnium to zirconium in the polyhafnium zirconoxane main chain. The present invention has found that it is precisely the atomic carbon prepared by the above method that can ensure a more accurate ratio of hafnium to zirconium in the polyhafnium zirconoxane main chain. The invention discloses a hafnium-zirconium composite ceramic precursor solution mixed with a first-grade mixture, which is then solidified and subjected to high-temperature cracking treatment to obtain a hafnium-zirconium-carbon solid solution as a ceramic matrix in a ceramic-based composite material. The invention finds that the hafnium-zirconium-carbon solid solution ceramic matrix obtained in a ceramic-based composite material using the hafnium-zirconium composite ceramic precursor solution has an ultra-high melting point and better ablation resistance than a mixed matrix of hafnium carbide and zirconium carbide obtained by using other hafnium-zirconium precursor solutions as reactants. The ceramic-based composite material can greatly improve its temperature resistance and ablation resistance, and is also more conducive to improving its mechanical properties.

[0025] According to some preferred embodiments, the molar amount of the ninhydrin is 0.27 to 1.5 times the sum of the molar amounts of the hafnate propyl ester and the zirconate propyl ester, preferably 0.5 to 0.8 times; and / or the molar amount of the phenolic epoxy vinyl ester resin is 0.9 to 5 times the sum of the molar amounts of the hafnate propyl ester and the zirconate propyl ester, preferably 1.5 to 3 times.

[0026] According to some preferred embodiments, the solid content of the hafnium-zirconium composite ceramic precursor solution is 40-60%, and the viscosity is 30-80 mPa·s; in the present invention, the solid content is the mass percentage of the remaining portion of the hafnium-zirconium composite ceramic precursor solution after solidification of the hafnium-zirconium composite ceramic precursor solution; in the present invention, the amount of the hafnium propyl ester and the zirconium propyl ester is such that the molar ratio of hafnium in the hafnium propyl ester to zirconium in the zirconium propyl ester is (0.1-99.9): (0.1-99.9); the amount of the xylene is such that the solid content of the hafnium-zirconium composite ceramic precursor solution is 40-60%, and the viscosity is 30-80 mPa·s; the molar ratio of hafnium to zirconium in the hafnium-zirconium composite ceramic precursor solution is (0.1-99.9): (0.1-99.9); since the densities of zirconium carbide and hafnium carbide are 6.6 g / cm 3 Left and right and 12.8g / cm 3 The density difference between the two is large, so the present invention can adjust the hafnium-zirconium atomic ratio to obtain a series of hafnium-zirconium-carbon solid solutions; and / or the hafnium-zirconium composite ceramic precursor solution forms a hafnium-zirconium-carbon solid solution as a ceramic matrix in the precursor impregnation and cracking process; for example, Figure 1 As shown, the microstructure of the heat-conducting ceramic-based composite material prepared by the present invention shows that a hafnium-zirconium-carbon solid solution is formed in the heat-conducting ceramic-based composite material.

[0027] The present invention does not specifically limit the impregnation, curing and cracking conditions specifically used in the precursor impregnation, curing and cracking process, and those skilled in the art can make routine selections. The present invention uses a hafnium-zirconium composite ceramic precursor solution as a reactant, and fills the hafnium-zirconium composite ceramic precursor solution into the pores through vacuum and pressure impregnation. After heating at 150-350°C, the ceramic precursor can be completely cured, and then undergoes a high-temperature cracking process. The above impregnation-curing-cracking process is repeated to finally obtain a heat-conducting ceramic-based composite material.

[0028] According to some preferred embodiments, step (4) includes the following sub-steps:

[0029] (a) placing a porous carbon / carbon substrate in a hafnium-zirconium composite ceramic precursor solution and impregnating it for 10 to 360 minutes, filling the hafnium-zirconium composite ceramic precursor solution into the internal pores to obtain a material impregnated with the hafnium-zirconium composite ceramic precursor solution; preferably, the impregnation is vacuum impregnation and pressure impregnation; the present invention does not specifically limit the process parameters of vacuum impregnation and pressure impregnation, which are well known to those skilled in the art and can be carried out using conventional parameters;

[0030] (b) curing the material impregnated with the hafnium-zirconium composite ceramic precursor solution, for example, curing under an inert atmosphere such as nitrogen and heating at 150-350° C., so that the hafnium-zirconium composite ceramic precursor solution inside the pores can be cross-linked and cured, and then placing the cured material in a reaction device, sealing, evacuating, and introducing an inert gas such as nitrogen at a flow rate of, for example, 500-5000 sccm, and cracking at 1500-1800° C., preferably 1600-1800° C., for 10-600 min; preferably, the curing is performed at 150-350° C. for 10-360 min; in the present invention, the heating rate to 150-350° C. and / or 1500-1800° C. can be, for example, 1-10° C. / min;

[0031] (c) After the cracking reaction in step (b) is completed, the temperature is controlled to be lowered, and after cooling to room temperature, the introduction of the inert gas is stopped, and the pressure is restored to atmospheric pressure; in the present invention, the cooling rate can be, for example, 1 to 5°C / minute;

[0032] (d) Repeating steps (a) to (c) at least once, for example, multiple times (twice or more), preferably 1 to 10 times.

[0033] According to some preferred embodiments, in step (3), after the precursor impregnation and cracking process is performed, the process further includes the step of performing multiple annealing treatments using a Joule heat ultrafast synthesis process; the Joule heat ultrafast synthesis process is performed in a Joule ultrafast heating device (Joule ultrafast heating device), and the heating rate of each annealing treatment is 180 to 260°C / s (for example, 180°C / s, 190°C / s, 200°C / s, 210°C / s, 220°C / s, 2 30℃ / s, 240℃ / s, 250℃ / s or 260℃ / s), the annealing temperature is 1600-2000℃ (for example, 1600℃, 1700℃, 1800℃, 1900℃ or 2000℃), the holding time of each annealing is 2-5min (for example, 2, 3, 4 or 5min), and after the holding is completed, it is naturally cooled to room temperature and then the next annealing treatment is performed; the number of annealing treatments is 3-5 times (for example, 3, 4 or 5 times).

[0034] The present invention preferably includes the step of performing multiple annealing treatments using a Joule heat ultrafast synthesis process after the precursor impregnation and cracking process. The present invention finds that performing multiple rapid annealing treatments using a Joule heat ultrafast synthesis process can promote matrix recrystallization and densification through uniform high-temperature rapid heat treatment, and can induce grain boundary redistribution of the ceramic-based composite material to form a ceramic grain boundary structure that is more conducive to toughness. Joule heat rapid annealing is beneficial to retaining the fine grain structure of the material and is more conducive to promoting the formation of a high-temperature stable phase, thereby improving the mechanical properties, temperature resistance and ablation resistance of the finally prepared ceramic-based composite material.

[0035] According to some preferred embodiments, in step (1): the high thermal conductivity fiber preform is a pointed wedge-shaped high thermal conductivity fiber preform; in the present invention, the structure of the pointed wedge-shaped high thermal conductivity fiber preform is as follows. Figure 2 As shown; the preparation of the pointed wedge-shaped high thermal conductivity fiber preform is: mixing the thin-diameter mesophase pitch-based carbon fiber and the PAN-based carbon fiber to obtain a thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth, and then using a lamination and stitching process to make the thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth into a pointed wedge-shaped high thermal conductivity fiber preform; in the present invention, when the pointed wedge-shaped high thermal conductivity fiber preform is used, the obtained thermal conductive ceramic-based composite material is in a pointed wedge shape.

[0036] Since the fiber diameter of general mesophase pitch-based carbon fibers can reach 14μm, they exhibit poor flexibility and are difficult to meet large bending requirements. As a result, the existing preforms woven with general mesophase pitch-based carbon fibers and / or PAN-based carbon fibers are usually flat preforms. However, the ceramic-based composite materials currently made using this conventional structural preform are in the shape of a flat plate. This conventional shape cannot meet the application requirements in certain specific scenarios. In order to obtain a ceramic-based composite material of a specific shape, the traditional preparation technology usually first prepares a flat-plate-shaped ceramic-based composite material and then processes it into a specific shape. This method that requires reprocessing leads to large waste of ceramic-based composite materials and problems of fiber breakage and discontinuity of fibers. Ultimately, the ceramic-based composite materials of a specific shape prepared by traditional technology have deficiencies in terms of thermal conductivity, ablation resistance and / or mechanical properties.

[0037] The present invention preferably designs a fiber preform of a novel structure, that is, a pointed wedge-shaped high thermal conductivity fiber preform is used as a preform for a ceramic-based composite material. The main structural feature of the pointed wedge-shaped high thermal conductivity fiber preform in the present invention is that along a certain fiber direction, the surface of the preform gradually becomes pointed, and the geometric shape is a pointed wedge (a shape in which one end of the preform is pointed and the other end is thick). One end of the pointed wedge-shaped high thermal conductivity fiber preform of the present invention is a pointed end area, and the other end is a thick end area. The present invention finds that the use of such a pointed wedge-shaped preform can obtain a directly integrated pointed wedge-shaped ceramic-based composite material. The pointed wedge-shaped ceramic-based composite material has better structural adaptability and functionality in specific application scenarios, and such a pointed wedge-shaped structure can improve the stress distribution and local strengthening effect of the material. In certain applications, the pointed wedge shape contributes to the optimal fluid flow. ization, reducing frictional resistance, especially in the fields of aerospace, power machinery, etc., the pointed wedge-shaped structure can effectively improve the flow state of airflow and liquid flow, improve energy efficiency, and can better disperse the concentrated area of ​​external force, reduce crack propagation, and improve fatigue resistance under high temperature and high pressure environment; the present invention can realize the weaving of the pointed wedge-shaped high thermal conductivity fiber preform by mixing the fine-diameter mesophase pitch-based carbon fiber and carbon fiber, which gives full play to the high flexibility and high thermal conductivity of the fine-diameter mesophase pitch-based carbon fiber, while the simple PAN-based and general asphalt-based carbon fiber cannot meet the design requirements due to their poor flexibility; and the present invention can realize the controllable adjustment of the thermal conductivity and mechanical properties of the finally prepared ceramic-based composite material by regulating the volume ratio of the fine-diameter mesophase pitch-based carbon fiber to the carbon fiber in the pointed wedge-shaped high thermal conductivity fiber preform.

[0038] The present invention preferably uses a pointed wedge-shaped high-thermal conductivity fiber preform to directly integrate and form a pointed wedge-shaped ceramic-based composite material, which can take into account both fiber continuity and cost economy, and better ensure the thermal conductivity and mechanical properties of the ceramic-based composite material. This is also something that cannot be achieved by using a ceramic-based composite material made of a conventional structural preform and then processing it into a pointed wedge-shaped product after molding. This is because this method of first molding the ceramic-based composite material and then processing it into a product of a specific shape will cause the fibers in the tip area of ​​the product to no longer be continuous. At the same time, there is a large waste in the preparation process, and there are problems with the thermal conductivity, ablation resistance and mechanical properties of the obtained ceramic-based composite material.

[0039] According to some preferred embodiments, the diameter of the thinned mesophase asphalt-based carbon fiber used in the pointed wedge-shaped high thermal conductivity fiber preform is 7-9 μm, the tensile strength is 2-3 GPa, and the thermal conductivity is 600-800 W / m·K, indicating that it has excellent flexibility and can meet the nearly 180° bending of the tip area of ​​the pointed wedge-shaped high thermal conductivity fiber preform without breaking, thereby realizing the weaving of the pointed wedge-shaped high thermal conductivity fiber preform.

[0040] According to some preferred embodiments, in the thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth, the thin-diameter mesophase pitch-based carbon fiber and the PAN-based carbon fiber are vertically distributed, that is, when the thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth is mixed, the thin-diameter mesophase pitch-based carbon fiber and the PAN-based carbon fiber are perpendicular to each other; and / or the surface density of the thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth is 300-400 g / m 2 When the thin-diameter mesophase asphalt-based carbon fiber / carbon fiber bidirectional cloth is mixed in the present invention, the ratio of the thin-diameter mesophase asphalt-based carbon fiber to the PAN-based carbon fiber can be adjusted to meet the subsequent weaving of a pointed wedge-shaped high thermal conductivity fiber preform with a specific volume ratio of thin-diameter mesophase asphalt-based carbon fiber to PAN-based carbon fiber.

[0041] According to some preferred embodiments, the lamination and stitching process is: first, the thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth is folded in half along a direction perpendicular to the thin-diameter mesophase pitch-based carbon fiber, and then multiple pieces (two or more pieces) of the folded thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth are stacked and stitched to obtain a wedge-shaped high thermal conductivity fiber preform; in the present invention, when laminating, the tips of the folded thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth are made to correspond to the tips, and the thick ends are made to correspond to the thick ends, and then PAN-based carbon fiber is used to stitch the multiple folded thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloths into one piece; the present invention does not make specific restrictions on the stitching method used, and those skilled in the art can make conventional choices, for example, an orthogonal stitching method can be selected; the present invention does not make specific restrictions on the number of pieces of thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth used for stacking, and those skilled in the art can make conventional choices based on the thickness requirements of the wedge-shaped high thermal conductivity fiber preform.

[0042] According to some preferred embodiments, the volume ratio of the tapered mesophase pitch-based carbon fibers to the PAN-based carbon fibers in the pointed wedge-shaped high thermal conductivity fiber preform is (1-3):(1-3).

[0043] In the second aspect, the present invention provides a thermally conductive ceramic-based composite material prepared by the preparation method described in the first aspect of the present invention; the thermally conductive ceramic-based composite material prepared by the present invention has a hafnium-zirconium-carbon solid solution as a ceramic matrix, and has the advantages of high thermal conductivity, excellent mechanical properties and ablation resistance, which is manifested in a significant improvement in room temperature thermal conductivity and mechanical properties, and a significant reduction in the offline ablation rate under an oxyacetylene ablation environment.

[0044] According to some preferred embodiments, the density of the thermal conductive ceramic matrix composite material is 3.0 to 5.0 g / cm 3and / or the thermal conductivity of the thermally conductive ceramic matrix composite material at room temperature is greater than or equal to 120W / (m·K), preferably greater than or equal to 210W / (m·K), the tensile strength at room temperature is greater than or equal to 100MPa, preferably greater than or equal to 146MPa, and the oxyacetylene wire ablation rate is less than or equal to 1×10 -3 mm / s.

[0045] The present invention will be further described below by way of examples, but the scope of protection of the present invention is not limited to these embodiments. The present invention may also have various other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art may make various corresponding changes and modifications based on the present invention, but these corresponding changes and modifications should all fall within the scope of protection of the claims attached to the present invention. Unless otherwise specified, the experimental methods used in the following examples and comparative examples are conventional methods. The materials, reagents, etc. used in the following examples and comparative examples, unless otherwise specified, can all be obtained from commercial channels.

[0046] Example 1

[0047] ① Preparation of high thermal conductivity fiber preform: Using fine braiding puncture process, we use thin-diameter mesophase pitch-based carbon fiber with a diameter of 7 μm, a tensile strength of 2.4 GPa, and a thermal conductivity of 800 W / m·K as raw materials to weave a high thermal conductivity fiber preform with a density of 0.8 g / cm 3 A flat plate-shaped high thermal conductivity fiber preform.

[0048] ② Preparation of porous carbon / carbon matrix: Chemical vapor deposition method was used to prepare pyrolytic carbon interface layer on the fiber surface of high thermal conductivity fiber preform, and the density of the prepared porous carbon / carbon matrix was 1.0 g / cm 3 porous carbon / carbon matrix.

[0049] ③ Preparation of hafnium-zirconium composite ceramic precursor solution: In the hafnium-zirconium composite ceramic precursor solution, the atomic molar ratio of hafnium to zirconium is 3:1, the solid content of the hafnium-zirconium composite ceramic precursor solution is 50%, and the viscosity is 55 mPa·s; the hafnium-zirconium composite ceramic precursor solution is prepared by uniformly mixing propyl hafnate and propyl zirconate (in an amount such that the molar ratio of hafnium in propyl hafnate to zirconium in propyl zirconate is 3:1) in xylene, and then adding ninhydrin as a ligand (propyl hafnate, zirconium The hafnium zirconium composite ceramic precursor solution was obtained by uniformly mixing hafnium propyl ester and ninhydrin (the molar ratio of hafnium propyl ester and ninhydrin is 3:1:3) and a phenolic epoxy vinyl ester resin (the molar ratio of hafnium propyl ester, propyl zirconate and phenolic epoxy vinyl ester resin is 3:1:10) to obtain a mixed solution, and reacting the mixed solution under an argon atmosphere at 5° C. for 120 minutes to obtain the hafnium zirconium composite ceramic precursor solution uniformly mixed at the atomic level. The amount of xylene used is such that the solid content of the hafnium zirconium composite ceramic precursor solution is 50% and the viscosity is 55 mPa·s.

[0050] ④ Preparation of heat-conducting ceramic-based composite materials: using hafnium-zirconium composite ceramic precursor solution as reactant, compounding porous carbon / carbon matrix, and preparing flat-plate heat-conducting ceramic-based composite materials with hafnium-zirconium-carbon solid solution as ceramic matrix through precursor impregnation and cracking process, the specific impregnation-curing-cracking process included in the precursor impregnation and cracking process is: placing the porous carbon / carbon matrix in the hafnium-zirconium composite ceramic precursor solution and performing vacuum impregnation for 60 minutes and pressurized impregnation for 60 minutes in sequence to obtain a material impregnated with the hafnium-zirconium composite ceramic precursor solution, the vacuum impregnation pressure is 200Pa, and the pressurized impregnation pressure is 1.5MPa; then the obtained hafnium-zirconium The material impregnated with the composite ceramic precursor solution was cured under a nitrogen atmosphere at a curing temperature of 260°C, a curing time of 120 min at 260°C, and a heating rate of 5°C / min to 260°C. The cured material was then placed in a reaction device, sealed, evacuated, and introduced with nitrogen inert gas at a flow rate of 1000 sccm. The temperature was controlled by a program at a heating rate of 5°C / min and pyrolyzed at 1600°C for 240 min. After the pyrolysis reaction was completed, the temperature was lowered at a rate of 5°C / min, cooled to room temperature, the nitrogen inert gas was turned off, and the material was returned to atmospheric pressure. The impregnation-curing-pyrolysis process was repeated multiple times until a density of 3.8 g / cm was obtained. 3 Flat-plate heat-conducting ceramic-based composite material.

[0051] The thermal conductivity of the thermal conductive ceramic matrix composite material prepared in this embodiment was measured to be 210 W / (m·K) at room temperature, the tensile strength was 146 MPa at room temperature, and the linear ablation rate was 0.53×10 -3 mm / s.

[0052] Example 2

[0053] ① Preparation of high thermal conductivity fiber preform: Using fine weaving puncture process, we use thin-diameter mesophase pitch-based carbon fiber with a diameter of 9 μm, a tensile strength of 2.4 GPa, and a thermal conductivity of 800 W / m·K as raw materials to weave a high thermal conductivity fiber preform with a density of 0.8 g / cm 3 A flat plate-shaped high thermal conductivity fiber preform.

[0054] ② Preparation of porous carbon / carbon matrix: Chemical vapor deposition method was used to prepare pyrolytic carbon interface layer on the fiber surface of high thermal conductivity fiber preform, and the density of the prepared porous carbon / carbon matrix was 1.0 g / cm 3 porous carbon / carbon matrix.

[0055] ③ Preparation of hafnium-zirconium composite ceramic precursor solution: In the hafnium-zirconium composite ceramic precursor solution, the atomic molar ratio of hafnium to zirconium is 3:1, the solid content of the hafnium-zirconium composite ceramic precursor solution is 50%, and the viscosity is 55 mPa·s; the hafnium-zirconium composite ceramic precursor solution is prepared by uniformly mixing propyl hafnate and propyl zirconate (in an amount such that the molar ratio of hafnium in propyl hafnate to zirconium in propyl zirconate is 3:1) in xylene, and then adding ninhydrin as a ligand (propyl hafnate, zirconium The hafnium zirconium composite ceramic precursor solution was obtained by uniformly mixing hafnium propyl ester and ninhydrin (the molar ratio of hafnium propyl ester and ninhydrin is 3:1:3) and a phenolic epoxy vinyl ester resin (the molar ratio of hafnium propyl ester, propyl zirconate and phenolic epoxy vinyl ester resin is 3:1:10) to obtain a mixed solution, and reacting the mixed solution under an argon atmosphere at 5° C. for 120 minutes to obtain the hafnium zirconium composite ceramic precursor solution uniformly mixed at the atomic level. The amount of xylene used is such that the solid content of the hafnium zirconium composite ceramic precursor solution is 50% and the viscosity is 55 mPa·s.

[0056] ④ Preparation of heat-conducting ceramic-based composite materials: using hafnium-zirconium composite ceramic precursor solution as reactant, compounding porous carbon / carbon matrix, and preparing flat-plate heat-conducting ceramic-based composite materials with hafnium-zirconium-carbon solid solution as ceramic matrix through precursor impregnation and cracking process, the specific impregnation-curing-cracking process included in the precursor impregnation and cracking process is: placing the porous carbon / carbon matrix in the hafnium-zirconium composite ceramic precursor solution and performing vacuum impregnation for 60 minutes and pressurized impregnation for 60 minutes in sequence to obtain a material impregnated with the hafnium-zirconium composite ceramic precursor solution, the vacuum impregnation pressure is 200Pa, and the pressurized impregnation pressure is 1.5MPa; then the obtained hafnium-zirconium The material impregnated with the composite ceramic precursor solution was cured under a nitrogen atmosphere at a curing temperature of 260°C, a curing time of 120 min at 260°C, and a heating rate of 5°C / min to 260°C. The cured material was then placed in a reaction device, sealed, evacuated, and introduced with nitrogen inert gas at a flow rate of 1000 sccm. The temperature was controlled by a program at a heating rate of 5°C / min and pyrolyzed at 1600°C for 240 min. After the pyrolysis reaction was completed, the temperature was lowered at a rate of 5°C / min, cooled to room temperature, the nitrogen inert gas was turned off, and the material was returned to atmospheric pressure. The impregnation-curing-pyrolysis process was repeated multiple times until a density of 3.8 g / cm was obtained. 3 Flat-plate heat-conducting ceramic-based composite material.

[0057] The thermal conductivity of the thermal conductive ceramic matrix composite material prepared in this embodiment was measured to be 226 W / (m·K) at room temperature, the tensile strength was 163 MPa at room temperature, and the linear ablation rate was 0.49×10 -3 mm / s.

[0058] Example 3

[0059] ① Preparation of high thermal conductivity fiber preform: Using fine weaving puncture process, we use thin-diameter mesophase pitch-based carbon fiber with a diameter of 5μm, a tensile strength of 2.4GPa, and a thermal conductivity of 800W / m·K as raw materials to weave a high thermal conductivity fiber preform with a density of 0.8g / cm 3 A flat plate-shaped high thermal conductivity fiber preform.

[0060] ② Preparation of porous carbon / carbon matrix: Chemical vapor deposition method was used to prepare pyrolytic carbon interface layer on the fiber surface of high thermal conductivity fiber preform, and the density of the prepared porous carbon / carbon matrix was 1.0 g / cm 3 porous carbon / carbon matrix.

[0061] ③ Preparation of hafnium-zirconium composite ceramic precursor solution: In the hafnium-zirconium composite ceramic precursor solution, the atomic molar ratio of hafnium to zirconium is 3:1, the solid content of the hafnium-zirconium composite ceramic precursor solution is 50%, and the viscosity is 55 mPa·s; the hafnium-zirconium composite ceramic precursor solution is prepared by uniformly mixing propyl hafnate and propyl zirconate (in an amount such that the molar ratio of hafnium in propyl hafnate to zirconium in propyl zirconate is 3:1) in xylene, and then adding ninhydrin as a ligand (propyl hafnate, zirconium The hafnium zirconium composite ceramic precursor solution was obtained by uniformly mixing hafnium propyl ester and ninhydrin (the molar ratio of hafnium propyl ester and ninhydrin is 3:1:3) and a phenolic epoxy vinyl ester resin (the molar ratio of hafnium propyl ester, propyl zirconate and phenolic epoxy vinyl ester resin is 3:1:10) to obtain a mixed solution, and reacting the mixed solution under an argon atmosphere at 5° C. for 120 minutes to obtain the hafnium zirconium composite ceramic precursor solution uniformly mixed at the atomic level. The amount of xylene used is such that the solid content of the hafnium zirconium composite ceramic precursor solution is 50% and the viscosity is 55 mPa·s.

[0062] ④ Preparation of heat-conducting ceramic-based composite materials: using hafnium-zirconium composite ceramic precursor solution as reactant, compounding porous carbon / carbon matrix, and preparing flat-plate heat-conducting ceramic-based composite materials with hafnium-zirconium-carbon solid solution as ceramic matrix through precursor impregnation and cracking process, the specific impregnation-curing-cracking process included in the precursor impregnation and cracking process is: placing the porous carbon / carbon matrix in the hafnium-zirconium composite ceramic precursor solution and performing vacuum impregnation for 60 minutes and pressurized impregnation for 60 minutes in sequence to obtain a material impregnated with the hafnium-zirconium composite ceramic precursor solution, the vacuum impregnation pressure is 200Pa, and the pressurized impregnation pressure is 1.5MPa; then the obtained hafnium-zirconium The material impregnated with the composite ceramic precursor solution was cured under a nitrogen atmosphere at a curing temperature of 260°C, a curing time of 120 min at 260°C, and a heating rate of 5°C / min to 260°C. The cured material was then placed in a reaction device, sealed, evacuated, and introduced with nitrogen inert gas at a flow rate of 1000 sccm. The temperature was controlled by a program at a heating rate of 5°C / min and pyrolyzed at 1600°C for 240 min. After the pyrolysis reaction was completed, the temperature was lowered at a rate of 5°C / min, cooled to room temperature, the nitrogen inert gas was turned off, and the material was returned to atmospheric pressure. The impregnation-curing-pyrolysis process was repeated multiple times until a density of 3.8 g / cm was obtained. 3 Flat-plate heat-conducting ceramic-based composite material.

[0063] The thermal conductivity of the thermal conductive ceramic matrix composite material prepared in this embodiment was measured to be 85W / (m·K) at room temperature, the tensile strength was 101MPa at room temperature, and the linear ablation rate was 0.74×10 -3 mm / s.

[0064] Example 4

[0065] ① Preparation of high thermal conductivity fiber preform: Using fine weaving puncture process, using mesophase pitch-based carbon fiber with a diameter of 10 μm, a tensile strength of 2.4 GPa, and a thermal conductivity of 800 W / m·K as raw material, weaving a high thermal conductivity fiber preform with a density of 0.8 g / cm 3 A flat plate-shaped high thermal conductivity fiber preform.

[0066] ② Preparation of porous carbon / carbon matrix: Chemical vapor deposition method was used to prepare pyrolytic carbon interface layer on the fiber surface of high thermal conductivity fiber preform, and the density of the prepared porous carbon / carbon matrix was 1.0 g / cm 3 porous carbon / carbon matrix.

[0067] ③ Preparation of hafnium-zirconium composite ceramic precursor solution: In the hafnium-zirconium composite ceramic precursor solution, the atomic molar ratio of hafnium to zirconium is 3:1, the solid content of the hafnium-zirconium composite ceramic precursor solution is 50%, and the viscosity is 55 mPa·s; the hafnium-zirconium composite ceramic precursor solution is prepared by uniformly mixing propyl hafnate and propyl zirconate (in an amount such that the molar ratio of hafnium in propyl hafnate to zirconium in propyl zirconate is 3:1) in xylene, and then adding ninhydrin as a ligand (propyl hafnate, zirconium The hafnium zirconium composite ceramic precursor solution was obtained by uniformly mixing hafnium propyl ester and ninhydrin (the molar ratio of hafnium propyl ester and ninhydrin is 3:1:3) and a phenolic epoxy vinyl ester resin (the molar ratio of hafnium propyl ester, propyl zirconate and phenolic epoxy vinyl ester resin is 3:1:10) to obtain a mixed solution, and reacting the mixed solution under an argon atmosphere at 5° C. for 120 minutes to obtain the hafnium zirconium composite ceramic precursor solution uniformly mixed at the atomic level. The amount of xylene used is such that the solid content of the hafnium zirconium composite ceramic precursor solution is 50% and the viscosity is 55 mPa·s.

[0068] ④ Preparation of heat-conducting ceramic-based composite materials: using hafnium-zirconium composite ceramic precursor solution as reactant, compounding porous carbon / carbon matrix, and preparing flat-plate heat-conducting ceramic-based composite materials with hafnium-zirconium-carbon solid solution as ceramic matrix through precursor impregnation and cracking process, the specific impregnation-curing-cracking process included in the precursor impregnation and cracking process is: placing the porous carbon / carbon matrix in the hafnium-zirconium composite ceramic precursor solution and performing vacuum impregnation for 60 minutes and pressurized impregnation for 60 minutes in sequence to obtain a material impregnated with the hafnium-zirconium composite ceramic precursor solution, the vacuum impregnation pressure is 200Pa, and the pressurized impregnation pressure is 1.5MPa; then the obtained hafnium-zirconium The material impregnated with the composite ceramic precursor solution was cured under a nitrogen atmosphere at a curing temperature of 260°C, a curing time of 120 min at 260°C, and a heating rate of 5°C / min to 260°C. The cured material was then placed in a reaction device, sealed, evacuated, and introduced with nitrogen inert gas at a flow rate of 1000 sccm. The temperature was controlled by a program at a heating rate of 5°C / min and pyrolyzed at 1600°C for 240 min. After the pyrolysis reaction was completed, the temperature was lowered at a rate of 5°C / min, cooled to room temperature, the nitrogen inert gas was turned off, and the material was returned to atmospheric pressure. The impregnation-curing-pyrolysis process was repeated multiple times until a density of 3.8 g / cm was obtained. 3 Flat-plate heat-conducting ceramic-based composite material.

[0069] The thermal conductivity of the thermal conductive ceramic matrix composite material prepared in this embodiment was measured to be 111 W / (m·K) at room temperature, the tensile strength was 119 MPa at room temperature, and the linear ablation rate was 0.68×10 -3 mm / s.

[0070] Example 5

[0071] ① Preparation of high thermal conductivity fiber preform: Using fine weaving puncture process, using mesophase pitch-based carbon fiber with a diameter of 14 μm, a tensile strength of 2.4 GPa, and a thermal conductivity of 800 W / m·K as raw material, weaving a high thermal conductivity fiber preform with a density of 0.8 g / cm 3 A flat plate-shaped high thermal conductivity fiber preform.

[0072] ② Preparation of porous carbon / carbon matrix: Chemical vapor deposition method was used to prepare pyrolytic carbon interface layer on the fiber surface of high thermal conductivity fiber preform, and the density of the prepared porous carbon / carbon matrix was 1.0 g / cm 3 porous carbon / carbon matrix.

[0073] ③ Preparation of hafnium-zirconium composite ceramic precursor solution: In the hafnium-zirconium composite ceramic precursor solution, the atomic molar ratio of hafnium to zirconium is 3:1, the solid content of the hafnium-zirconium composite ceramic precursor solution is 50%, and the viscosity is 55 mPa·s; the hafnium-zirconium composite ceramic precursor solution is prepared by uniformly mixing propyl hafnate and propyl zirconate (in an amount such that the molar ratio of hafnium in propyl hafnate to zirconium in propyl zirconate is 3:1) in xylene, and then adding ninhydrin as a ligand (propyl hafnate, zirconium The hafnium zirconium composite ceramic precursor solution was obtained by uniformly mixing hafnium propyl ester and ninhydrin (the molar ratio of hafnium propyl ester and ninhydrin is 3:1:3) and a phenolic epoxy vinyl ester resin (the molar ratio of hafnium propyl ester, propyl zirconate and phenolic epoxy vinyl ester resin is 3:1:10) to obtain a mixed solution, and reacting the mixed solution under an argon atmosphere at 5° C. for 120 minutes to obtain the hafnium zirconium composite ceramic precursor solution uniformly mixed at the atomic level. The amount of xylene used is such that the solid content of the hafnium zirconium composite ceramic precursor solution is 50% and the viscosity is 55 mPa·s.

[0074] ④ Preparation of heat-conducting ceramic-based composite materials: using hafnium-zirconium composite ceramic precursor solution as reactant, compounding porous carbon / carbon matrix, and preparing flat-plate heat-conducting ceramic-based composite materials with hafnium-zirconium-carbon solid solution as ceramic matrix through precursor impregnation and cracking process, the specific impregnation-curing-cracking process included in the precursor impregnation and cracking process is: placing the porous carbon / carbon matrix in the hafnium-zirconium composite ceramic precursor solution and performing vacuum impregnation for 60 minutes and pressurized impregnation for 60 minutes in sequence to obtain a material impregnated with the hafnium-zirconium composite ceramic precursor solution, the vacuum impregnation pressure is 200Pa, and the pressurized impregnation pressure is 1.5MPa; then the obtained hafnium-zirconium The material impregnated with the composite ceramic precursor solution was cured under a nitrogen atmosphere at a curing temperature of 260°C, a curing time of 120 min at 260°C, and a heating rate of 5°C / min to 260°C. The cured material was then placed in a reaction device, sealed, evacuated, and introduced with nitrogen inert gas at a flow rate of 1000 sccm. The temperature was controlled by a program at a heating rate of 5°C / min and pyrolyzed at 1600°C for 240 min. After the pyrolysis reaction was completed, the temperature was lowered at a rate of 5°C / min, cooled to room temperature, the nitrogen inert gas was turned off, and the material was returned to atmospheric pressure. The impregnation-curing-pyrolysis process was repeated multiple times until a density of 3.8 g / cm was obtained. 3 Flat-plate heat-conducting ceramic-based composite material.

[0075] The thermal conductivity of the thermal conductive ceramic matrix composite material prepared in this embodiment was measured to be 96W / (m·K) at room temperature, the tensile strength was 108MPa at room temperature, and the linear ablation rate was 0.70×10 -3 mm / s.

[0076] It can be seen from the above Examples 1 to 5 that, compared with Example 1, the diameter of the mesophase pitch-based carbon fiber used in Example 2 is increased from 7 μm to 9 μm. Due to the increase in diameter, the flexibility becomes worse, and the broken wire rate is slightly reduced, resulting in the thermal conductivity of the ceramic matrix composite material being increased from 210 W / (m·K) to 226 W / (m·K), the tensile strength being increased from 146 MPa to 163 MPa, and the line ablation rate being increased from 0.53×10 -3 mm / s is reduced to 0.49×10 -3 Compared with Example 1, the diameter of the mesophase pitch-based carbon fiber used in Example 3 is reduced from 7 μm to 5 μm. The smaller diameter helps improve flexibility, but the tensile strength it can withstand is reduced, and its broken rate is greatly increased, resulting in the thermal conductivity of the ceramic matrix composite material being reduced from 210 W / (m·K) to 85 W / (m·K), the tensile strength being reduced from 146 MPa to 101 MPa, and the linear ablation rate being reduced from 0.53×10 -3 mm / s increased to 0.74×10-3 mm / s. Compared with Example 1, the diameter of the mesophase pitch-based carbon fiber used in Example 4 was increased from 7 μm to 10 μm. Due to the larger diameter, the flexibility became worse and the broken wire rate became higher, resulting in the thermal conductivity of the ceramic matrix composite material decreasing from 210 W / (m·K) to 111 W / (m·K), the tensile strength decreasing from 146 MPa to 119 MPa, and the linear ablation rate decreasing from 0.53×10 -3 mm / s increased to 0.68×10 - 3 mm / s. Compared with Example 1, the diameter of the mesophase pitch-based carbon fiber used in Example 5 was increased from 7 μm to 14 μm. Due to the larger diameter, the flexibility was extremely poor, and the broken wire rate was very high, resulting in the thermal conductivity of the ceramic matrix composite material being reduced from 210 W / (m·K) to 96 W / (m·K), the tensile strength being reduced from 146 MPa to 108 MPa, and the linear ablation rate being reduced from 0.53×10 -3 mm / s increased to 0.70×10 -3 mm / s.

[0077] Examples 6 to 10

[0078] Examples 6 to 11 are basically the same as Example 1. The specific process parameters and the properties of the finally prepared ceramic matrix composite materials are shown in Table 1 below. The other preparation processes are the same as those in Example 1.

[0079] Table 1

[0080]

[0081]

[0082]

[0083] As can be seen from Table 1 above, compared with Example 1, the hafnium-zirconium atomic ratio of the hafnium-zirconium composite ceramic precursor solution used in Example 6 is increased from 3:1 to 10:1, which significantly increases the proportion of hafnium in the hafnium-zirconium-carbon solid solution, resulting in a density of the ceramic matrix composite material from 3.8 g / cm 3 Increased to 4.3g / cm 3 The oxyacetylene wire ablation rate also increased from 0.53×10 -3 mm / s decreased to 0.21×10 - 3 mm / s, and the ablation resistance is enhanced. Compared with Example 1, the hafnium-zirconium atomic ratio of the hafnium-zirconium composite ceramic precursor solution used in Example 7 is reduced from 3:1 to 1:1, which significantly reduces the proportion of hafnium in the hafnium-zirconium-carbon solid solution, resulting in a density of the ceramic matrix composite material from 3.8 g / cm 3 Reduced to 3.55g / cm 3The oxyacetylene wire ablation rate also increased from 0.53×10 -3 mm / s increased to 0.61×10 -3 mm / s, and the ablation resistance is reduced. Compared with Example 1, the hafnium-zirconium atomic ratio of the hafnium-zirconium composite ceramic precursor solution used in Example 8 is reduced from 3:1 to 1:3, which significantly reduces the proportion of hafnium in the hafnium-zirconium-carbon solid solution, resulting in a decrease in the density of the ceramic matrix composite material from 3.8 g / cm 3 Reduced to 3.26g / cm 3 The oxyacetylene wire ablation rate also increased from 0.53×10 -3 mm / s increased to 0.77×10 -3 mm / s, and the ablation resistance is reduced. Compared with Example 1, the hafnium-zirconium atomic ratio of the hafnium-zirconium composite ceramic precursor solution used in Example 9 is reduced from 3:1 to 1:10, which significantly reduces the proportion of hafnium in the hafnium-zirconium-carbon solid solution, resulting in a decrease in the density of the composite material from 3.8 g / cm 3 Reduced to 3.11g / cm 3 The oxyacetylene wire ablation rate also increased from 0.53×10 -3 mm / s increased to 0.92×10 -3 mm / s, the anti-ablation performance is reduced. Compared with Example 1, the density of the porous carbon / carbon matrix used in Example 10 is increased from 1.0 g / cm 3 Increased to 1.1g / cm 3 , which reduces the internal pore volume and the content of hafnium-zirconium-carbon solid solution in the thermal conductivity ceramic matrix composite material, resulting in the density of the composite material from 3.8g / cm 3 Reduced to 3.64g / cm 3 The oxyacetylene wire ablation rate also increased from 0.53×10 -3 mm / s increased to 0.59×10 -3 mm / s, the anti-ablation performance is reduced. Compared with Example 1, the density of the porous carbon / carbon matrix used in Example 11 is reduced from 1.0 g / cm 3 Reduced to 0.9g / cm 3 , which increases the internal pore volume and improves the Hf-Zr-C solid solution content in the thermal conductivity ceramic matrix composite material, resulting in a decrease in the density of the composite material from 3.8 g / cm 3 Increased to 3.97g / cm 3 The oxyacetylene wire ablation rate also increased from 0.53×10 -3 mm / s decreased to 0.47×10 -3 mm / s, and the anti-ablation performance is enhanced.

[0084] Example 12

[0085] ① is the same as step ① in Example 1.

[0086] ② is the same as step ② of Example 1.

[0087] ③ is the same as step ③ of Example 1.

[0088] ④ Preparation of heat-conducting ceramic-based composite materials: using hafnium-zirconium composite ceramic precursor solution as reactant, compounding porous carbon / carbon matrix, and preparing flat-plate heat-conducting ceramic-based composite materials with hafnium-zirconium-carbon solid solution as ceramic matrix through precursor impregnation and cracking process, the specific impregnation-curing-cracking process included in the precursor impregnation and cracking process is: placing the porous carbon / carbon matrix in the hafnium-zirconium composite ceramic precursor solution and performing vacuum impregnation for 60 minutes and pressurized impregnation for 60 minutes in sequence to obtain a material impregnated with the hafnium-zirconium composite ceramic precursor solution, the vacuum impregnation pressure is 200Pa, and the pressurized impregnation pressure is 1.5MPa; then the obtained hafnium-zirconium The material impregnated with the composite ceramic precursor solution was cured under a nitrogen atmosphere at a curing temperature of 260°C, a curing time of 120 min at 260°C, and a heating rate of 5°C / min to 260°C. The cured material was then placed in a reaction device, sealed, evacuated, and introduced with nitrogen inert gas at a flow rate of 1000 sccm. The temperature was controlled by a program at a heating rate of 5°C / min and pyrolyzed at 1600°C for 240 min. After the pyrolysis reaction was completed, the temperature was lowered at a rate of 5°C / min, cooled to room temperature, the nitrogen inert gas was turned off, and the material was returned to atmospheric pressure. The impregnation-curing-pyrolysis process was repeated multiple times until a density of 3.8 g / cm was obtained. 3 The flat-plate thermally conductive ceramic-based composite material is prepared. After the precursor impregnation and cracking process is completed, the flat-plate thermally conductive ceramic-based composite material is further annealed three times using a Joule heat ultrafast synthesis process; wherein, the Joule heat ultrafast synthesis process is carried out in a Joule ultrafast heating device, the heating rate of each annealing treatment is 200°C / s, the annealing treatment is carried out in a nitrogen atmosphere, the annealing temperature is 1800°C, and the holding time for each annealing at 1800°C is 3 minutes. After the holding period is completed, it is naturally cooled to room temperature before the next annealing treatment is carried out.

[0089] The thermal conductivity of the thermal conductive ceramic matrix composite material finally prepared in this embodiment was measured to be 210 W / (m·K) at room temperature, the tensile strength was 155 MPa at room temperature, and the linear ablation rate was 0.38×10 -3 mm / s.

[0090] Example 13

[0091] Example 13 is substantially the same as Example 12, except that:

[0092] ④ Preparation of heat-conducting ceramic-based composite materials: using hafnium-zirconium composite ceramic precursor solution as reactant, compounding porous carbon / carbon matrix, and preparing flat-plate heat-conducting ceramic-based composite materials with hafnium-zirconium-carbon solid solution as ceramic matrix through precursor impregnation and cracking process, the specific impregnation-curing-cracking process included in the precursor impregnation and cracking process is: placing the porous carbon / carbon matrix in the hafnium-zirconium composite ceramic precursor solution and performing vacuum impregnation for 60 minutes and pressurized impregnation for 60 minutes in sequence to obtain a material impregnated with the hafnium-zirconium composite ceramic precursor solution, the vacuum impregnation pressure is 200Pa, and the pressurized impregnation pressure is 1.5MPa; then the obtained hafnium-zirconium The material impregnated with the composite ceramic precursor solution was cured under a nitrogen atmosphere at a curing temperature of 260°C, a curing time of 120 min at 260°C, and a heating rate of 5°C / min to 260°C. The cured material was then placed in a reaction device, sealed, evacuated, and introduced with nitrogen inert gas at a flow rate of 1000 sccm. The temperature was controlled by a program at a heating rate of 5°C / min and pyrolyzed at 1600°C for 240 min. After the pyrolysis reaction was completed, the temperature was lowered at a rate of 5°C / min, cooled to room temperature, the nitrogen inert gas was turned off, and the material was returned to atmospheric pressure. The impregnation-curing-pyrolysis process was repeated multiple times until a density of 3.8 g / cm was obtained. 3 The flat-plate thermally conductive ceramic-based composite material is annealed after the precursor impregnation and cracking process is completed; wherein, the annealing treatment is carried out in a nitrogen atmosphere, the annealing temperature is 1800°C, the holding time at 1800°C is 9 minutes, and the heating rate to 1800°C is 10°C / min.

[0093] The thermal conductivity of the thermally conductive ceramic-based composite material finally prepared in this embodiment was measured to be 210 W / (m·K) at room temperature, and the tensile strength at room temperature was 93 MPa.

[0094] Example 14

[0095] ① Weaving fine-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth: The fine-diameter mesophase pitch-based carbon fiber and PAN-based carbon fiber are mixed to obtain fine-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth, so that the fine-diameter mesophase pitch-based carbon fiber and PAN-based carbon fiber are vertically distributed, and the surface density of the fine-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth is 365g / m 2 The thin-diameter mesophase pitch-based carbon fiber used is a thin-diameter mesophase pitch-based carbon fiber with a diameter of 7 μm, a tensile strength of 2.4 GPa, and a thermal conductivity of 800 W / m·K.

[0096] ② Preparation of a pointed wedge-shaped high thermal conductivity fiber preform: A stacking and stitching process is adopted to weave a thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth to obtain a pointed wedge-shaped high thermal conductivity fiber preform, specifically: first, the thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth is folded in half along a direction perpendicular to the thin-diameter mesophase pitch-based carbon fiber, and then multiple pieces of the folded thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth are stacked and stitched to obtain a pointed wedge-shaped high thermal conductivity fiber preform; during the stacking, the tips of the folded thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth correspond to the tips, and the thick ends correspond to the thick ends, and then PAN-based carbon fiber is used to stitch the stacked multiple pieces of the folded thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth into one piece to obtain a pointed wedge-shaped high thermal conductivity fiber preform; the volume ratio of the thin-diameter mesophase pitch-based carbon fiber to the PAN-based carbon fiber in the obtained pointed wedge-shaped high thermal conductivity fiber preform is 2:1, and the density of the pointed wedge-shaped high thermal conductivity fiber preform is 0.75 g / cm 3 .

[0097] ③ Preparation of wedge-shaped porous carbon / carbon matrix: A pyrolytic carbon interface layer was prepared on the fiber surface of the wedge-shaped high thermal conductivity fiber preform by chemical vapor deposition, and a density of 0.95 g / cm was obtained. 3 wedge-shaped porous carbon / carbon matrix.

[0098] ④ Preparation of hafnium-zirconium composite ceramic precursor solution: In the hafnium-zirconium composite ceramic precursor solution, the atomic molar ratio of hafnium to zirconium is 3:1, the solid content of the hafnium-zirconium composite ceramic precursor solution is 50%, and the viscosity is 55 mPa·s; the hafnium-zirconium composite ceramic precursor solution is prepared by uniformly mixing propyl hafnate and propyl zirconate (in an amount such that the molar ratio of hafnium in propyl hafnate to zirconium in propyl zirconate is 3:1) in xylene, and then adding ninhydrin as a ligand (propyl hafnate, zirconium The hafnium zirconium composite ceramic precursor solution was obtained by uniformly mixing hafnium propyl ester and ninhydrin (the molar ratio of hafnium propyl ester and ninhydrin is 3:1:3) and a phenolic epoxy vinyl ester resin (the molar ratio of hafnium propyl ester, propyl zirconate and phenolic epoxy vinyl ester resin is 3:1:10) to obtain a mixed solution, and reacting the mixed solution under an argon atmosphere at 5° C. for 120 minutes to obtain the hafnium zirconium composite ceramic precursor solution uniformly mixed at the atomic level. The amount of xylene used is such that the solid content of the hafnium zirconium composite ceramic precursor solution is 50% and the viscosity is 55 mPa·s.

[0099] ⑤ Preparation of thermal conductivity ceramic-based composite materials: using a hafnium-zirconium composite ceramic precursor solution as a reactant, compounding a wedge-shaped prosthetic porous carbon / carbon matrix, and preparing a wedge-shaped thermal conductivity ceramic-based composite material with a hafnium-zirconium-carbon solid solution as a ceramic matrix through a precursor impregnation and cracking process, wherein the precursor impregnation and cracking process includes a specific impregnation-curing-cracking process as follows: placing the wedge-shaped prosthetic porous carbon / carbon matrix in a hafnium-zirconium composite ceramic precursor solution and sequentially performing vacuum impregnation for 60 minutes and pressurized impregnation for 60 minutes to obtain a material impregnated with the hafnium-zirconium composite ceramic precursor solution, wherein the vacuum impregnation pressure is 200 Pa and the pressurized impregnation pressure is 1.5 MPa; and then The material impregnated with the obtained hafnium-zirconium composite ceramic precursor solution was cured in a nitrogen atmosphere at a curing temperature of 260°C, a curing time of 120 min at 260°C, and a heating rate of 5°C / min to 260°C. The cured material was then placed in a reaction device, sealed, evacuated, and introduced with nitrogen inert gas at a flow rate of 1000 sccm. The temperature was controlled by a program at a heating rate of 5°C / min and cracked at 1600°C for 240 min. After the cracking reaction was completed, the temperature was lowered at a rate of 5°C / min, cooled to room temperature, the nitrogen inert gas was turned off, and the material was returned to atmospheric pressure. The impregnation-curing-cracking process was repeated multiple times until a density of 3.8 g / cm was obtained. 3 Sharp wedge-shaped thermal conductivity ceramic matrix composite material.

[0100] The thermal conductivity of the wedge-shaped thermally conductive ceramic matrix composite material prepared in this embodiment was measured to be 202 W / (m·K) at room temperature, the tensile strength was 134 MPa at room temperature, and the linear ablation rate was 0.57×10 -3 mm / s.

[0101] Comparative Example 1

[0102] Comparative Example 1: A flat plate-shaped heat-conducting ceramic-based composite material was obtained by the same method as in Example 1, and then machined into a pointed wedge-shaped heat-conducting ceramic-based composite material.

[0103] The thermal conductivity of the wedge-shaped thermal conductive ceramic matrix composite material prepared in this comparative example is measured to be 75W / (m·K) at room temperature, the tensile strength is 96MPa at room temperature, and the linear ablation rate is 0.81×10 -3 mm / s.

[0104] Comparative Example 2

[0105] ①Same as step ① of Example 14.

[0106] ② Preparation of a flat-plate high thermal conductivity fiber preform: A lamination and stitching process is adopted to obtain a flat-plate high thermal conductivity fiber preform by weaving a thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth. Specifically, multiple pieces of thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth are stacked and stitched together to obtain a flat-plate high thermal conductivity fiber preform; the volume ratio of the thin-diameter mesophase pitch-based carbon fiber to the PAN-based carbon fiber in the obtained flat-plate high thermal conductivity fiber preform is 2:1, and the density of the flat-plate high thermal conductivity fiber preform is 0.75g / cm 3 ; The flat-plate-shaped high thermal conductivity fiber preform obtained in step ② is used to replace the pointed wedge-shaped high thermal conductivity fiber preform in Example 14 to carry out the same subsequent steps ③, step ④ and step ⑤ as in Example 14.

[0107] The thermal conductivity of the flat plate-shaped heat-conducting ceramic matrix composite material prepared in this comparative example is measured to be 206 W / (m·K) at room temperature, the tensile strength is 138 MPa at room temperature, and the linear ablation rate is 0.55×10 -3 mm / s.

[0108] In this comparative example, the flat plate-shaped heat-conducting ceramic matrix composite material is machined into a pointed wedge-shaped heat-conducting ceramic matrix composite material, and the thermal conductivity of the pointed wedge-shaped heat-conducting ceramic matrix composite material at room temperature is measured to be 72W / (m·K), the tensile strength at room temperature is 91MPa, and the linear ablation rate is 0.85×10 -3 mm / s.

[0109] Although the performance of the flat-plate thermally conductive ceramic-based composite material prepared in this comparative example is basically the same as that of the pointed wedge-shaped thermally conductive ceramic-based composite material prepared in Example 14, when the flat-plate thermally conductive ceramic-based composite material prepared in this comparative example is processed into a pointed wedge-shaped thermally conductive ceramic-based composite material by traditional machining, this traditional method will cause the fibers in the tip area of ​​the product to no longer be continuous, resulting in a significant decrease in the thermal conductivity, ablation resistance and mechanical properties of the prepared pointed wedge-shaped thermally conductive ceramic-based composite material.

[0110] Comparative Example 3

[0111] ① is the same as step ① in Example 1.

[0112] ② is the same as step ② of Example 1.

[0113] ③ Preparation of hafnium-zirconium composite ceramic precursor solution: In the hafnium-zirconium composite ceramic precursor solution, the atomic molar ratio of hafnium to zirconium is 3:1, and the solid content of the hafnium-zirconium composite ceramic precursor solution is 50%. The hafnium-zirconium composite ceramic precursor solution is prepared by uniformly mixing propyl hafnate and propyl zirconate (in an amount such that the molar ratio of hafnium in hafnium ester to zirconium in zirconate is 3:1) in xylene, and then adding acetylacetone as a ligand (hafnium ester The invention relates to a method for preparing a hafnium-zirconium composite ceramic precursor solution. The method comprises the following steps: uniformly mixing hafnium propyl ester, propyl zirconate and acetylacetone (the molar ratio of hafnium propyl ester, propyl zirconate and acetylacetone is 3:1:3) and allyl phenolic resin (the molar ratio of hafnium propyl ester, propyl zirconate and allyl phenolic resin is 3:1:10) to obtain a mixed solution, reacting the mixed solution under an argon atmosphere at 15° C. for 70 minutes to obtain a molecular-level mixed hafnium-zirconium composite ceramic precursor solution. The amount of xylene used is such that the solid content of the hafnium-zirconium composite ceramic precursor solution is 50%.

[0114] ④ Preparation of thermal conductivity ceramic-based composite materials: The hafnium-zirconium composite ceramic precursor solution obtained in step ③ is used as a reactant to compound the porous carbon / carbon matrix, and a thermal conductivity ceramic-based composite material is prepared by a precursor impregnation and cracking process, wherein the precursor impregnation and cracking process includes a specific impregnation-curing-cracking process as follows: placing the porous carbon / carbon matrix in the hafnium-zirconium composite ceramic precursor solution and sequentially performing vacuum impregnation for 60 minutes and pressurized impregnation for 60 minutes to obtain a material impregnated with the hafnium-zirconium composite ceramic precursor solution, wherein the vacuum impregnation pressure is 200 Pa and the pressurized impregnation pressure is 1.5 MPa; then the obtained hafnium-zirconium composite ceramic precursor is placed in the hafnium-zirconium composite ceramic precursor solution. The material impregnated with the solution was cured in a nitrogen atmosphere at a curing temperature of 260°C, a curing time of 120 min at 260°C, and a heating rate of 5°C / min to 260°C. The cured material was then placed in a reaction device, sealed, evacuated, and introduced with nitrogen inert gas at a flow rate of 1000 sccm. The temperature was controlled by a program at a heating rate of 5°C / min and pyrolyzed at 1600°C for 240 min. After the pyrolysis reaction was completed, the temperature was lowered at a rate of 5°C / min, cooled to room temperature, the nitrogen inert gas was turned off, and the pressure was restored to atmospheric pressure. The impregnation-curing-pyrolysis process was repeated multiple times until a density of 3.8 g / cm was obtained. 3 A flat plate-shaped heat-conducting ceramic matrix composite material with hafnium carbide and zirconium carbide as a ceramic matrix.

[0115] The thermal conductivity of the flat plate-shaped heat-conducting ceramic matrix composite material prepared in this comparative example is measured to be 210 W / (m·K) at room temperature, the tensile strength is 138 MPa at room temperature, and the linear ablation rate is 1.1×10 -3 mm / s.

[0116] Comparing Example 1 with Comparative Example 3, it can be seen that by using the hafnium-zirconium composite ceramic precursor solution of the present invention as the impregnation solution, a hafnium-zirconium-carbon solid solution ceramic matrix can be obtained in the ceramic-based composite material, which is beneficial to improving the ablation resistance and mechanical properties of the ceramic-based composite material.

[0117] Parts of the present invention that are not described in detail are well known to those skilled in the art.

[0118] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A method for preparing a heat-conducting ceramic-based composite material, characterized in that: The method comprises the following steps: (1) Weaving thin-diameter mesophase pitch-based carbon fibers into a high thermal conductivity fiber preform; the diameter of the thin-diameter mesophase pitch-based carbon fibers is 7-9 μm; (2) preparing an interface layer on the fiber surface of a high thermal conductivity fiber preform by chemical vapor deposition to obtain a porous carbon / carbon matrix; (3) A hafnium-zirconium composite ceramic precursor solution is reacted with a porous carbon / carbon matrix through a precursor impregnation and cracking process to obtain a heat-conducting ceramic-based composite material; the hafnium-zirconium composite ceramic precursor solution is prepared by: using xylene to evenly mix hafnium propyl ester and zirconate propyl ester, then adding ninhydrin as a ligand and adding phenolic epoxy vinyl ester resin and mixing them evenly to obtain a mixed solution, and reacting the mixed solution in an argon atmosphere at 5°C to 10°C for 100 to 150 minutes to obtain the hafnium-zirconium composite ceramic precursor solution.

2. The preparation method according to claim 1, characterized in that In step (1): The thinned mesophase pitch-based carbon fibers have a tensile strength of 2-3 GPa and a thermal conductivity of 600-800 W / m·K. Weaving the thinned mesophase pitch-based carbon fibers into a high thermal conductivity fiber preform using a fine weaving and puncturing process; and / or The density of the high thermal conductivity fiber preform is 0.7-1.0 g / cm 3 .

3. The preparation method according to claim 1, characterized in that In step (2): The density of the porous carbon / carbon matrix is ​​0.9-1.2 g / cm 3 and / or The interface layer is one or more of a pyrolytic carbon interface layer, a boron nitride interface layer, and a silicon carbide interface layer.

4. The preparation method according to claim 1, wherein: The molar amount of the ninhydrin is 0.5 to 0.8 times the sum of the molar amounts of the hafnate propyl ester and the zirconate propyl ester; and / or The molar amount of the phenolic epoxy vinyl ester resin is 1.5 to 3 times the sum of the molar amounts of the propyl hafnate and the propyl zirconate.

5. The preparation method according to claim 1, wherein: The hafnium-zirconium composite ceramic precursor solution has a solid content of 40-60% and a viscosity of 30-80 mPa·s; The molar ratio of hafnium to zirconium in the hafnium-zirconium composite ceramic precursor solution is (0.1-99.9): (0.1-99.9); and / or The hafnium-zirconium composite ceramic precursor solution forms a hafnium-zirconium-carbon solid solution as a ceramic matrix during the precursor impregnation and cracking process.

6. The preparation method according to claim 1, characterized in that Step (3) includes the following sub-steps: (a) impregnating the porous carbon / carbon substrate in a hafnium-zirconium composite ceramic precursor solution for 10 to 360 minutes to obtain a material impregnated with the hafnium-zirconium composite ceramic precursor solution; the impregnation being vacuum impregnation and pressure impregnation; (b) curing the material impregnated with the hafnium-zirconium composite ceramic precursor solution, then placing it in a reaction device, sealing it, evacuating it, introducing an inert gas, and cracking it at 1500-1800° C. for 10-600 minutes; the curing is performed at 150-350° C. for 10-360 minutes; (c) After the cracking reaction in step (b) is completed, the temperature is lowered under program control, and after cooling to room temperature, the introduction of the inert gas is stopped, and the pressure is restored to atmospheric pressure; (d) Repeat steps (a) to (c) at least once.

7. The preparation method according to claim 6, characterized in that In step (d): Repeat steps (a) to (c) 1 to 10 times.

8. The preparation method according to any one of claims 1 to 7, characterized in that In step (3), after the precursor impregnation and cracking process is performed, the method further includes the step of performing multiple annealing treatments using a Joule heat ultrafast synthesis process; The Joule heat ultrafast synthesis process is carried out in a Joule ultrafast heating device, with a heating rate of 180-260°C / s for each annealing treatment, an annealing temperature of 1600-2000°C, a holding time of 2-5 minutes for each annealing treatment, and natural cooling to room temperature after the holding period before the next annealing treatment; The annealing treatment is performed 3 to 5 times.

9. The preparation method according to any one of claims 1 to 7, characterized in that In step (1): The high thermal conductivity fiber preform is a wedge-shaped high thermal conductivity fiber preform; The preparation of the pointed wedge-shaped high thermal conductivity fiber preform is as follows: thin-diameter mesophase pitch-based carbon fiber and PAN-based carbon fiber are mixed to obtain thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth, and then the thin-diameter mesophase pitch-based carbon fiber / carbon fiber bidirectional cloth is made into a pointed wedge-shaped high thermal conductivity fiber preform by using a lamination and stitching process.

10. The thermally conductive ceramic-based composite material prepared by the preparation method according to any one of claims 1 to 9, characterized in that: The density of the thermal conductive ceramic matrix composite material is 3.0-5.0 g / cm 3 and / or The thermal conductivity of the thermal conductive ceramic matrix composite material at room temperature is greater than or equal to 120W / (m·K), the tensile strength at room temperature is greater than or equal to 100MPa, and the oxyacetylene wire ablation rate is less than or equal to 1×10 -3 mm / s.

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