Active and passive synergistic anti-cyclic ablation composite material with heat conduction rod structure and preparation method of active and passive synergistic anti-cyclic ablation composite material

Abstract

The invention discloses an active and passive synergistic anti-cyclic ablation composite material with a heat conduction rod structure and a preparation method thereof, and belongs to the technical field of composite materials. A central area and a non-central area are arranged on an ablation surface of the composite material, ZrC is taken as a main phase in the central area, SiC is taken as a main phase in the non-central area, and a Cu heat conduction rod for improving heat conduction capability is arranged in a main body structure of the whole composite material. Through partition modification, the sweating cooling effect that ZrC serves as the main portion of a central area to resist ablation and SiO2, Cu and oxides thereof serve as the main portions of a non-ablation central area is achieved, the surface temperature of the composite material in the ablation process is reduced through the combination of heat conduction rod structural design and active and passive synergistic protection, the temperature gradient is slowed down, and long-life cyclic ablation resistance of the composite material is achieved.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite materials, and in particular relates to an active-passive coordinated anti-cyclic ablation composite material with a heat-conducting rod structure and a preparation method thereof. Background Art

[0002] With the rapid advancement of aerospace technology, new-generation aircraft are moving toward faster flight speeds, longer service lives, and greater reusability. Aerodynamic compression and friction during cruise and reentry flight generate high-enthalpy gases, presenting severe challenges to thermal protection materials, including high-temperature oxidation, high-speed airflow and particle scouring, and the coupling of thermal and mechanical loads. Carbon / carbon (C / C) composites offer low density, high specific strength, high specific modulus, low thermal expansion coefficient, and excellent thermal shock resistance. In particular, their high-temperature mechanical properties increase with increasing temperature, making them commonly used as thermal structural materials in aerospace. However, the strong oxidation sensitivity of C / C composites limits their long-term service life in oxygen-containing environments. Matrix modification technology, by introducing oxygen-barrier / anti-ablation components into C / C composites, effectively slows the intrinsic oxidation reaction of carbon materials in high-temperature oxygen environments, thereby extending their service life.

[0003] Matrix modification technology is divided into active "sweating" cooling type and passive anti-ablation type according to the type of modified components. The active "sweating" cooling type usually introduces low-melting-point metals (such as Cu and Ti) into C / C composites, relying on the volatilization of metals and their oxides to dissipate heat in high-temperature environments and slow down the oxidation reaction rate. However, this method achieves the purpose of heat reduction by consuming the material itself and is only suitable for short-term thermal protection. The passive anti-ablation type mainly introduces high-melting-point ultra-high-temperature ceramics (UHTCs) into the interior of C / C composites, forming a high-melting-point oxide film in a high-temperature oxygen-containing environment to prevent oxygen from penetrating into the matrix. However, UHTCs and their oxides usually have low thermal conductivity, making it difficult to effectively transfer surface heat during the ablation process, triggering stagnation ablation and ultimately causing failure of the composite material. Reference 1, “Yi Zhang, Dou Hu, Lingxiang Guo, et al. La2O3-modified C / C-ZrC composites with long-term cyclic ablation resistance[J].Journal of the American Ceramic Society, 2025, 108(4):e20302.”, points out that the low thermal conductivity of the in-situ ZrO2 oxide film on the surface and the ZrC inside the composite during the ablation process leads to low thermal conductivity in the longitudinal direction of the composite. At the same time, influenced by the structure of the 2.5D needle-punched C / C composite, the thermal conductivity of the non-woven fabric layer in the axial direction is high (~72 W / (m·k)), but its radial thermal conductivity is extremely low (2-10 W / (m·k)). The laminated structure of the non-woven fabric layer limits the longitudinal heat dissipation capacity of the composite, making it difficult to dissipate heat from the sample surface during ablation, resulting in a gradual increase in surface temperature and failure of the composite. In addition, in a high and low temperature alternating environment, ZrO2 undergoes phase change due to temperature changes, causing volume shrinkage / expansion, which leads to cracks in the oxide film, which is not conducive to its long-term ablation protection performance.

[0004] In actual service environments, different parts of thermal protection materials face different thermal loads. The existence of temperature gradients will cause different degrees of deformation in different parts of the homogeneous material, especially in high and low temperature alternating environments, which will induce cracks inside the composite material. Reference 2 "Dou Hu, Qiangang Fu, Xiaoxuan Li, et al. Discussion on structural parameters of the multilayer ZrC / TaC coatings based on stressanalysis and ablation behaviors[J]. Surface&Coatings Technology, 2022, 435:128243." simulated the ZrC coating under a heat flux density of 2.4 MW / m 2 The temperature and stress fields after 60 s of ablation under an oxyacetylene flame are shown in Figure 3. The results show that the temperature in the ablation center is the highest, and a significant temperature gradient is generated with the edge area where the temperature is low, resulting in the maximum thermal stress in the edge area. In addition, ZrC in the edge area is oxidized to form ZrO2, and powdering oxidation occurs in the absence of a low-melting-point phase to promote sintering, and the oxide film is very easy to peel off.

[0005] As the service temperatures of aircraft hot-end components continue to rise, traditional passive ablation-resistant composite materials are no longer able to meet the thermal protection requirements. Furthermore, when subjected to large temperature gradients, integrally modified C / C composites can crack due to concentrated thermal stresses, destabilizing the oxide film and reducing its ability to prevent oxygen penetration into the matrix, leading to composite failure. Summary of the Invention

[0006] The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide an active-passive collaborative anti-cyclic ablation composite material with a heat-conducting rod structure and a preparation method thereof, so as to solve technical problems such as phase change cracking of thermal protection materials in high and low temperature alternating environments, weak heat conduction ability, insufficient wide temperature range protection performance, thermal stress concentration induced by temperature gradient, and short service life.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions: An active-passive coordinated anti-cyclic ablation composite material with a heat-conducting rod structure comprises a main structure, wherein one end surface of the main structure is an ablation surface, and the opposite surface is a non-ablation surface; The main structure is divided into a central region and a non-central region, the upper end surface of the central region is part of the ablation surface, the lower end surface of the central region is inside the non-central region, and the side of the central region is wrapped by the non-central region; the central region is mainly composed of ZrC, the non-central region is mainly composed of SiC, and Cu is distributed in both the central region and the non-central region; Heat conducting rods are distributed in both the central area and the non-central area. The outer end surface of the heat conducting rod is a non-ablated surface, and the inner end surface is in the main structure. The heat conducting rod is made of Cu.

[0008] A further improvement of the present invention is: Preferably, the central area and the non-central area are coaxial.

[0009] Preferably, the diameter of the heat conducting rod is 1-2 mm, the distance between the edges of the heat conducting rod is 3-6 mm, and the length of the heat conducting rod is 60-80% of the thickness of the main structure.

[0010] A method for preparing the active-passive coordinated anti-cyclic ablation composite material having the above-mentioned thermal conductive rod structure comprises the following preparation steps: S1, opening a plurality of heat conduction holes inward from the non-ablated surface of the main structure, wherein the main structure is a C / C composite material; S2, infiltrating La2O3 slurry into the ablation surface through vacuum filtration in the main structure, and obtaining C / C-La2O3 composite material after drying; S3, filling Cu powder into the thermal conductive holes in the C / C-La2O3 composite material to obtain a C / C-La2O3-Cu composite material; S4, laying a layer of Cu-Si alloy powder on the bottom of a graphite crucible, placing a C / C-La2O3-Cu composite material on the Cu-Si alloy powder, with the ablated surface facing upward and the non-ablated surface in contact with the Cu-Si alloy powder on the bottom layer, placing a hollow cylindrical mold on the ablated surface of the C / C-La2O3-Cu composite material, adding Zr-Cu alloy powder to the hollow cylindrical mold as the infiltration powder in the central area, and adding Cu-Si alloy powder as the infiltration powder in the non-central area, the infiltration powder in the non-central area fills the area outside the hollow cylindrical mold, and completely covers the C / C-La2O3-Cu composite material; S5, placing the graphite crucible loaded with the C / C-La2O3-Cu composite material and the infiltration powder in a vacuum hot pressing furnace, and obtaining a Cu and Si zone-modified C / C-ZrC-Cu-La2O3 composite material after vacuum negative pressure reaction infiltration; S6, Cu powder was added to the thermal conductive holes of the Cu and Si partitioned modified C / C-ZrC-Cu-La2O3 composite material, and vacuum negative pressure reactive infiltration was carried out in a vacuum hot pressing furnace to obtain an active-passive synergistic anti-cyclic ablation composite material with a thermal conductive rod structure.

[0011] Preferably, in S2, the infiltrated La2O3 slurry accounts for 5-20 wt.% of the mass of the C / C-La2O3 composite material.

[0012] Preferably, in S2, during the infiltration of La2O3 slurry, the vacuum filtration times are 2-4 times and the drying temperature is 70-100°C.

[0013] Preferably, in S4, in the Cu-Si alloy powder, the mass fraction of Cu powder is 75-90 wt.%, and the mass fraction of Si powder is 10-25 wt.%.

[0014] Preferably, in S4, in the Zr-Cu alloy powder, the mass fraction of Zr powder is 60-80 wt.%, and the mass fraction of Cu powder is 20-40 wt.%.

[0015] Preferably, in S5 and S6, the heating and cooling process of vacuum negative pressure reaction infiltration is: heating to 850-1050 °C at 8-13 °C / min; heating to 1100-1400 °C at 3-7 °C / min; after heat treatment for 0.5-3 h, reducing the temperature to 750-900 °C at 3-7 °C / min, and then cooling to room temperature with the furnace.

[0016] Preferably, in S4, the hollow cylindrical mold and the C / C-La2O3-Cu composite material are coaxial.

[0017] Compared with the prior art, the present invention has the following beneficial effects: The present invention discloses an active-passive collaborative anti-cyclic ablation composite material with a heat-conducting rod structure. In order to solve the problems that the thermal stress in the edge area of ​​the overall modified C / C composite material is large due to the existence of temperature gradient, which causes cracking inside the matrix, and the single ZrC undergoes powdering and oxidation in the low-temperature area (1000-2000 ℃) during the ablation process, causing the oxide film to peel off, the wide temperature range protection capability is insufficient, and the ablation surface temperature of the sample gradually increases with the ablation time, the composite material is provided with a central area and a non-central area on the ablation surface, wherein the central area is mainly ZrC and the non-central area is mainly SiC. A heat-conducting rod for improving thermal conductivity is provided in the main structure of the entire composite material. The composite material has a heat flux density of 4.2 MW / m with a cycle of 40 s. 2After the oxyacetylene test, compared with the composite material without zoning modification and thermal conductive rod structure design, no peeling and cracking of the oxide film occurred, the ablation time was increased from 240 s to 720 s, the number of thermal shocks was increased from 6 to 18 times, and the surface temperature of the sample dropped by ~154 ° C during the ablation process; the ablation rate was negative, indicating that no ablation phenomenon occurred in the composite material, and the sample thickened. The oxide film in the non-ablation center area was dense and complete, and had excellent wide temperature range protection performance. Specific analysis shows that the present invention also has the following advantages: (1) Aiming at the problem that the radial thermal conductivity of the non-woven fabric layer of the traditional 2.5D needle-punched C / C composite material is low, the surface heat is difficult to be discharged during the ablation process, and stagnation ablation is easily caused, the present invention punches holes on the non-ablation surface of the C / C composite material to design a composite material with a heat conducting rod structure design, and connects the non-woven fabric layer and the mesh layer through the heat conducting rod, thereby improving the longitudinal thermal conductivity of the composite material.

[0018] (2) Through zoning modification, during the ablation process, the central area with higher temperature is mainly composed of ZrC and Cu, which can effectively resist high temperature during the ablation process, while the non-central area with relatively low temperature is mainly composed of SiC and Cu, which form glass phase SiO2 with high oxygen barrier coefficient and Cu oxide after oxidation, thereby improving the wide temperature range protection effect of the composite material; through zoning modification, relying on the "sweating" cooling effect of Cu in the ablation center area and SiO2 and Cu and their oxides in the non-ablation center area, combined with the structural design of the thermal conductive rod, the active and passive coordinated protection reduces the surface temperature of the composite material during the ablation process and slows down the temperature gradient; at the same time, during the ablation process, SiC is oxidized, and the edge area is mainly composed of glassy SiO2, which can play a role similar to "glue" and firmly bond to the matrix; in addition, the thermal expansion coefficient of SiO2 is closer to that of C / C composite material than that of ZrO2.

[0019] (3) To address the problem of ZrO2, the oxidation product of ZrC, being prone to phase transition and cracking under high and low temperature alternating conditions, the present invention introduces La2O3 into the C / C composite material through vacuum filtration, effectively inhibiting the transformation of t-ZrO2 to m-ZrO2 during the cooling process after ablation, thereby alleviating the cracking of the oxide film. Simultaneously, combined with the rapid heat conduction of the heat conducting rod, the thermal conductivity of the composite material is improved, which helps alleviate the problem of La element continuously precipitating from ZrO2 due to temperature rise.

[0020] The present invention also discloses a method for preparing an active and passive coordinated protection anti-cyclic ablation composite material with a thermal conductive rod structural design. The preparation method disclosed in the present invention first prepares a thermal conductive hole groove on the non-ablation surface of the C / C composite material, introduces La2O3 by a vacuum filtration process and adds Cu powder into the thermal conductive hole groove, then combines the reaction infiltration process to realize the partition modification design, and performs sealing treatment to prepare the active and passive coordinated protection anti-cyclic ablation composite material with a thermal conductive rod structural design. This method introduces La2O3 to inhibit the problems of ZrO2 being difficult to sinter and prone to cracking due to phase change in a high and low temperature alternating environment; it can modify the composite material in different zones according to the actual service environment of the composite material by controlling the diameter and depth of the graphite paper hollow cylindrical mold, and realize a functional zoned structural design in which the central area is mainly ZrC for ablation resistance and the non-central area is mainly SiC and Cu for "sweating" cooling. The surface temperature of the sample is reduced by the "sweating" cooling effect, and the active and passive coordinated protection reduces the surface temperature of the composite material during the ablation process, slowing down stagnation point ablation; the zoned modified structural design improves the wide temperature range protection capability of the composite material, slows down the thermal stress caused by the temperature gradient between the central area and the non-central area, and improves the composite material's anti-cyclic ablation performance; by controlling the diameter, depth and distribution density of the heat conducting rod, the thermal conductivity of the composite material is further improved, and the long-life anti-cyclic ablation of the composite material is achieved.

[0021] Furthermore, the preparation method of the present invention can achieve controllable preparation of the composition and structure of different regions of the composite material by changing the diameter and height of the graphite paper hollow cylindrical mold and the infiltration powder in different regions according to the actual service environment requirements of the composite material, and has good universality and application prospects.

[0022] Furthermore, the design and preparation of the heat-conducting rod in the preparation method of the present invention has the advantages of strong designability, convenient operation, and low cost. The structure and composition of the heat-conducting rod can achieve different degrees of active heat reduction by changing the diameter, depth, distribution density and internal filler type of the pre-punched holes according to the actual service environment requirements. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 Flowchart for preparing active and passive coordinated protection anti-cyclic ablation composite material with a heat-conducting rod structure design according to Example 1 of the present invention; Figure 2 The powder spreading method of the graphite crucible when preparing the active and passive coordinated protection anti-cyclic ablation composite material with a heat-conducting rod structure design according to Example 1 of the present invention; Figure 3 A cross-sectional structural diagram of the active and passive coordinated protection anti-cyclic ablation composite material with a heat-conducting rod structure, prepared in Example 1 of the present invention; Figure 4Microscopic morphology of the active and passive coordinated protection anti-cyclic ablation composite material with a heat-conducting rod structure, prepared in Example 1 of the present invention; (a) is a schematic diagram of the overall structure of the composite material; (b) is the interface between the central and non-central regions of the composite material's ablation surface; (c) is a cross-sectional morphology of the heat-conducting rod; and (d) is an enlarged view. Figure 5 This is a comparison diagram of the surface temperature curves of the composite material during the ablation process of Example 1 of the present invention and Comparative Example 1; Figure 6 Microscopic morphology of different areas of the active and passive coordinated protection anti-cyclic ablation composite material with a heat-conducting rod structure design prepared in Example 1 of the present invention after ablation; Figure 7 This is the XRD pattern of the surface of the active and passive coordinated protection anti-cyclic ablation composite material with a heat-conducting rod structure design after ablation prepared in Example 1 of the present invention; Figure 8 These are macroscopic images of the composite materials after ablation of Example 1 of the present invention and Comparative Example 1. DETAILED DESCRIPTION

[0024] The present invention is described in further detail below with reference to the accompanying drawings: To facilitate understanding of the features and effects of the present invention by those skilled in the art, the following provides a general description and definition of the terms and expressions used in the specification and claims. Unless otherwise indicated, all technical and scientific terms used herein have the ordinary meanings as understood by those skilled in the art regarding the present invention. In the event of conflict, the definitions in this specification shall prevail.

[0025] In this document, unless otherwise specified, “include,” “including,” “contains,” “has” or similar terms cover the meanings of “consisting of” and “mainly consisting of,” for example, “A includes a” covers the meanings of “A includes a and other” and “A only includes a.”

[0026] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0027] The following examples were prepared using conventional instruments and equipment in the art. Experimental methods in the following examples, where specific conditions are not specified, were generally performed under conventional conditions or according to the conditions recommended by the manufacturer. The various raw materials used in the following examples, unless otherwise specified, were conventional commercially available products, with specifications conventional in the art. In the present specification and the following examples, unless otherwise specified, "%" indicates percentage by weight, "part" indicates parts by weight, and "ratio" indicates weight ratio.

[0028] See also Figure 1 The first aspect of the present invention discloses a method for preparing an active-passive coordinated anti-cyclic ablation composite material having a heat-conducting rod structure, comprising the following steps: S1, according to the service conditions of C / C composite materials, one end surface is the ablation surface, the other end surface is the non-ablation surface, and several cylindrical holes on the non-ablation surface serve as heat conduction holes; S2, placing the C / C composite material with the ablated surface facing upward on filter paper in a vacuum filtration apparatus, pouring La2O3 slurry, wherein the La2O3 slurry is obtained by mixing La2O3 powder and anhydrous ethanol; and introducing La2O3 into the C / C matrix by vacuum filtration, followed by drying to obtain a C / C-La2O3 composite material; S3, filling Cu powder into the thermal conductive holes of the C / C-La2O3 composite material to obtain a C / C-La2O3-Cu composite material; S4, see Figure 2 , a C / C La2O3-Cu composite material is placed in a graphite crucible, a hollow cylinder of a set size wrapped with graphite paper is used as a mold, and the mold is placed on the ablation surface of the C / C-La2O3-Cu composite material so that the center of the hollow cylinder coincides with the center of the ablation surface of the C / C-La2O3-Cu composite material, Zr-Cu alloy powder is added to the hollow cylindrical mold as the infiltration powder in the central area, and Cu-Si alloy powder is added as the infiltration powder in the non-central area, and the infiltration powder in the non-central area fills the area outside the hollow cylindrical mold and completely covers the C / C-La2O3-Cu composite material; S5, placing the graphite crucible loaded with the C / C-La2O3-Cu composite material and the infiltration powder in a vacuum hot pressing furnace, and obtaining a Cu and Si zone-modified C / C-ZrC-Cu-La2O3 composite material after vacuum negative pressure reaction infiltration; S6, Cu powder is added again into the thermal conductive holes of the non-ablative surface of the Cu-Si partitioned modified C / C-ZrC-Cu- La2O3 composite material, and the material is placed in a vacuum hot pressing furnace and sealed at 1100-1400 °C to obtain a Cu-Si partitioned modified C / C-ZrC-Cu- La2O3 composite material with a thermal conductive rod structure design, that is, an active and passive collaborative protection anti-cyclic ablation composite material with a thermal conductive rod structure design. During the above infiltration process, the Zr-Cu alloy powder in the hollow cylindrical mold infiltrates downwards, and the infiltration depth is determined according to the actual situation. The external Cu-Si powder infiltrates toward the non-central area, and the thermal holes are filled with Cu powder to form a Figure 3 structure.

[0029] In some embodiments of the present invention, in S1, the density of the selected C / C composite material is 1.0-1.4 g / cm 3 , porosity 30%-50%.

[0030] In some embodiments of the present invention, in S1, the diameter of the columnar pores on the surface of the C / C composite material is 1-2 mm, the distance between the pores is 3-6 mm, and the depth of the columnar pores is 60-80% of the thickness of the C / C composite material.

[0031] In some embodiments of the present invention, in S2, in the La2O3 slurry, the mass fraction of La2O3 powder is 5-15 wt.%, and the mass fraction of anhydrous ethanol is 85-95 wt.%.

[0032] In some embodiments of the present invention, the vacuum filtration times of La2O3 in S2 is 2-4 times, the mass fraction of La2O3 in C / C-La2O3 after filtration is about 5-20 wt.%, and the drying temperature is 70-100 °C.

[0033] In some embodiments of the present invention, in S3 , the Cu powder filled in the thermal via has a particle size of about 1-5 μm and is evenly filled into the thermal via.

[0034] In some embodiments of the present invention, in S4, the order of adding the infiltration powder is as follows: first, a layer of Cu-Si alloy powder is laid on the bottom of a graphite crucible with an inner cavity coated with graphite paper, and the non-ablated surface of the C / C-La2O3-Cu composite material is contacted with the Cu-Si powder, with the ablated surface facing up; a hollow cylinder with a diameter of 8-20 mm and a depth of 3-5 mm wrapped in graphite paper is used as a mold, and is placed on the ablated surface of the C / C-La2O3-Cu composite material so that the center of the hollow cylinder coincides with the center of the ablated surface of the C / C-La2O3-Cu composite material.

[0035] Add about 2-4 mm of Zr-Cu alloy powder into the hollow cylindrical mold; fill the area outside the hollow cylinder with Cu-Si alloy powder until the C / C-La2O3-Cu composite material is completely covered, and the Cu-Si alloy powder exceeds the upper surface of the C / C-La2O3-Cu composite material by 3-5 mm.

[0036] Preferably, in the above-mentioned Cu-Si alloy powder, the mass fraction of Cu powder is 75-90 wt.%, and the mass fraction of Si powder is 10-25 wt.%.

[0037] Preferably, in the above Zr-Cu alloy powder, the mass fraction of Zr powder is 60-80 wt.%, and the mass fraction of Cu powder is 20-40 wt.%.

[0038] In some embodiments of the present invention, in S5, the vacuum pressure is 1-50 Pa.

[0039] In some embodiments of the present invention, in S5, the temperature rise and fall program of the reactive infiltration process is: heating at 8-13 ° C / min to 850-1050 ° C; heating at 3-7 ° C / min to 1100-1400 ° C, after heat treatment for 0.5-3 h, reducing to 750-900 ° C at 3-7 ° C / min, and then cooling to room temperature with the furnace. In this process, the low-temperature section heats up quickly and the high-temperature section heats up slowly, leaving enough time for the reaction to occur. The temperature control process of this step optimizes the performance of the composite material.

[0040] In this process, as a preferred solution, the temperature of the reactive infiltration is 1180-1420°C. The reactive infiltration temperature affects the viscosity of the powder after melting, and further affects the degree of infiltration into the C / C matrix.

[0041] In some embodiments of the present invention, the sealing process parameters are the same as the reactive infiltration process parameters described above.

[0042] The second aspect of the present invention discloses an active-passive cooperative anti-cyclic ablation composite material with a heat-conducting rod structure, such as Figure 3 As shown, it includes a main structure, one end face of the main structure is an ablation surface, and the opposite face is a non-ablation surface; the ablation surface includes a central area arranged in the center and a non-central area arranged around the central area; the central area has ZrC as the main phase, the non-central area has SiC as the main phase, and Cu is distributed in both the central area and the non-central area; the central area of ​​the ablation surface has ZrC as the main phase, the non-central area has SiC as the main phase, and Cu is uniformly distributed on the ablation surface; a number of thermal conductive rods with Cu as filler are distributed in the entire composite material.

[0043] It should be noted that some Zr has infiltrated into the heat conducting rod in the central area, but Cu is still the main component.

[0044] It should be noted that the ablation surface and the non-ablation surface in the structure are not just a plane, but a region with a certain thickness.

[0045] The following is further described with reference to specific embodiments.

[0046] Example 1 A method for preparing an active-passive coordinated protection anti-cyclic ablation composite material with a heat-conducting rod structure design comprises the following steps: Step 1: Take a piece of 1.1 g / cm 3 2. C / C composite material with a size of Φ30 mm × 5 mm was pre-drilled with columnar holes on its surface with a pore diameter of 1.5 mm, a depth of 4 mm, and a distance of 4 mm between two holes. After ultrasonic cleaning for 30 min, it was placed in a 70 °C oven to dry and wait for use; Step 2: Weigh La2O3 powder and place it in a beaker. Add an appropriate amount of anhydrous ethanol, where the mass fractions of La2O3 powder and anhydrous ethanol are 10 wt.% and 90 wt.%, respectively. Place the beaker on a magnetic stirrer and stir for 30 minutes until there are no obvious agglomerated particles in the La2O3 slurry. Set aside for later use. Step 3: Place the pre-perforated C / C composite material with the ablation surface facing upward on filter paper in a vacuum filtration device. Turn on the vacuum pump and pour La2O3 slurry into the material in multiple steps. The La2O3 slurry enters the interior of the C / C composite material under the suction force of the vacuum pump. Remove the sample and dry it in a 100°C oven for 24 hours before use. Repeat the above steps three times. The mass fraction of La2O3 in the C / C-La2O3 is 12.4 wt.%; Step 4: Cu powder with a particle size of 3-5 μm is added into the thermal conductive holes of C / C-La2O3 to obtain a C / C-La2O3-Cu composite material; Step 5: Place a layer of Cu-Si alloy powder on the bottom of the graphite crucible, where the mass fractions of Cu powder and Si powder are 85 wt.% and 15 wt.%, respectively. Place the non-ablated surface of the C / C-La2O3-Cu composite material in contact with the Cu-Si powder, with the ablated surface facing up. Wrap a hollow cylinder with a diameter of 16 mm and a depth of 5 mm with graphite paper as a mold and place it on the ablated surface of the C / C-La2O3-Cu composite material so that the center of the hollow cylinder coincides with the center of the ablated surface of the C / C-La2O3-Cu composite material. Add about 3 mm of Zr-Cu alloy powder into the hollow cylinder, where the mass fractions of Zr powder and Cu powder are 70 wt.% and 30 wt.%, respectively. Fill the area outside the hollow cylinder with the above-mentioned Cu-Si alloy powder until the C / C-La2O3-Cu composite material is completely covered. Step 6: Place the graphite crucible in a vacuum hot press furnace, turn on the vacuum pump to make the pressure in the furnace 1-50 Pa, first heat it to 900 ° C at 10 ° C / min, then heat it to 1300 ° C at 5 ° C / min, keep it for 2 hours, then reduce it to 800 ° C at 5 ° C / min, and then cool it to room temperature in the furnace to obtain Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material; Step 7: Add Cu powder with a particle size of 3-5 μm into the heat conduction holes on the non-ablative surface of the Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material, place it in a vacuum hot pressing furnace, and follow the same heating and cooling procedures as in step 6 to prepare a Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material with a thermal conductive rod structure design, that is, an active and passive collaborative protection anti-cyclic ablation composite material with a thermal conductive rod structure design.

[0047] The composite material prepared in this example was heated to a heat flux of 4.2 MW / m 2 After ablation under oxyacetylene flame for 40s×18, the oxide film formed on the surface of the composite material was dense and stable, and no peeling occurred during the ablation process. The mass ablation rate was 0.57 mg / s and the thickness increase rate was 0.58 μm / s.

[0048] Example 2 A method for preparing an active-passive coordinated protection anti-cyclic ablation composite material with a heat-conducting rod structure design comprises the following steps: Step 1: Take a piece of 1.2 g / cm 3 2. C / C composite material with a size of Φ30 mm × 5 mm was punched with columnar holes on its surface with a pore diameter of 2 mm, a depth of 4 mm, and a distance of 5 mm between two holes. After ultrasonic cleaning for 30 min, it was placed in an 80 °C oven to dry and wait for use; Step 2: Weigh La2O3 powder and place it in a beaker. Add an appropriate amount of anhydrous ethanol, where the mass fractions of La2O3 powder and anhydrous ethanol are 20 wt.% and 80 wt.%, respectively. Place the beaker on a magnetic stirrer and stir for 30 minutes until there are no obvious agglomerated particles in the La2O3 slurry. Set aside for later use. Step 3: Place the pre-perforated C / C composite material with the ablation surface facing upward on filter paper in a vacuum filtration device. Turn on the vacuum pump and pour La2O3 slurry into the C / C composite material in multiple batches. The La2O3 slurry enters the interior of the C / C composite material under the suction force of the vacuum pump. Remove the sample and dry it in a 70°C oven for 24 hours before use. Repeat the above steps twice. The mass fraction of La2O3 in the C / C-La2O3 is 7.6 wt.%; Step 4: Cu powder with a particle size of 3-5 μm is added into the thermal conductive holes of C / C-La2O3 to obtain a C / C-La2O3-Cu composite material; Step 5: Place a layer of Cu-Si alloy powder on the bottom of the graphite crucible, where the mass fractions of Cu powder and Si powder are 80 wt.% and 20 wt.%, respectively. Place the non-ablated surface of the C / C-La2O3-Cu composite material in contact with the Cu-Si powder, with the ablated surface facing up. Wrap a hollow cylinder with a diameter of 12 mm and a depth of 5 mm with graphite paper as a mold and place it on the ablated surface of the C / C-La2O3-Cu composite material so that the center of the hollow cylinder coincides with the center of the ablated surface of the C / C-La2O3-Cu composite material. Add about 3 mm of Zr-Cu alloy powder into the hollow cylinder, where the mass fractions of Zr powder and Cu powder are 75 wt.% and 25 wt.%, respectively. Fill the area outside the hollow cylinder with the above-mentioned Cu-Si alloy powder until the C / C-La2O3-Cu composite material is completely covered. Step 6: Place the graphite crucible in a vacuum hot press furnace, turn on the vacuum pump to make the pressure in the furnace 1-50 Pa, first heat it to 900 ° C at 12 ° C / min, then heat it to 1300 ° C at 5 ° C / min, keep it for 1 hour, then reduce it to 800 ° C at 5 ° C / min, and then cool it to room temperature in the furnace to obtain Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material; Step 7: Add Cu powder with a particle size of 3-5 μm into the heat conduction holes on the non-ablative surface of the Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material, place it in a vacuum hot pressing furnace, and follow the same heating and cooling procedures as in step 6 to prepare a Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material with a thermal conductive rod structure design, that is, an active and passive collaborative protection anti-cyclic ablation composite material with a thermal conductive rod structure design.

[0049] Example 3 A method for preparing an active-passive coordinated protection anti-cyclic ablation composite material with a heat-conducting rod structure design comprises the following steps: Step 1: Take a piece of 1.2 g / cm 3 2. A C / C composite material with a size of Φ30 mm × 5 mm was drilled with columnar holes on its surface, with a pore diameter of 1.5 mm, a depth of 3 mm, and a distance of 4 mm between two holes. After ultrasonic cleaning for 30 min, it was placed in a 70 °C oven to dry and wait for use; Step 2: Weigh La2O3 powder and place it in a beaker. Add an appropriate amount of anhydrous ethanol, where the mass fractions of La2O3 powder and anhydrous ethanol are 15 wt.% and 85 wt.%, respectively. Place the beaker on a magnetic stirrer and stir for 30 minutes until there are no obvious agglomerated particles in the La2O3 slurry. Set aside for later use. Step 3: Place the pre-perforated C / C composite material with the ablation surface facing upward on filter paper in a vacuum filtration device. Turn on the vacuum pump and pour La2O3 slurry into the C / C composite material in multiple batches. The La2O3 slurry enters the interior of the C / C composite material under the suction force of the vacuum pump. Remove the sample and dry it in a 70°C oven for 24 hours before use. Repeat the above steps twice. The mass fraction of La2O3 in the C / C-La2O3 is 7.6 wt.%; Step 4: Cu powder with a particle size of 3-5 μm is added into the thermal conductive holes of C / C-La2O3 to obtain a C / C-La2O3-Cu composite material; Step 5: Place a layer of Cu-Si alloy powder on the bottom of the graphite crucible, where the mass fractions of Cu powder and Si powder are 75 wt.% and 25 wt.%, respectively. Place the non-ablated surface of the C / C-La2O3-Cu composite material in contact with the Cu-Si powder, with the ablated surface facing up. Wrap a hollow cylinder with a diameter of 14 mm and a depth of 4 mm with graphite paper as a mold and place it on the ablated surface of the C / C-La2O3-Cu composite material so that the center of the hollow cylinder coincides with the center of the ablated surface of the C / C-La2O3-Cu composite material. Add about 3 mm of Zr-Cu alloy powder into the hollow cylinder, where the mass fractions of Zr powder and Cu powder are 65 wt.% and 35 wt.%, respectively. Fill the area outside the hollow cylinder with the above-mentioned Cu-Si alloy powder until the C / C-La2O3-Cu composite material is completely covered. Step 6: Place the graphite crucible in a vacuum hot press furnace, turn on the vacuum pump to make the pressure in the furnace 1-50 Pa, first heat it to 1000 ° C at 12 ° C / min, then heat it to 1350 ° C at 6 ° C / min, keep it for 2 hours, then reduce it to 850 ° C at 7 ° C / min, and then cool it to room temperature in the furnace to obtain Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material; Step 7: Add Cu powder with a particle size of 3-5 μm into the heat conduction holes on the non-ablative surface of the Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material, place it in a vacuum hot pressing furnace, and follow the same heating and cooling procedures as in step 6 to prepare a Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material with a thermal conductive rod structure design, that is, an active and passive collaborative protection anti-cyclic ablation composite material with a thermal conductive rod structure design.

[0050] Example 4 A method for preparing an active-passive coordinated protection anti-cyclic ablation composite material with a heat-conducting rod structure design comprises the following steps: Step 1: Take a piece of 1.3 g / cm 3 2. C / C composite material with a size of Φ30 mm × 5 mm was punched with columnar holes on its surface with a pore diameter of 1 mm, a depth of 4 mm, and a distance of 3 mm between two holes. After ultrasonic cleaning for 30 min, it was placed in a 70 °C oven to dry and wait for use; Step 2: Weigh La2O3 powder and place it in a beaker. Add an appropriate amount of anhydrous ethanol, where the mass fractions of La2O3 powder and anhydrous ethanol are 15 wt.% and 85 wt.%, respectively. Place the beaker on a magnetic stirrer and stir for 30 minutes until there are no obvious agglomerated particles in the La2O3 slurry. Set aside for later use. Step 3: Place the pre-perforated C / C composite material with the ablation surface facing upward on filter paper in a vacuum filtration device. Turn on the vacuum pump and pour La2O3 slurry into the C / C composite material in multiple batches. The La2O3 slurry enters the interior of the C / C composite material under the suction force of the vacuum pump. Remove the sample and dry it in a 70°C oven for 24 hours before use. Repeat the above steps four times. The mass fraction of La2O3 in the C / C-La2O3 is 11.6 wt.%; Step 4: Cu powder with a particle size of 3-5 μm is added into the thermal conductive holes of C / C-La2O3 to obtain a C / C-La2O3-Cu composite material; Step 5: Place a layer of Cu-Si alloy powder on the bottom of the graphite crucible, where the mass fractions of Cu powder and Si powder are 80 wt.% and 20 wt.%, respectively. Place the non-ablated surface of the C / C-La2O3-Cu composite material in contact with the Cu-Si powder, with the ablated surface facing up. Wrap a hollow cylinder with a diameter of 18 mm and a depth of 5 mm with graphite paper as a mold and place it on the ablated surface of the C / C-La2O3-Cu composite material so that the center of the hollow cylinder coincides with the center of the ablated surface of the C / C-La2O3-Cu composite material. Add about 4 mm of Zr-Cu alloy powder into the hollow cylinder, where the mass fractions of Zr powder and Cu powder are 75 wt.% and 25 wt.%, respectively. Fill the area outside the hollow cylinder with the above-mentioned Cu-Si alloy powder until the C / C-La2O3-Cu composite material is completely covered. Step 6: Place the graphite crucible in a vacuum hot press furnace, turn on the vacuum pump to make the pressure in the furnace 1-50 Pa, first heat it to 950 ° C at 10 ° C / min, then heat it to 1300 ° C at 5 ° C / min, keep it for 3 hours, then reduce it to 900 ° C at 6 ° C / min, and then cool it to room temperature in the furnace to obtain Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material; Step 7: Add Cu powder with a particle size of 3-5 μm into the heat conduction holes on the non-ablative surface of the Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material, place it in a vacuum hot pressing furnace, and follow the same heating and cooling procedures as in step 6 to prepare a Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material with a thermal conductive rod structure design, that is, an active and passive collaborative protection anti-cyclic ablation composite material with a thermal conductive rod structure design.

[0051] Example 5 A method for preparing an active-passive coordinated protection anti-cyclic ablation composite material with a heat-conducting rod structure design comprises the following steps: Step 1: Take a piece of 1.3 g / cm 3 2. C / C composite material with a size of Φ30 mm × 5 mm was punched with columnar holes on its surface with a pore diameter of 1 mm, a depth of 4 mm, and a distance of 3 mm between two holes. After ultrasonic cleaning for 30 min, it was placed in a 70 °C oven to dry and wait for use; Step 2: Weigh La2O3 powder and place it in a beaker. Add an appropriate amount of anhydrous ethanol, where the mass fractions of La2O3 powder and anhydrous ethanol are 5 wt.% and 95 wt.%, respectively. Place the beaker on a magnetic stirrer and stir for 30 minutes until there are no obvious agglomerated particles in the La2O3 slurry. Set aside for later use. Step 3: Place the pre-perforated C / C composite material with the ablation surface facing upward on filter paper in a vacuum filtration device. Turn on the vacuum pump and pour La2O3 slurry into it in multiple batches. The La2O3 slurry enters the interior of the C / C composite material under the suction force of the vacuum pump. Remove the sample and place it in an 80°C oven to dry for 24 hours before use. Repeat the above steps four times. The mass fraction of La2O3 in the C / C-La2O3 is 10.6 wt.%; Step 4: Cu powder with a particle size of 3-5 μm is added into the thermal conductive holes of C / C-La2O3 to obtain a C / C-La2O3-Cu composite material; Step 5: Place a layer of Cu-Si alloy powder on the bottom of the graphite crucible, where the mass fractions of Cu powder and Si powder are 90 wt.% and 10 wt.%, respectively. Place the non-ablated surface of the C / C-La2O3-Cu composite material in contact with the Cu-Si powder, with the ablated surface facing up. Wrap a hollow cylinder with a diameter of 18 mm and a depth of 5 mm with graphite paper as a mold and place it on the ablated surface of the C / C-La2O3-Cu composite material so that the center of the hollow cylinder coincides with the center of the ablated surface of the C / C-La2O3-Cu composite material. Add about 4 mm of Zr-Cu alloy powder into the hollow cylinder, where the mass fractions of Zr powder and Cu powder are 60 wt.% and 40 wt.%, respectively. Fill the area outside the hollow cylinder with the above-mentioned Cu-Si alloy powder until the C / C-La2O3-Cu composite material is completely covered. Step 6: Place the graphite crucible in a vacuum hot press furnace, turn on the vacuum pump to make the pressure in the furnace 1-50 Pa, first heat it to 950 ° C at 10 ° C / min, then heat it to 1100 ° C at 5 ° C / min, keep it for 3 hours, then reduce it to 900 ° C at 6 ° C / min, and then cool it to room temperature in the furnace to obtain Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material; Step 7: Add Cu powder with a particle size of 3-5 μm into the heat conduction holes on the non-ablative surface of the Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material, place it in a vacuum hot pressing furnace, and follow the same heating and cooling procedures as in step 6 to prepare a Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material with a thermal conductive rod structure design, that is, an active and passive collaborative protection anti-cyclic ablation composite material with a thermal conductive rod structure design.

[0052] Example 6 A method for preparing an active-passive coordinated protection anti-cyclic ablation composite material with a heat-conducting rod structure design comprises the following steps: Step 1: Take a piece of 1.3 g / cm 32. C / C composite material with a size of Φ30 mm × 5 mm was punched with columnar holes on its surface with a pore diameter of 1 mm, a depth of 4 mm, and a distance of 3 mm between two holes. After ultrasonic cleaning for 30 min, it was placed in a 70 °C oven to dry and wait for use; Step 2: Weigh La2O3 powder and place it in a beaker. Add an appropriate amount of anhydrous ethanol, where the mass fractions of La2O3 powder and anhydrous ethanol are 20 wt.% and 80 wt.%, respectively. Place the beaker on a magnetic stirrer and stir for 30 minutes until there are no obvious agglomerated particles in the La2O3 slurry. Set aside for later use. Step 3: Place the pre-perforated C / C composite material with the ablation surface facing upward on filter paper in a vacuum filtration device. Turn on the vacuum pump and pour La2O3 slurry into it in multiple batches. The La2O3 slurry enters the interior of the C / C composite material under the suction force of the vacuum pump. Remove the sample and place it in a 90°C oven to dry for 24 hours before use. Repeat the above steps four times. The mass fraction of La2O3 in C / C-La2O3 is 13.8 wt.%; Step 4: Cu powder with a particle size of 3-5 μm is added into the thermal conductive holes of C / C-La2O3 to obtain a C / C-La2O3-Cu composite material; Step 5: Place a layer of Cu-Si alloy powder on the bottom of the graphite crucible, where the mass fractions of Cu powder and Si powder are 90 wt.% and 10 wt.%, respectively. Place the non-ablated surface of the C / C-La2O3-Cu composite material in contact with the Cu-Si powder, with the ablated surface facing up. Wrap a hollow cylinder with a diameter of 18 mm and a depth of 5 mm with graphite paper as a mold and place it on the ablated surface of the C / C-La2O3-Cu composite material so that the center of the hollow cylinder coincides with the center of the ablated surface of the C / C-La2O3-Cu composite material. Add about 4 mm of Zr-Cu alloy powder into the hollow cylinder, where the mass fractions of Zr powder and Cu powder are 80 wt.% and 20 wt.%, respectively. Fill the area outside the hollow cylinder with the above-mentioned Cu-Si alloy powder until the C / C-La2O3-Cu composite material is completely covered. Step 6: Place the graphite crucible in a vacuum hot press furnace, turn on the vacuum pump to make the pressure in the furnace 1-50 Pa, first heat it to 950 ° C at 10 ° C / min, then heat it to 1400 ° C at 5 ° C / min, keep it for 0.5 h, then reduce it to 900 ° C at 6 ° C / min, and then cool it to room temperature in the furnace to obtain a Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material; Step 7: Add Cu powder with a particle size of 3-5 μm into the heat conduction holes on the non-ablative surface of the Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material, place it in a vacuum hot pressing furnace, and follow the same heating and cooling procedures as in step 6 to prepare a Cu-Si partitioned modified C / C-ZrC-Cu-La2O3 composite material with a thermal conductive rod structure design, that is, an active and passive collaborative protection anti-cyclic ablation composite material with a thermal conductive rod structure design.

[0053] Comparative Example 1 Step 1: Take a piece of 1.2 g / cm 3 , C / C composite material with size of Φ30 mm × 5 mm, after ultrasonic cleaning for 30 min, put into 70 ℃ oven to dry and wait for use; Step 2: Weigh La2O3 powder and place it in a beaker. Add an appropriate amount of anhydrous ethanol, where the mass fractions of La2O3 powder and anhydrous ethanol are 20 wt.% and 80 wt.%, respectively. Place the beaker on a magnetic stirrer and stir for 30 minutes until there are no obvious agglomerated particles in the La2O3 slurry. Set aside for later use. Step 3: Place the C / C composite with the ablated surface facing upward on filter paper in a vacuum filtration device. Turn on the vacuum pump and pour La2O3 slurry into the C / C composite several times. The La2O3 slurry enters the interior of the C / C composite under the suction force of the vacuum pump. Remove the sample and dry it in a 70°C oven for 24 hours before use. Repeat the above steps three times. The mass fraction of La2O3 in C / C-La2O3 is 11.5 wt.%; Step 4: Place a layer of Zr-Cu alloy powder on the bottom of the graphite crucible, where the mass fractions of Zr powder and Cu powder are 70 wt.% and 30 wt.%, respectively. Place the C / C-La2O3 composite material on the Zr-Cu alloy powder, and continue to add Zr-Cu alloy powder until the C / C-La2O3 composite material is completely covered. Step 5: Place the graphite crucible in a vacuum hot pressing furnace, turn on the vacuum pump to make the pressure in the furnace 1-50 Pa, first heat it to 900 °C at 10 °C / min, then heat it to 1300 °C at 5 °C / min, keep it for 2 hours, then reduce it to 800 °C at 5 °C / min, and then cool it to room temperature with the furnace to obtain La2O3 modified C / C-ZrC composite material without thermal conductive rod and partition modification structure design.

[0054] The composite material prepared in this comparative example was heated to a heat flux of 4.2 MW / m 2 After ablation under oxyacetylene flame for 40s×6, the oxide film formed on the surface of the composite material has many pores and cracks, and peeling occurs during the ablation process. The mass ablation rate is 3.25 mg / s and the linear ablation rate is 0.18 μm / s.

[0055] See also Figure 4 This is a microscopic morphology of the active and passive coordinated protection anti-cyclic ablation composite material with a heat-conducting rod structure design prepared in Example 1 of the present invention. Figure 4 (a) is a schematic diagram of the overall structure of the prepared composite material. Figure 4 (b) is the interface between the central area and the non-central area of ​​the composite material ablation surface. Area I is mainly ZrC, and area II is mainly SiC. Figure 4 (c) is the cross-sectional morphology of the heat conducting rod. From its enlarged view (d), we can see that the heat conducting rod is mainly composed of Cu. Figure 5 Figure 2 shows the surface temperature curves of the composite materials during the ablation process of Example 1 of the present invention and Comparative Example 1. It can be seen that the surface temperature of the cyclic ablation-resistant composite material with the thermal conductive rod and partitioned modified structure decreased by approximately 154°C during the ablation process compared to Comparative Example 1 without the structural design. The composite material prepared in Example 1 has good thermal conductivity, the temperature remains stable, and there is no continuous increase trend. The cyclic ablation life is increased from 240 s to 720 s. Figure 6 This is a microscopic image of different regions of the active and passive coordinated protection anti-cyclic ablation composite material with a thermal conductive rod structure, prepared in Example 1 of the present invention, after ablation. After 720 seconds of oxyacetylene ablation, the surface of different regions is covered with a dense oxide film, demonstrating excellent protection performance over a wide temperature range. Figure 7 The XRD pattern of the active and passive coordinated protection anti-cyclic ablation composite material with a heat-conducting rod structure prepared in Example 1 of the present invention after ablation shows that a large amount of t-ZrO2 still exists on the surface of the sample after oxyacetylene ablation for 720 seconds, indicating that the phase transformation of ZrO2 is suppressed during the cooling process. Figure 8 These are macroscopic pictures of the composite materials after ablation of Example 1 and Comparative Example 1 of the present invention. It can be seen that the cyclic ablation-resistant composite material designed with a heat-conducting rod and a partitioned modified structure shows obvious zoning characteristics after ablation. The central area is mainly composed of a white ZrO2 film, and the non-central area is mainly composed of a yellow SiO2. The oxide film is dense and crack-free, and no peeling occurs during the ablation process. However, after 240 s of oxyacetylene ablation, the carbon phase inside the matrix of the composite material of Comparative Example 1 is exposed on the surface, and the oxide film peels off during the ablation process.

[0056] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An active-passive collaborative anti-cyclic ablation composite material with a heat-conducting rod structure, characterized in that: It comprises a main body structure, wherein one end surface of the main body structure is an ablation surface and the opposite surface is a non-ablation surface; The main structure is divided into a central region and a non-central region, the upper end surface of the central region is part of the ablation surface, the lower end surface of the central region is inside the non-central region, and the side of the central region is wrapped by the non-central region; the central region is mainly composed of ZrC, the non-central region is mainly composed of SiC, and Cu is distributed in both the central region and the non-central region; Heat conducting rods are distributed in both the central area and the non-central area. The outer end surface of the heat conducting rod is a non-ablated surface, and the inner end surface is in the main structure. The heat conducting rod is made of Cu.

2. The active-passive coordinated anti-cyclic ablation composite material with a thermal conductive rod structure according to claim 1, characterized in that: The central area and the non-central area are coaxial.

3. The active-passive coordinated anti-cyclic ablation composite material with a thermal conductive rod structure according to claim 1, characterized in that: The diameter of the heat conducting rod is 1-2 mm, the distance between the edges of the heat conducting rod is 3-6 mm, and the length of the heat conducting rod is 60-80% of the thickness of the main structure.

4. A method for preparing the active-passive coordinated anti-cyclic ablation composite material with a thermally conductive rod structure according to claim 1, characterized in that: The method comprises the following preparation steps: S1, opening a plurality of heat conduction holes inward from the non-ablated surface of the main structure, wherein the main structure is a C / C composite material; S2, infiltrating La2O3 slurry into the ablation surface through vacuum filtration in the main structure, and obtaining C / C-La2O3 composite material after drying; S3, filling Cu powder into the thermal conductive holes in the C / C-La2O3 composite material to obtain a C / C-La2O3-Cu composite material; S4, laying a layer of Cu-Si alloy powder on the bottom of a graphite crucible, placing a C / C-La2O3-Cu composite material on the Cu-Si alloy powder, with the ablated surface facing upward and the non-ablated surface in contact with the Cu-Si alloy powder on the bottom layer, placing a hollow cylindrical mold on the ablated surface of the C / C-La2O3-Cu composite material, adding Zr-Cu alloy powder to the hollow cylindrical mold as the infiltration powder in the central area, and adding Cu-Si alloy powder as the infiltration powder in the non-central area, the infiltration powder in the non-central area fills the area outside the hollow cylindrical mold, and completely covers the C / C-La2O3-Cu composite material; S5, placing the graphite crucible loaded with the C / C-La2O3-Cu composite material and the infiltration powder in a vacuum hot pressing furnace, and obtaining a Cu and Si zone-modified C / C-ZrC-Cu-La2O3 composite material after vacuum negative pressure reaction infiltration; S6, Cu powder was added to the thermal conductive holes of the Cu and Si partitioned modified C / C-ZrC-Cu-La2O3 composite material, and vacuum negative pressure reactive infiltration was carried out in a vacuum hot pressing furnace to obtain an active-passive synergistic anti-cyclic ablation composite material with a thermal conductive rod structure.

5. The method for preparing the active-passive coordinated anti-cyclic ablation composite material with a thermal conductive rod structure according to claim 4, characterized in that: In S2, the infiltrated La2O3 slurry accounts for 5-20 wt.% of the mass of the C / C-La2O3 composite material.

6. The method for preparing the active-passive coordinated anti-cyclic ablation composite material with a thermal conductive rod structure according to claim 4, characterized in that: In S2, during the infiltration of La2O3 slurry, the vacuum filtration times are 2-4 times and the drying temperature is 70-100℃.

7. The method for preparing the active-passive coordinated anti-cyclic ablation composite material with a thermally conductive rod structure according to claim 4, characterized in that: In S4, in the Cu-Si alloy powder, the mass fraction of Cu powder is 75-90 wt.%, and the mass fraction of Si powder is 10-25 wt.%.

8. The method for preparing the active-passive coordinated anti-cyclic ablation composite material with a thermally conductive rod structure according to claim 4, characterized in that: In S4, in the Zr-Cu alloy powder, the mass fraction of Zr powder is 60-80 wt.%, and the mass fraction of Cu powder is 20-40 wt.%.

9. The method for preparing the active-passive coordinated anti-cyclic ablation composite material with a thermally conductive rod structure according to claim 4, characterized in that: In S5 and S6, the heating and cooling process of vacuum negative pressure reaction infiltration is as follows: heating to 850-1050 °C at 8-13 °C / min; heating to 1100-1400 °C at 3-7 °C / min; after holding treatment for 0.5-3 h, reducing the temperature to 750-900 °C at 3-7 °C / min, and then cooling to room temperature with the furnace.

10. The method for preparing the active-passive coordinated anti-cyclic ablation composite material with a thermally conductive rod structure according to claim 4, characterized in that: In S4, the hollow cylindrical mold and the C / C-La2O3-Cu composite material are coaxial.

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