A method for preparing a high ceramic yield zirconium carbide-silicon carbide aerogel composite

Abstract

The application relates to a preparation method of a ZrC-SiC aerogel composite with high ceramic yield, belonging to the field of thermal protection materials. Monomer-grade small-molecule phenol and aldehyde are used as carbon source precursors, silicon sources and zirconium sources are introduced, a molecular-level uniform Zr-Si-O-C hybrid network is constructed through a step-by-step sol-gel method, and the stoichiometric ratio of C / (Zr+Si) is accurately controlled based on the network, so that the system is subjected to impregnation, normal-pressure drying and high-temperature carbon thermal reduction, thereby obtaining a ZrC-SiC aerogel composite with high ceramic yield, and realizing the transformation of the material from a carbon-based composite system to a carbide ceramic-based aerogel. The high-density chemical crosslinking network formed by in-situ condensation of small molecules endows the aerogel skeleton with excellent mechanical strength, overcomes the capillary contraction cracking in the normal-pressure drying process, eliminates the dependence on the high-energy-consumption supercritical drying process, and is helpful to the large-scale engineering preparation of the thermal protection material.

Description

Technical Field

[0001] This invention relates to a method for preparing ZrC-SiC aerogel composite material with high ceramic yield, belonging to the field of thermal protection material preparation. Background Technology

[0002] With the rapid development of hypersonic aircraft and space travel technology, thermal protection systems have placed unprecedentedly stringent requirements on materials for lightweighting, oxidation resistance, and efficient thermal insulation performance.

[0003] Aerogels, as lightweight three-dimensional porous materials, have attracted widespread attention in the field of thermal protection due to their high porosity, low thermal conductivity, and flexible composition design. However, traditional oxide aerogels (such as SiO2, Al2O3, ZrO2, etc.) often undergo severe sintering, shrinkage, or even structural collapse in environments exceeding 1200℃, leading to a significant degradation in their thermal protection performance. Organic aerogels (such as phenolic aerogels, polyimide aerogels, etc.) are highly susceptible to oxidative combustion or thermal oxidative degradation in high-temperature aerobic environments, resulting in very limited long-term service temperatures. To overcome this limitation, non-sintering ceramic components and antioxidants are introduced into the three-dimensional porous aerogel framework to prepare zirconium carbide-silicon carbide (ZrC-SiC) ceramic aerogel-based composite materials, which not only meet the requirements of lightweight and thermal insulation but also exhibit good high-temperature oxidation resistance and thermal stability.

[0004] However, research on ZrC-SiC aerogel-based materials is still limited. Problems in the preparation process include low ceramic conversion rates and an excessive carbon content, leading to a significant decrease in the material's antioxidant properties. Furthermore, when the organic network is too large, the relative spacing between the silicon and zirconium sources within the network increases. During carbothermal reduction, the diffusion paths between C, Si, and Zr elements become longer, easily resulting in uneven distribution of the formed carbides and causing component segregation. To achieve the transformation from carbon-based composite materials to carbide-based composite materials, this invention constructs a molecularly uniform Zr-Si-OC hybrid network using a stepwise sol-gel method. Based on this network, the stoichiometric ratio of C / (Zr+Si) is precisely controlled. After impregnation, atmospheric pressure drying, and high-temperature carbothermal reduction, a high-ceramic-yield ZrC-SiC aerogel composite material is obtained, realizing the transformation of the material from a carbon-based composite system to a carbide ceramic-based aerogel. Meanwhile, the high-density chemical cross-linking network formed by in-situ polycondensation of small molecules endows the aerogel skeleton with excellent mechanical strength, effectively overcoming capillary shrinkage and cracking during atmospheric pressure drying, eliminating the dependence on high-energy-consuming supercritical drying processes, and providing a new, efficient, and low-cost approach for the large-scale engineering preparation of this type of thermal protection material. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing a ZrC-SiC aerogel composite material with high ceramic yield. Monomer-grade small molecule phenols and aldehydes are used as carbon source precursors, with organosilicon and organozirconium as silicon and zirconium sources, respectively. A hybrid network is constructed via a stepwise sol-gel method, followed by impregnation, atmospheric pressure drying, and high-temperature carbothermic reduction to obtain a ZrC-SiC aerogel composite material with excellent oxidation resistance and thermal insulation properties. The room temperature thermal conductivity of this composite material is 0.061 W∙m. -1 ∙K -1 After being tested under a butane flame at 1250 ℃ for 30 min, the oxide layer thickness was only 580 μm and the back temperature was only 105 ℃, demonstrating ideal anti-oxidation and heat insulation performance. After being tested under an oxyacetylene flame at 1832 ℃ for 30 min, the back temperature stabilized at 221 ℃ and there was no damage to the surface, demonstrating excellent anti-oxidation and heat insulation function under high temperature conditions, proving that the material has the application potential for thermal protection in extreme environments.

[0006] The objective of this invention is achieved through the following technical solution:

[0007] This invention discloses a method for preparing a ZrC-SiC aerogel composite material with high ceramic yield, comprising the following steps:

[0008] Step 1: Preparation of phenolic solution: Dissolve phenolic monomers and aldehyde monomers in anhydrous ethanol to prepare a phenolic solution with a mass fraction of 15-50%.

[0009] Step 2, Preparation of Si-modified solution: The pre-hydrolyzed Si source is added to the above phenolic solution and stirred to carry out a polycondensation reaction to obtain a Si-modified phenolic precursor solution;

[0010] Step 3: Preparation of Zr modified solution: Add Zr source to the Si modified phenolic precursor solution and continue stirring to carry out polycondensation reaction to obtain Zr-Si modified phenolic precursor blend solution;

[0011] Step 4: Impregnation and composite: The above Zr-Si modified phenolic precursor blend solution is impregnated and composited with the fiber preform under vacuum pressure.

[0012] Step 5, Gel Aging: The impregnated material is subjected to an aging reaction in an oven to obtain a phenolic-Zr-Si gel composite material;

[0013] Step 6: Drying at atmospheric pressure: Place the above phenolic-Zr-Si gel composite material in a forced-air drying oven for atmospheric pressure gradient temperature rise drying to obtain phenolic-Zr-Si aerogel composite material;

[0014] Step 7, Carbothermic Reduction: The phenolic-Zr-Si aerogel composite material obtained above is subjected to high-temperature carbothermic reduction treatment under an inert atmosphere to obtain ZrC-SiC aerogel composite material.

[0015] Furthermore, the phenols mentioned in step one are one or more of phenol, resorcinol, phloroglucinol, cresol, and bisphenol A; the aldehydes are one or more of formaldehyde, acetaldehyde, furfural, and glyoxal.

[0016] Furthermore, the Si source mentioned in step two is one or more of the following: tetraethyl orthosilicate, methyl orthosilicate, methyltriethoxysilane, tetrapropoxysilane, 3-aminopropyltriethoxysilane, ethyltrimethylsilane, polycarbosilane, trimethylphenylsilane, water glass, and silica sol.

[0017] Furthermore, the Zr source mentioned in step three is one or more of zirconium oxychloride octahydrate, zirconium oxynitrate hydrate, zirconium sulfate tetrahydrate, zirconium acetylacetonate, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide, zirconium tert-butoxide, zirconium acetate, zirconium dichlorocerocene, zirconium tetrachloride, and zirconium silicate.

[0018] Furthermore, in the Zr-Si modified phenolic precursor blend solution, the molar ratio of Zr to Si is 0.2:1 to 3:1; and the molar ratio of the total carbon provided by phenolic and aldehyde monomers to the total (Si+Zr) provided by Si and Zr sources is 3:1 to 8:1, so as to meet the stoichiometric ratio for generating carbide ceramic phase and limit the free carbon content in the final product.

[0019] Furthermore, in step two, the stirring time after adding the Si source to the phenolic sol is 0.2-12 h; in step three, the stirring time after adding the Zr source to the phenolic sol is 0.2-12 h.

[0020] Furthermore, the vacuum impregnation and lamination process described in step four takes 10-180 minutes.

[0021] Furthermore, the fiber preform mentioned in step four is one or more of the following: high silica fiber preform, carbon fiber preform, quartz fiber preform, mullite fiber preform, alumina fiber preform, zirconia fiber preform, and basalt fiber preform.

[0022] Furthermore, the aging temperature of the gel described in step five is 30-180 °C, and the aging time is 5-120 h.

[0023] Furthermore, the atmospheric pressure gradient heating drying temperature described in step six is ​​30-180 °C, and the drying time is 6-120 h.

[0024] Furthermore, the temperature of the high-temperature carbothermal reduction treatment in step seven is 1000-1800 ℃.

[0025] A ZrC-SiC aerogel composite material with high ceramic yield is prepared by a method for preparing the ZrC-SiC aerogel composite material with high ceramic yield.

[0026] An antioxidant application of a high ceramic yield ZrC-SiC aerogel composite material, specifically its application in the preparation of antioxidant and long-lasting thermal insulation components for extreme aerospace environments.

[0027] Beneficial effects:

[0028] (1) The present invention discloses a method for preparing ZrC-SiC aerogel composite material with high ceramic yield, which controls the C / (Zr+Si) atomic ratio to near the theoretically required value, fundamentally reducing residual free carbon or unreacted oxides, promoting the transformation of the material from carbon-based composite system to carbide ceramic-based aerogel, and achieving high ceramic conversion rate.

[0029] (2) The present invention discloses a method for preparing ZrC-SiC aerogel composite material with high ceramic yield. By stepwise controlling the sol-gel process of Si source and Zr source, a molecularly uniform Zr–Si–O–C precursor can be obtained without introducing phase separation, and then transformed into a uniform co-continuous ZrC-SiC nanocrystalline framework.

[0030] (3) The present invention discloses a method for preparing ZrC-SiC aerogel composite material with high ceramic yield, which abandons the traditional supercritical drying process and achieves a yield as low as 0.061 W·m through atmospheric pressure gradient heating drying. -1 ·K -1 Its thermal conductivity has opened up a path for high-performance, low-cost mass production.

[0031] (4) The present invention discloses a method for preparing ZrC-SiC aerogel composite material with high ceramic yield. The obtained material forms a viscous flow ZrO2-SiO2 glass phase in situ on the surface in a high-temperature oxygen flame. It is not only dense but also has the function of self-healing cracks. After testing in a butane flame at 1250℃ for 30 min, the oxide layer is only 580 μm thick and the back temperature is as low as 105℃. Even after testing in an oxyacetylene flame at 1830℃ for 30 min, the ablation surface is still intact and the back temperature is maintained at 221℃, achieving the dual functions of anti-oxidation and heat insulation. Attached Figure Description

[0032] Figure 1Images of ZrC-SiC aerogel composites with different C / (Zr+Si) stoichiometric ratios are shown. Figure 1 (a) is a ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 2:1. Figure 1 (b) is a ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 3:1. Figure 1 (c) is a ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 4:1. Figure 1 (d) ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 6:1. Figure 1 (e) is a ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 8:1. Figure 1 (f) is a ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 9:1.

[0033] Figure 2 Microstructure diagrams of ZrC-SiC aerogel composites with different C / (Zr+Si) stoichiometric ratios are shown. Figure 2 (a) is a ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 2:1. Figure 2 (b) is a ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 3:1. Figure 2 (c) is a ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 4:1. Figure 2 (d) is a ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 6:1. Figure 2 (e) is a ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 8:1. Figure 2 (f) is a ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 9:1.

[0034] Figure 3 Thermogravimetric-differential scanning calorimetry (TGC) curves of ZrC-SiC aerogel composites with different C / (Zr+Si) stoichiometric ratios are shown below. Figure 3 (a) is a ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 3:1. Figure 3 (b) is a ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 4:1. Figure 3 (c) is a ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 6:1. Figure 3(d) is a ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 8:1.

[0035] Figure 4 The ablation surface morphology of ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 6:1 before and after 30 min in a butane flame at 1250℃.

[0036] Figure 5 The ablation surface morphology of ZrC-SiC aerogel composite material with a C / (Zr+Si) stoichiometric ratio of 6:1 before and after 1800s in an oxyacetylene flame at 1830℃. Detailed Implementation

[0037] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0038] Example 1

[0039] A method for preparing ZrC-SiC aerogel composite material with high ceramic yield, the specific implementation steps are as follows:

[0040] Resorcinol and formaldehyde monomers were dissolved in anhydrous ethanol to prepare a 35% (w / w) phenolic solution. Pre-hydrolyzed tetraethyl orthosilicate was added to the phenolic solution, and the mixture was stirred for 30 min to carry out a polycondensation reaction, yielding a Si-modified phenolic precursor solution. Zirconium propoxide was added to the Si-modified phenolic precursor solution, and the polycondensation reaction was continued to obtain a Zr-Si modified phenolic precursor blend solution, wherein the stoichiometric ratio C / (Zr+Si) = 6:1 and the molar ratio Zr:Si = 1:1. Subsequently, the Zr-Si modified phenolic precursor blend solution and a carbon fiber preform were impregnated and composited under vacuum pressure for 1 h, and then aged in an 80℃ oven for 24 h to obtain a phenolic-Zr-Si gel composite material. The phenolic-Zr-Si gel composite material was subjected to atmospheric pressure gradient temperature rise drying in a forced-air drying oven (40℃ 4h - 60℃ 4h - 80℃ 4h - 100℃ 2h) to obtain a phenolic-Zr-Si aerogel composite material. The obtained phenolic-Zr-Si aerogel composite material was then heated to 1000℃ under an inert atmosphere to undergo a carbonization reaction for 2h, followed by a carbothermic reduction reaction at 1600℃ for 2h to obtain a ZrC-SiC aerogel composite material.

[0041] Example 2

[0042] A method for preparing ZrC-SiC aerogel composite material with high ceramic yield, the specific implementation steps are as follows:

[0043] Phenol and furfural were dissolved in anhydrous ethanol to prepare a 35% (w / w) phenolic solution. Pre-hydrolyzed tetraethyl silicate and methyltriethoxysilane were added to the phenolic solution, and the mixture was stirred for 30 min to carry out a polycondensation reaction, yielding a Si-modified phenolic precursor solution. Zirconium oxychloride octahydrate was added to the Si-modified phenolic precursor solution, and the polycondensation reaction was continued to obtain a Zr-Si-modified phenolic precursor blend solution, wherein the stoichiometric ratio C / (Zr+Si) = 4:1 and the molar ratio Zr:Si = 0.78:1. Subsequently, the Zr-Si-modified phenolic precursor blend solution was impregnated with a quartz fiber preform under vacuum pressure for 1 h, and then aged in an oven at 80 °C for 24 h to obtain a phenolic-Zr-Si gel composite material. The phenolic-Zr-Si gel composite material was subjected to atmospheric pressure gradient temperature rise drying in a forced-air drying oven (40℃ 4h - 60℃ 4h - 80℃ 4h - 100℃ 2h) to obtain the phenolic-Zr-Si aerogel composite material. The obtained phenolic-Zr-Si aerogel composite material was then heated to 1000℃ under an inert atmosphere to undergo a carbonization reaction for 2h, followed by a carbothermic reduction reaction at 1600℃ for 2h to obtain the ZrC-SiC aerogel composite material.

[0044] Example 3

[0045] A method for preparing ZrC-SiC aerogel composite material with high ceramic yield, the specific implementation steps are as follows:

[0046] Resorcinol and furfural were dissolved in anhydrous ethanol to prepare a 45% (w / w) phenolic solution. Pre-hydrolyzed tetraethyl silicate was added to the phenolic solution, and the mixture was stirred for 30 min to carry out a polycondensation reaction, yielding a Si-modified phenolic precursor solution. Zirconium butoxide was added to the Si-modified phenolic precursor solution, and the polycondensation reaction was continued to obtain a Zr-Si modified phenolic precursor blend solution, wherein the stoichiometric ratio C / (Zr+Si) = 6:1 and the molar ratio Zr:Si = 1:1. Subsequently, the Zr-Si modified phenolic precursor blend solution was impregnated with a mullite fiber preform under vacuum pressure for 1 h, and then aged in an 80℃ oven for 24 h to obtain a phenolic-Zr-Si gel composite material. The phenolic-Zr-Si gel composite material was subjected to atmospheric pressure gradient temperature rise drying in a forced-air drying oven (40℃ 4h - 60℃ 4h - 80℃ 4h - 100℃ 2h) to obtain a phenolic-Zr-Si aerogel composite material. The obtained phenolic-Zr-Si aerogel composite material was then heated to 1000℃ under an inert atmosphere to undergo a carbonization reaction for 2h, followed by a carbothermic reduction reaction at 1500℃ for 2h to obtain a ZrC-SiC aerogel composite material.

[0047] Comparative Example 1

[0048] A method for preparing a ZrC-SiC aerogel composite material with high ceramic yield includes the following steps:

[0049] Example 1 was repeated, but with a stoichiometric ratio of C / (Zr+Si) = 2:1. An aerogel structure could not be formed, and the material was obtained as a powder after frequent pressure drying.

[0050] Comparative Example 2

[0051] A method for preparing a ZrC-SiC aerogel composite material with high ceramic yield includes the following steps:

[0052] Repeat Example 1, but with a stoichiometric ratio of C / (Zr+Si) = 3:1.

[0053] Comparative Example 3

[0054] A method for preparing a ZrC-SiC aerogel composite material with high ceramic yield includes the following steps:

[0055] Repeat Example 1, but with a stoichiometric ratio of C / (Zr+Si) = 4:1.

[0056] Comparative Example 4

[0057] A method for preparing a ZrC-SiC aerogel composite material with high ceramic yield includes the following steps:

[0058] Repeat Example 1, but with a stoichiometric ratio of C / (Zr+Si) = 8:1.

[0059] Comparative Example 5

[0060] A method for preparing a ZrC-SiC aerogel composite material with high ceramic yield includes the following steps:

[0061] Example 1 was repeated, but with a stoichiometric ratio of C / (Zr+Si) = 9:1. The resulting material was similar to pure carbon aerogel, exhibiting severe pulverization after butane flame testing at 1250°C, and its antioxidant properties were significantly reduced.

[0062] Comparative Example 6

[0063] A method for preparing a ZrC-SiC aerogel composite material with high ceramic yield includes the following steps:

[0064] Repeat Example 1, but with a molar ratio of Zr:Si = 0.78:1.

[0065] Comparative Example 7

[0066] A method for preparing a ZrC-SiC aerogel composite material with high ceramic yield includes the following steps:

[0067] Repeat Example 1, but with a molar ratio of Zr:Si = 1.5:1.

[0068] The microstructure and crystal phase distribution of the composite material were analyzed using transmission electron microscopy. The residual weight and ceramic conversion rate of the composite material were analyzed using thermogravimetric-differential scanning calorimetry (TGC-DSC). The composite material was tested in a butane flame at 1250℃ for 30 min, and the change in oxide layer thickness was recorded. The high-temperature ablation and oxidation properties of the composite material were tested according to the national standard GJB 323B-2018 "Test Methods for Ablation of Ablation Materials". The hot-end surface temperature was 1830℃, and the total heating time was 1800 s. The ablation condition of the ablated surface and the temperature rise curve of the back side were recorded to evaluate its high-temperature oxidation resistance and thermal insulation properties. The test results are shown in Table 1.

[0069] Table 1. Comparison of residual weight, thermal conductivity, oxide layer thickness, and back temperature rise of different samples.

[0070]

[0071] As shown in Table 1, the composite material obtained in this invention exhibits a high ceramic conversion rate and low thermal conductivity, indicating ideal oxidation resistance and thermal insulation capabilities. Examples 1 and Comparative Examples 2, 3, and 4 demonstrate that precisely controlling the stoichiometric ratio of C / (Zr+Si) can significantly improve the ceramic yield and oxidation resistance of the material (e.g., ceramic yield increases from 57.78% to 69.08%, and oxide layer thickness decreases from 2540 μm to 580 μm). Examples 1 and Comparative Examples 6 and 7 show that adjusting the molar ratio of Zr / Si can reduce the thermal conductivity of the composite material and significantly improve its thermal insulation capabilities (thermal conductivity decreases from 0.081 W·m). -1 ∙K -1 Reduced to 0.061 W∙m -1 ∙K -1 (The back temperature rise after the oxyacetylene test decreased from 498℃ to 221℃). As can be seen from Example 1 and Comparative Examples 1 and 5, if the stoichiometric ratio of C / (Zr+Si) exceeds the range of 3:1 to 8:1, when C / (Zr+Si) < 3:1, as shown in Comparative Example 1, the material obtained after atmospheric pressure drying is a powdery material that cannot form an aerogel material and cannot perform the functions of heat insulation and anti-oxidation; when C / (Zr+Si) > 8:1, as shown in Comparative Example 5, the obtained material is similar to pure carbon aerogel in terms of heat insulation and anti-oxidation performance, but after the butane flame test at 1250℃, it exhibits severe pulverization and cannot perform the function of anti-oxidation.

[0072] The above detailed description further illustrates the purpose, technical solution, and beneficial effects of the invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a ZrC-SiC aerogel composite material with high ceramic yield, characterized in that: Includes the following steps: Step 1: Preparation of phenolic solution: Dissolve phenolic monomers and aldehyde monomers in anhydrous ethanol to prepare a phenolic solution with a mass fraction of 15-50%. Step 2, Preparation of Si-modified solution: The pre-hydrolyzed Si source is added to the above phenolic solution and stirred to carry out a polycondensation reaction to obtain a Si-modified phenolic precursor solution; Step 3: Preparation of Zr modified solution: Add Zr source to the Si modified phenolic precursor solution and continue stirring to carry out polycondensation reaction to obtain Zr-Si modified phenolic precursor blend solution; Step 4, Impregnation and Composite: The above Zr-Si modified phenolic precursor blend solution is impregnated and composited with the fiber felt under vacuum pressure; Step 5, Gel Aging: The impregnated material is subjected to an aging reaction in an oven to obtain a phenolic-Zr-Si gel composite material; Step 6: Drying at atmospheric pressure: The above phenolic-Zr-Si gel composite material is placed in a forced-air drying oven for drying under atmospheric pressure gradient temperature to obtain phenolic-Zr-Si aerogel composite material; Step 7, Carbothermic Reduction: The phenolic-Zr-Si aerogel composite material obtained above is subjected to high-temperature carbothermic reduction treatment under an inert atmosphere to obtain ZrC-SiC aerogel composite material.

2. The method as described in claim 1, characterized in that: The phenols mentioned in step one are one or more of phenol, resorcinol, phloroglucinol, cresol, and bisphenol A; the aldehydes are one or more of formaldehyde, acetaldehyde, furfural, and glyoxal.

3. The method as described in claim 1, characterized in that: The Si source mentioned in step two is one or more of the following: tetraethyl orthosilicate, methyl orthosilicate, methyltriethoxysilane, tetrapropoxysilane, 3-aminopropyltriethoxysilane, ethyltrimethylsilane, polycarbosilane, trimethylphenylsilane, water glass, and silica sol.

4. The method as described in claim 1, characterized in that: The Zr source mentioned in step three is one or more of the following: zirconium oxychloride octahydrate, zirconium oxynitrate hydrate, zirconium sulfate tetrahydrate, zirconium acetylacetonate, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide, zirconium tert-butoxide, zirconium acetate, zirconium dichlorocerocene, zirconium tetrachloride, and zirconium silicate.

5. The method as described in claim 1, characterized in that: In the Zr-Si modified phenolic precursor blend solution, the molar ratio of Zr to Si is 0.2:1 to 3:1; and the stoichiometric ratio of the total carbon provided by phenolic and aldehyde monomers to the total (Si+Zr) provided by Si and Zr sources is 3:1 to 8:1, so as to meet the stoichiometric ratio for generating carbide ceramic phase and limit the free carbon content in the final product.

6. The method as described in claim 1, characterized in that: The stirring time after adding the Si source to the phenolic sol in step two is 0.2-12 h; the stirring time after adding the Zr source to the phenolic sol in step three is 0.2-12 h.

7. The method as described in claim 1, characterized in that: The vacuum impregnation and lamination process described in step four takes 10-180 minutes. The aging temperature of the gel described in step five is 30-180 °C, and the aging time is 5-120 h; The atmospheric pressure gradient heating drying temperature described in step six is ​​30-180 °C, and the drying time is 6-120 h; The temperature of the high-temperature carbothermal reduction treatment in step seven is 1000-1800 ℃.

8. The method as described in claim 1, characterized in that: The fiber preform mentioned in step four is one or more of the following: high silica fiber preform, carbon fiber preform, quartz fiber preform, mullite fiber preform, alumina fiber preform, zirconia fiber preform, and basalt fiber preform.

9. A ZrC-SiC aerogel composite material with high ceramic yield, characterized in that: This is a ZrC-SiC aerogel composite material with high ceramic yield prepared by the preparation method according to any one of claims 1 to 8.

10. The antioxidant application of the ZrC-SiC aerogel composite material as described in claim 9, characterized in that: Applications in the preparation of antioxidant and long-lasting thermal insulation components for extreme aerospace environments.

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