A ceramic-modified C / C composite material with a ZrC-SiC-PyC interface layer and its preparation method

Abstract

This invention discloses a ceramic-modified C / C composite material with a ZrC-SiC-PyC interface layer and its preparation method, belonging to the technical field of ceramic-modified carbon / carbon composite material preparation. The preparation method is as follows: ZrSi2 powder is introduced into a low-density C / C composite material using the SI method to obtain a low-density C / C composite material containing ZrSi2 powder; the low-density C / C composite material containing ZrSi2 powder is then processed into a low-density C / C composite material with a ZrC-SiC-PyC interface layer using a first RMI method; PyC is deposited onto the low-density C / C composite material with the ZrC-SiC-PyC interface layer using chemical vapor deposition; and then a ceramic-modified C / C composite material with a ZrC-SiC-PyC interface layer is prepared using a second RMI method. This invention combines the SI and RMI methods to prepare a ceramic-modified C / C composite material with a ZrC-SiC-PyC interface layer. Constructing a ceramic interface layer on the carbon fiber surface effectively reduces the erosion of the carbon fiber by the ceramic melt during the RMI preparation of the ceramic-modified C / C composite material.

Description

Technical Field

[0001] This invention belongs to the field of ceramic modified carbon / carbon composite material preparation technology, specifically relating to a ceramic modified C / C composite material with a ZrC-SiC-PyC interface layer and its preparation method. Background Technology

[0002] The high-temperature resistance, ablation resistance, and excellent high-temperature mechanical properties of carbon / carbon (C / C) composites have made them highly valuable in the development of aerospace vehicles. However, due to the inherent susceptibility of carbon materials to oxidation, C / C composites exhibit poor structural stability and a sharp decline in performance under extreme high-temperature oxygen-rich environments, severely limiting their application and development. To address this issue, introducing ultra-high-temperature ceramic phases, such as silicon carbide (SiC) and zirconium carbide (ZrC), into C / C composites—that is, preparing ultra-high-temperature ceramic-modified C / C composites—can effectively improve their oxidation resistance and simultaneously significantly enhance their ablation resistance.

[0003] Currently, commonly used ceramic-modified C / C composite materials processes include polymer impregnation pyrolysis (PIP), chemical vapor infiltration (CVI), and reactive melting infiltration (RMI). PIP utilizes the self-pyrolysis reaction of ceramic organic precursors to produce ceramics, while CVI utilizes the chemical reaction between gaseous components. The ceramic phases produced by these two methods do not react with the C / C composite material itself, representing externally introduced ceramic phases. Reactive melting infiltration (RMI), on the other hand, utilizes the infiltration of melt into pores and the chemical reaction between transition elements and carbon materials to synthesize a large amount of ceramic phases in situ within the C / C composite material. The literature “Zhao ZG, Li KZ, Li W, et al. Ablation behavior of C / C-ZrC-SiC composites prepared by reactive melt infiltration under oxyacetylene torch at two heat fluxes[J].Ceramics International, 2018, 44(14): 17345-17358” describes the preparation of C / C-ZrC-SiC composites using ZrSi2 as raw material via RMI (Reactive Melt Infiltration). After oxyacetylene ablation testing, the composites exhibited good linear and mass ablation rates, but their mechanical properties were poor. This is because during RMI, the molten metal penetrates into the C / C composite and reacts with the carbon matrix. This chemical reaction is highly reactive, and the mass of the supplied molten metal is much greater than the mass of the carbon matrix, resulting in the complete consumption of the carbon matrix and forcing the carbon fibers to react with the molten metal. When the carbon fibers are eroded by the molten metal, the structural integrity is compromised, the load-bearing capacity is reduced, and ultimately, the mechanical properties of the composites significantly decrease. To address this issue, the literature “Sun Q, Zhang HF, Huang CB, et al. Fabrication of C / C-SiC-ZrB2 Ultra-High Temperature Composites through Liquid-Solid Chemical Reaction[J]. Crystals, 2021, 11(11).” first introduced ZrB2 powder into the C / C composite material using a slurry impregnation method, and then finally prepared the C / C-ZrB2-SiC composite material using RMI. Due to the presence of ZrB2 powder, most of the carbon fibers inside the composite material were not completely corroded by the molten metal, thus exhibiting good load-bearing capacity.The literature “Ye ZY, Wang YL, Xiong X, et al. Microstructure, interfacial and mechanical properties of SiC interphase modified C / C-SiC composites prepared by reactive meltinfiltration[J]. Journal of the European Ceramic Society, 2024, 44(15)” uses chemical vapor infiltration (CVI) to first construct a SiC interface layer on the carbon fiber surface, then deposit pyrolytic carbon, and finally prepare C / C-SiC composites by reactive meltinfiltration (RMI). The study found that the Si melt only reacted with the pyrolytic carbon, and the SiC interface layer effectively prevented the melt from eroding the carbon fiber. Compared with the C / C-SiC composites without an interface layer, the bending performance of the C / C-SiC composites with the SiC interface layer was improved by 35.69%. However, the CVI process for preparing the interface layer is complex and expensive, and there is an urgent need for a simple and low-cost process to achieve rapid preparation of the interface layer. Summary of the Invention

[0004] To overcome the shortcomings of the prior art, the present invention aims to propose a ceramic-modified C / C composite material with a ZrC-SiC-PyC interface layer and its preparation method. The ceramic-modified C / C composite material with a ZrC-SiC-PyC interface layer is prepared by combining the SI method and the RMI method. Constructing a ceramic interface layer on the carbon fiber surface can effectively reduce the erosion of the carbon fiber by the ceramic melt during the preparation of the ceramic-modified C / C composite material by the RMI method.

[0005] To achieve the above objectives, the present invention employs the following technical solution:

[0006] This invention provides a method for preparing ceramic-modified C / C composite materials with a ZrC-SiC-PyC interface layer, comprising the following steps:

[0007] A low-density C / C composite material containing ZrSi2 powder was prepared by introducing ZrSi2 powder into the interior of the low-density C / C composite material using the SI method.

[0008] The low-density C / C composite material containing ZrSi2 powder was prepared into a low-density C / C composite material with a ZrC-SiC-PyC interface layer by the first RMI method.

[0009] PyC was deposited onto a low-density C / C composite material with a ZrC-SiC-PyC interface layer using chemical vapor deposition, resulting in a low-density C / C composite material with a ZrC-SiC-PyC interface layer after PyC deposition. Then, a ceramic-modified C / C composite material with a ZrC-SiC-PyC interface layer was prepared by a second RMI method.

[0010] In one embodiment, the process of introducing ZrSi2 powder into a low-density C / C composite material using the SI method to obtain a low-density C / C composite material containing ZrSi2 powder is as follows:

[0011] The C / C composite material was immersed in ZrSi2 slurry and then placed in a vacuum environment of -0.09MPa for 30 minutes. After being taken out, it was rinsed and dried to obtain a low-density C / C composite material with ZrSi2 powder dispersed inside. This step was repeated 1-5 times to obtain a low-density C / C composite material containing ZrSi2 powder.

[0012] In one embodiment, the ZrSi2 slurry is prepared as follows:

[0013] A phenolic resin solution was prepared by adding phenolic resin powder to anhydrous ethanol.

[0014] ZrSi2 powder with a particle size of 1-3 micrometers was added to a phenolic resin solution to prepare a ZrSi2 slurry.

[0015] In one embodiment, the mass ratio of the phenolic resin powder to anhydrous ethanol is 1:10; and the mass ratio of the ZrSi2 powder to the phenolic resin powder is 1:6.

[0016] In one embodiment, the process of preparing a low-density C / C composite material containing ZrSi2 powder into a low-density C / C composite material with a ZrC-SiC-PyC interface layer by a first RMI method is as follows:

[0017] The low-density C / C composite material containing ZrSi2 powder was placed in a graphite crucible, and then the graphite crucible was placed in a vacuum high-temperature graphitization furnace. Under the vacuum conditions of -0.09MPa inside the vacuum high-temperature graphitization furnace, the furnace was heated to 2000℃ at a heating rate of 5℃ / min and held for 2 hours. Then it was cooled to room temperature at a cooling rate of 5℃ / min.

[0018] In one embodiment, the ZrC-SiC-PyC interface layer in the low-density C / C composite material with the ZrC-SiC-PyC interface layer comprises ZrC and SiC granular phases and a PyC phase on the outer side of the carbon fiber. The ZrC and SiC granular phases are generated by a chemical reaction between ZrSi2 and PyC and are uniformly coated on the surface of the PyC phase on the outer side of the carbon fiber, forming a granular ZrC-SiC-PyC interface phase.

[0019] In one embodiment, the process of depositing PyC onto a low-density C / C composite material with a ZrC-SiC-PyC interface layer using chemical vapor deposition is as follows:

[0020] The low-density C / C composite material with a ZrC-SiC-PyC interface layer was placed in an isothermal chemical vapor deposition furnace, which was heated to 1200℃ at a heating rate of 10℃ / h, during which argon gas was continuously introduced at a flow rate of 50 sccm.

[0021] After the temperature is raised to 1200℃, natural gas is introduced into the isothermal chemical vapor deposition furnace at a flow rate of 500 sccm, while the argon flow rate is set to 1500 sccm. The furnace is then held at 1200℃ for 4 to 16 hours. After that, the natural gas supply is stopped, the argon flow rate is adjusted to 50 sccm, and the furnace is allowed to cool naturally to room temperature. The PyC deposition is then complete.

[0022] In one embodiment, the carbon fibers in the low-density C / C composite material with a ZrC-SiC-PyC interface layer after PyC deposition are, from the inside out, a PyC layer, a ZrC-SiC particle layer, and a deposited PyC layer.

[0023] The deposited PyC layer will serve as an internal carbon source to provide reaction materials for the preparation of ceramic-modified C / C composite materials.

[0024] In one embodiment, the process of preparing the ceramic-modified C / C composite material with a ZrC-SiC-PyC interface layer by the second RMI method is as follows:

[0025] The low-density C / C composite material with ZrC-SiC-PyC interface layer after PyC deposition was placed in a graphite crucible. ZrSi2 powder with a particle size of 1-3 micrometers was used to completely bury the low-density C / C composite material with ZrC-SiC-PyC interface layer after PyC deposition. Then it was placed in a vacuum high-temperature graphitization furnace. Under the vacuum conditions of -0.09MPa inside the vacuum high-temperature graphitization furnace, the temperature was heated to 2000℃ at a heating rate of 5℃ / min and held for 2h. Then it was cooled to room temperature at a cooling rate of 5℃ / min.

[0026] Another aspect of the present invention provides a ceramic modified C / C composite material with a ZrC-SiC-PyC interface layer prepared by the above-mentioned method for preparing ceramic modified C / C composite material with a ZrC-SiC-PyC interface layer, the material comprising a C / C-ZrC-SiC composite matrix phase and carbon fibers located inside the C / C-ZrC-SiC composite matrix phase.

[0027] The matrix phase of the C / C-ZrC-SiC composite material is a ceramic phase generated by the reaction of deposited PyC with ZrSi2.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] This invention provides a method for preparing ceramic-modified C / C composite materials with a ZrC-SiC-PyC interfacial layer. First, this invention prepares a ZrC-SiC-PyC interfacial layer in low-density C / C composite materials using a two-step method involving SI and RMI. Compared to CVD and PIP methods, the proposed method demonstrates significant advantages in terms of operational difficulty and cost control. By adjusting the ZrSi2 content introduced into the low-density C / C composite material via the SI method, ceramic interfacial layers of varying thicknesses can be obtained. The ZrC-SiC-PyC interfacial layer prepared according to this invention has a rougher surface compared to the ceramic interfacial layer prepared by the CVD method, which facilitates the interlocking effect between the interfacial layer and the matrix, and also guides crack deflection, increasing the bonding strength between the interface and the matrix and improving the cohesion of the composite matrix. Secondly, the ZrC-SiC-PyC interfacial layer effectively protects the structural integrity of carbon fibers and improves the mechanical properties of the modified C / C composite material. Typically, in the RMI method for preparing ceramic-modified C / C composites, the PyC content within the low-density C / C composite is insufficient to meet the massive chemical reaction requirements of the ceramic melt. This leads to the ceramic melt completely consuming the PyC before reacting with the carbon fibers, destroying the original structural characteristics of the carbon fibers and ultimately causing them to lose their load-bearing capacity. Consequently, the mechanical properties of the modified C / C composite are severely degraded. Constructing a ceramic interface layer on the outside of the carbon fibers primarily serves to prevent the complete reaction between the ceramic melt and PyC, reducing the likelihood of carbon fiber erosion by the melt and improving the mechanical properties of the ceramic-modified C / C composite. Bending mechanics tests show that the bending strength of ceramic-modified C / C composites with a ZrC-SiC-PyC interface layer is 26.8%–54.9% higher than that without the interface layer. Finally, the ZrC-SiC ceramic-modified C / C composite material prepared based on the ZrC-SiC-PyC interface layer exhibits a more compatible coefficient of thermal expansion with the ceramic matrix compared to a single ZrC or SiC interface layer. When the modified C / C composite material is applied in extreme thermal environments, the ZrC-SiC-PyC interface layer can effectively alleviate the internal stress caused by the difference in thermal expansion coefficients, ensuring the stability of the composite material structure.

[0030] This invention uses a combination of SI and RMI methods to prepare ceramic-modified C / C composite materials with ZrC-SiC-PyC interfacial layers. The presence of the ceramic phase interfacial layer can slow down the erosion of carbon fibers by the ceramic melt, protect the integrity of the carbon fiber structure, and help the ceramic-modified C / C composite materials exhibit higher mechanical properties. Attached Figure Description

[0031] Figure 1 Low-magnification image of the microstructure of the ZrC-SiC-PyC interface layer;

[0032] Figure 2 High-magnification image of the microstructure of the ZrC-SiC-PyC interface layer;

[0033] Figure 3 The image shows the microstructure of the ZrC-SiC-PyC interface layer after PyC deposition.

[0034] Figure 4 Microscopic morphology photograph of C / C-ZrC-SiC composite material with ZrC-SiC-PyC interface layer. Detailed Implementation

[0035] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0036] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0037] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0038] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”

[0039] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0040] This invention relates to the field of ceramic-modified carbon / carbon composite material preparation technology, specifically proposing a method for preparing ceramic-modified carbon / carbon (C / C) composite materials with a zirconium carbide (ZrC)-silicon carbide (SiC)-pyrolytic carbon (PyC) interface layer by combining slurry impregnation (SI) and reactive melting infiltration (RMI).

[0041] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0042] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.

[0043] This embodiment provides a method for preparing ceramic-modified C / C composite materials with a ZrC-SiC-PyC interface layer, and its technical solution will be specifically illustrated through three examples.

[0044] The specific process of the above embodiments is as follows:

[0045] Step 1, Preparation of ZrSi2 slurry:

[0046] I. Preparation of Phenolic Resin Solution. To prepare the phenolic resin solution, add the phenolic resin powder to anhydrous ethanol. First, stir in a magnetic stirrer for 5 minutes, then place in an ultrasonic cleaner and sonicate for 30 minutes to completely dissolve the phenolic resin powder in the anhydrous ethanol. Finally, a clear and uniform phenolic resin solution is obtained.

[0047] The amount of phenolic resin powder and anhydrous ethanol used is based on the mass ratio of the two, that is, phenolic resin: anhydrous ethanol = 1:10, and the ratio is a mass ratio.

[0048] II. Preparation of ZrSi2 slurry. Add ZrSi2 powder with a particle size of 1-3 micrometers to the above phenolic resin solution, and then place the solution in a magnetic stirrer and stir continuously for 3 hours to obtain a well-dispersed ZrSi2 slurry.

[0049] The amount of ZrSi2 powder used is determined based on the amount of phenolic resin powder used above, that is, ZrSi2 powder:phenolic resin powder = 1:6, and the ratio is a mass ratio.

[0050] Step 2: Introduce ZrSi2 powder into the low-density C / C composite material using the SI method:

[0051] Ⅰ Vacuum impregnation of ZrSi2 slurry. A slurry with a density of 0.8~1.0 g / cm³ is used. 3 The C / C composite material was immersed in the ZrSi2 slurry described in step 1, and then the ZrSi2 slurry containing the C / C composite material was placed in a vacuum impregnation chamber. The vacuum pump connected to the vacuum impregnation chamber was turned on, and the vacuum degree inside the vacuum impregnation chamber was reduced to -0.09 MPa. After turning off the vacuum pump, the ZrSi2 slurry containing the C / C composite material was placed under a vacuum degree of -0.09 MPa for 30 minutes. Subsequently, the vacuum in the vacuum impregnation chamber was de-vacuumed and returned to normal pressure, and the ZrSi2 slurry containing the carbon / carbon composite material was removed.

[0052] II. Cleaning and drying the C / C composite material. The C / C composite material was removed from the ZrSi2 slurry and its surface was rinsed with anhydrous ethanol to remove residual slurry. Subsequently, the C / C composite material was dried in a 70°C oven to obtain a low-density C / C composite material with ZrSi2 powder dispersed internally.

[0053] To control the amount of ZrSi2 introduced into the low-density C / C composite material, the method described in step 2 needs to be repeated 1 to 5 times. Finally, a low-density C / C composite material containing 15% to 50% ZrSi2 powder can be obtained, where the proportion is a mass percentage.

[0054] Table 1 Parameters of each embodiment in step 2

[0055]

[0056] Step 3: Prepare low-density C / C composite materials with ZrC-SiC-PyC interface layers using the RMI method:

[0057] The low-density C / C composite material containing ZrSi2 powder described in step 2 was placed in a graphite crucible, which was then placed in a vacuum high-temperature graphitization furnace. The furnace was heated to 2000°C at a rate of 5°C / min and held at that temperature for 2 hours, followed by a cooling to room temperature at a rate of 5°C / min. The vacuum level inside the furnace was maintained at -0.09 MPa during the heating and cooling processes. After removing the sample, a low-density C / C composite material with a ZrC-SiC-PyC interface layer was obtained.

[0058] Step 4: Prepare ceramic-modified C / C composite materials using the RMI method:

[0059] Ⅰ Chemical vapor infiltration deposition of PyC:

[0060] The low-density C / C composite material with a ZrC-SiC-PyC interface layer described in step 3 was placed in an isothermal chemical vapor deposition furnace. The furnace was heated to 1200°C at a rate of 10°C / h, while argon gas was continuously introduced at a flow rate of 50 sccm. After the furnace reached the target temperature, natural gas was introduced into the furnace at a flow rate of 500 sccm, while the argon gas flow rate was set to 1500 sccm. The furnace was maintained at 1200°C for 4–16 hours. Then, the natural gas supply was stopped, the argon gas flow rate was adjusted to 50 sccm, and the furnace was allowed to cool naturally to room temperature. After removing the sample, the low-density C / C composite material with a ZrC-SiC-PyC interface layer after PyC deposition was obtained.

[0061] II. Preparation of ceramic-modified C / C composites with ZrC-SiC-PyC interfacial layers by RMI method:

[0062] The low-density C / C composite material with a ZrC-SiC-PyC interface layer after PyC deposition was placed in a graphite crucible. ZrSi2 powder with a particle size of 1-3 micrometers was spread around the C / C composite material until it was completely embedded in the powder. The graphite crucible was then placed in a vacuum high-temperature graphitization furnace, and the furnace was heated to 2000℃ at a rate of 5℃ / min and held for 2 hours, then cooled to room temperature at a rate of 5℃ / min. The vacuum level inside the furnace was maintained at -0.09 MPa during the heating and cooling processes. After removing the sample, the C / C-ZrC-SiC composite material, i.e., a ceramic-modified C / C composite material with a ZrC-SiC-PyC interface layer, was obtained.

[0063] Table 2 Parameters for each embodiment in step 4

[0064]

[0065] Scanning electron microscopy observation of low-density C / C composite materials with ZrC-SiC-PyC interface layers, as shown in the attached figure. Figure 1 and Figure 2 As shown in the figure, the ZrC-SiC-PyC interface layer comprises ZrC and SiC granular phases and a PyC phase on the outer side of the carbon fibers. The ZrC and SiC granular phases are generated by a chemical reaction between ZrSi2 and PyC, and uniformly coat the surface of the PyC phase on the outer side of the carbon fibers, forming a granular ZrC-SiC-PyC interface phase. Scanning electron microscopy was used to observe the low-density C / C composite material with the ZrC-SiC-PyC interface layer after PyC deposition, as shown in the figure description. Figure 3As shown in the figure, the ZrC-SiC-PyC interface layer structure around the carbon fibers is clearly visible at this point. From the inside out, it consists of carbon fibers, a PyC layer, a ZrC-SiC particle layer, and a deposited PyC layer. The deposited PyC layer will serve as the internal carbon source, providing reaction materials for the preparation of ceramic-modified C / C composite materials. The final prepared C / C-ZrC-SiC composite material was observed using a scanning electron microscope, as shown in the attached figure description. Figure 4 As shown. In step 4, the deposited PyC reacts with ZrSi2 to produce a large amount of ceramic phase, which becomes the matrix phase of the C / C-ZrC-SiC composite material. The carbon fibers located inside the matrix phase are not eroded by the ZrSi2 melt due to the presence of the ZrC-SiC-PyC interface phase, thus maintaining the integrity of the fiber structure.

[0066] Table 3 Mechanical property test parameters of C / C-ZrC-SiC composite materials prepared in each embodiment

[0067]

[0068] This invention employs a combination of SI and RMI methods to rapidly prepare ceramic-modified C / C composite materials containing an interface layer, significantly improving the mechanical properties of the material and broadening the engineering application range of ceramic-modified C / C composite materials.

[0069] Mechanical properties were tested on the ceramic-modified C / C composite materials with ZrC-SiC-PyC interface layers prepared in various embodiments of the present invention, namely C / C-ZrC-SiC composite materials. The results showed that the flexural strength of the composite material was 90~110 MPa, which was 26.8%~54.9% higher than that of the C / C-ZrC-SiC composite material without ZrC-SiC-PyC interface layer (flexural strength was 71 MPa).

[0070] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

Claims

1. A method for producing a ceramic modified C / C composite material having a ZrC-SiC-PyC interfacial layer, characterized in that, The method comprises the following steps: The ZrSi2 powder is introduced into the low-density C / C composite material by the SI method, and the low-density C / C composite material containing the ZrSi2 powder is prepared, and the specific process is as follows: the C / C composite material is soaked in the ZrSi2 slurry, and then is placed in a set vacuum environment of-0.09 MPa for 30 min; after being taken out, the C / C composite material is washed and dried to obtain the low-density C / C composite material with the ZrSi2 powder dispersed in the interior; the step is repeated 1-5 times to obtain the low-density C / C composite material containing the ZrSi2 powder; The low-density C / C composite material containing the ZrSi2 powder is prepared into the low-density C / C composite material with the ZrC-SiC-PyC interface layer by the first RMI method, and the specific process is as follows: the low-density C / C composite material containing the ZrSi2 powder is placed in a graphite crucible, and then the graphite crucible is placed in a vacuum high-temperature graphitization furnace; under the vacuum condition of-0.09 MPa in the vacuum high-temperature graphitization furnace, the vacuum high-temperature graphitization furnace is heated to 2000 ℃ at a heating rate of 5 ℃ / min, and then is cooled to room temperature at a cooling rate of 5 ℃ / min. The PyC is deposited on the low-density C / C composite material with the ZrC-SiC-PyC interface layer by the chemical vapor deposition method to obtain the low-density C / C composite material with the ZrC-SiC-PyC interface layer after the PyC is deposited, and the specific process is as follows: the low-density C / C composite material with the ZrC-SiC-PyC interface layer is placed in an isothermal chemical vapor deposition furnace; the isothermal chemical vapor deposition furnace is heated to 1200 ℃ at a heating rate of 10 ℃ / h, and argon gas is continuously introduced at a flow rate of 50 sccm during the heating; after being heated to 1200 ℃, the isothermal chemical vapor deposition furnace is introduced with natural gas at a flow rate of 500 sccm, and the flow rate of the argon gas is set to 1500 sccm; the isothermal chemical vapor deposition furnace is kept at 1200 ℃ for 4-16 h, then the introduction of the natural gas is stopped, the flow rate of the argon gas is adjusted to 50 sccm, and the isothermal chemical vapor deposition furnace is naturally cooled to room temperature, and the deposition of the PyC is completed. The ceramic modified C / C composite material with the ZrC-SiC-PyC interface layer is prepared by the second RMI method, and the specific process is as follows: the low-density C / C composite material with the ZrC-SiC-PyC interface layer after the PyC is deposited is placed in a graphite crucible, and the low-density C / C composite material with the ZrC-SiC-PyC interface layer after the PyC is deposited is completely buried by the ZrSi2 powder with a particle size of 1-3 microns; the low-density C / C composite material with the ZrC-SiC-PyC interface layer after the PyC is deposited is placed in a vacuum high-temperature graphitization furnace; under the vacuum condition of-0.09 MPa in the vacuum high-temperature graphitization furnace, the vacuum high-temperature graphitization furnace is heated to 2000 ℃ at a heating rate of 5 ℃ / min, and then is cooled to room temperature at a cooling rate of 5 ℃ / min.

2. The method of producing a ceramic modified C / C composite material having a ZrC-SiC-PyC interfacial layer according to claim 1, characterized in that, The ZrSi2 slurry is prepared by the following method: The phenolic resin powder is added to anhydrous ethanol to prepare a phenolic resin solution; The ZrSi2 powder with a particle size of 1-3 microns is added to the phenolic resin solution to obtain the ZrSi2 slurry.

3. The method of producing a ceramic modified C / C composite material having a ZrC-SiC-PyC interfacial layer according to claim 2, characterized in that, The mass ratio of the phenolic resin powder and anhydrous ethanol is 1:10; the mass ratio of the ZrSi2 powder and the phenolic resin powder is 1:

6.

4. The method of producing a ceramic modified C / C composite material having a ZrC-SiC-PyC interfacial layer according to claim 1, characterized in that, The ZrC-SiC-PyC interface layer in the low-density C / C composite material with the ZrC-SiC-PyC interface layer comprises ZrC and SiC particle phases and a carbon fiber outer PyC phase, wherein the ZrC and SiC particle phases are generated by chemical reaction of ZrSi2 and PyC and uniformly coated on the surface of the carbon fiber outer PyC phase to form a granular ZrC-SiC-PyC interface phase.

5. The method of producing a ceramic modified C / C composite material having a ZrC-SiC-PyC interfacial layer according to claim 1, characterized by, The carbon fiber periphery in the low-density C / C composite material with the ZrC-SiC-PyC interface layer after deposition of the PyC comprises, from inside to outside, a PyC layer, a ZrC-SiC particle layer and a deposited PyC layer. The deposited PyC layer will provide reaction raw materials for preparation of the ceramic modified C / C composite material as an internal carbon source.

6. A ceramic modified C / C composite material with ZrC-SiC-PyC interface layer prepared by the method of any one of claims 1 to 5, characterized in that, The C / C-ZrC-SiC composite material substrate phase and the carbon fiber inside the C / C-ZrC-SiC composite material substrate phase. The C / C-ZrC-SiC composite material substrate phase is a ceramic phase generated by reaction of the deposited PyC and ZrSi2.

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