Carbon fiber reinforced (TiZrHfNbTa) C ceramic-based composite material as well as interface regulation and control preparation method and application thereof

Abstract

The invention discloses a carbon fiber reinforced (TiZrHfNbTa) C ceramic-based composite material as well as an interface regulation and control preparation method and application thereof, and belongs to the technical field of ultrahigh-temperature ceramic-based composite materials. The carbon fiber reinforced (TiZrHfNbTa) C ceramic-based composite material comprises carbon fibers and a ceramic matrix, a graphene bonding layer interface and a pyrolytic carbon layer interface are arranged between the carbon fibers and the ceramic matrix, the pyrolytic carbon layer interface and the graphene bonding layer interface sequentially wrap the carbon fibers from inside to outside, the interface bonding strength is high, the toughening effect of the fibers is fully exerted, and the carbon fiber reinforced (TiZrHfNbTa) C ceramic-based composite material is suitable for being used as a high-temperature-resistant composite material. The mechanical property of the composite material is remarkably improved, meanwhile, the composite material has the high-temperature-resistant characteristic of ultra-high-temperature ceramics, and the composite material has wide application prospects in extreme environments such as thermal protection systems in the aerospace field and leading edge components of hypersonic aircrafts.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of ultra-high-temperature ceramic matrix composites, and particularly relates to a carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material and an interface regulation preparation method and application thereof. BACKGROUND

[0002] The carbon fiber reinforced ultra-high-temperature ceramic matrix composite material not only realizes a significant improvement in fracture toughness that a single ceramic material is difficult to achieve, but also has the advantages of low density, high mechanical strength and excellent thermal shock resistance. However, the full play of the mechanical properties of the composite material highly depends on the efficient load transfer mechanism between the fiber and the matrix, and the insufficient interface bonding strength has become a key bottleneck restricting the performance improvement. This problem mainly originates from the poor intrinsic wettability between the carbon fiber and the ceramic matrix, resulting in weak interface bonding, thereby causing load transfer failure and failing to fully play the mechanical properties of the fiber. Therefore, the accurate regulation of the fiber-matrix interface structure and the enhancement of the interface bonding become a core problem for fully playing the carbon fiber reinforcement potential.

[0003] At present, the method for improving the interface bonding between the fiber and the ceramic matrix usually introduces an interface layer, such as a PyC, SiC and TiC coating. The PyC has good compatibility with the carbon fiber due to its dense structure, and has good carbon fiber protection capability. However, the dense and smooth and chemically inert surface of the PyC still cannot improve the poor interface bonding. The SiC / TiC coating can improve the interface bonding strength, but the preparation process involves in-situ reaction with the carbon fiber, which causes great damage to the fiber structure. SUMMARY

[0004] In order to overcome the above-mentioned shortcomings of the prior art, the purpose of the present application is to provide a carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material and an interface regulation preparation method and application thereof, so as to solve the technical problems that the dense and smooth and chemically inert surface of the PyC coating still cannot improve the poor interface bonding, and the SiC / TiC coating can improve the interface bonding strength, but the preparation process involves in-situ reaction with the carbon fiber, causing damage to the fiber structure.

[0005] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions: The present application provides a carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material, comprising carbon fibers and a ceramic matrix, wherein there are a graphene adhesive layer interface and a pyrolytic carbon layer interface between the carbon fibers and the ceramic matrix, and the pyrolytic carbon layer interface and the graphene adhesive layer interface successively wrap the carbon fibers from inside to outside.

[0006] The application further provides an interface regulation preparation method of the carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material as described above, comprising the following steps: 1) dispersing the chopped carbon fiber into a glucose solution, performing a solvothermal reaction to deposit a PyC coating layer, and then sequentially performing cleaning, drying and pyrolysis to obtain the carbon fiber with the PyC coating layer; 2) mixing the carbon fiber with the PyC coating layer with a molten salt medium and a transition metal powder, performing a molten salt reaction through a molten salt method to prepare a carbide coating layer on the surface of the carbon fiber, and preparing the carbon fiber coated with the carbide / PyC double coating layer; 3) mixing the carbon fiber coated with the carbide / PyC double coating layer with (TiZrHfNbTa)C high-entropy carbide powder, and preparing the carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material through a spark plasma sintering process.

[0007] In an embodiment, the ratio of the amount of the chopped carbon fiber to the glucose solution is 1-2 g: 50-100 mL; and the glucose content in the glucose solution is 5-10 wt%.

[0008] In an embodiment, the temperature of the solvothermal reaction is 160-200 DEG C, and the time is 6-12 h; and the temperature of the pyrolysis is 800 DEG C-1000 DEG C, and the pyrolysis time is 1-2 h.

[0009] In an embodiment, the molten salt medium is an equimolar mixture of NaCl and KCl; and the molar ratio of the carbon fiber with the PyC coating layer, the transition metal powder and the molten salt medium is 1:0.1-0.5:5-10.

[0010] In an embodiment, the transition metal powder is one of Ta powder, Nb powder, Zr powder, Hf powder or Ti powder.

[0011] In an embodiment, the temperature of the molten salt reaction is 1000-1200 DEG C, the molten salt reaction time is 1-2 h, and the protective atmosphere is argon.

[0012] In an embodiment, the spark plasma sintering process is as follows: the sintering temperature is 1800-2000 DEG C, the holding time is 10-20 min, the heating / cooling rate is 100 DEG C / min, the applied pressure is 40 MPa, and the protective atmosphere is argon.

[0013] In an embodiment, the volume ratio of the carbon fiber coated with the carbide / PyC double coating layer to the (TiZrHfNbTa)C high-entropy carbide powder is 10-20 vol%: 90-80 vol%.

[0014] The application further provides application of the carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material in the thermal protection field.

[0015] The application further provides application of the carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material prepared by the interface regulation method of the carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material in the thermal protection field.

[0016] Compared with the prior art, the application has the following beneficial effects: The application provides an interface regulation method of a carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material, which mainly comprises the following steps: 1) dispersing short-cut carbon fibers into a glucose solution, then transferring the short-cut carbon fibers into an autoclave for a solvothermal reaction, and then cleaning and drying the product and pyrolyzing the product to obtain carbon fibers with a pyrolytic carbon (PyC) coating; 2) mixing the carbon fibers with the PyC coating with a molten salt medium and transition metal powder, and preparing a carbide coating on the surface of the carbon fibers by a molten salt method; and 3) mixing the carbon fibers coated with the carbide / PyC double coating with (TiZrHfNbTa)C high-entropy carbide powder, and preparing a carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material by a spark plasma sintering process. Figure 1 and Figure 2 As shown in the drawings, during sintering, the carbide coating undergoes bidirectional diffusion, a part of which diffuses into the ceramic matrix to form a solid solution, and another part of which diffuses into the PyC coating and induces PyC catalytic graphitization to generate a graphene bonding layer in situ; and the thickness of the graphene bonding layer is regulated by adjusting the thickness of the carbide coating, that is, the interface structure is regulated to enhance the interface bonding. The carbide coating is widely applicable, and carbides capable of forming a solid solution with the matrix can all be used as the carbide coating. The prepared composite material also has excellent strength and toughness. Different from the traditional method of modifying the surface of carbon fibers by a single physical or chemical method, the method innovatively constructs a “PyC / carbide” double-coating structure on the surface of the carbon fibers as an interface regulator. The method generates a graphene bonding layer at the interface by constructing a special double-coating structure on the surface of the carbon fibers and utilizing in-situ reaction during sintering, so as to accurately regulate the interface structure and significantly enhance the bonding strength. The preparation method is simple in operation process and easy to control the interface structure.

[0017] Further, the application accurately and conveniently regulates the interface structure of the composite material. The thickness of the graphene bonding layer generated in situ can be controlled by only adjusting the thickness of the carbide coating (that is, adjusting the molar ratio of the carbon fibers and the transition metal powder), so as to optimize the interface bonding strength. The method has a wide process window and good repeatability.

[0018] The carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material prepared by the interface regulation preparation method of the carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material has the advantages that the PyC layer of the inner layer can effectively protect the carbon fiber from damage in subsequent high-temperature treatment and reaction; and the carbide layer of the outer layer, through element diffusion, strengthens part of the matrix and induces the PyC layer adjacent thereto to catalytically graphitize to generate graphene as a bonding layer in-situ during the spark plasma sintering process. The multiple interface design of "protection-strengthening-bridging" fundamentally solves the balance problem of protecting the fiber and strengthening the interface combination.

[0019] The carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material prepared by the interface regulation preparation method of the carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material has the advantages that the PyC layer of the inner layer can effectively protect the carbon fiber from damage in subsequent high-temperature treatment and reaction; and the carbide layer of the outer layer, through element diffusion, strengthens part of the matrix and induces the PyC layer adjacent thereto to catalytically graphitize to generate graphene as a bonding layer in-situ during the spark plasma sintering process. The multiple interface design of "protection-strengthening-bridging" fundamentally solves the balance problem of protecting the fiber and strengthening the interface combination. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 is a scanning electron microscope (SEM) image of the carbon fiber with a TiC / PyC double-coated layer prepared in Example 3 of the present application; Figure 2 is a scanning electron microscope (SEM) image of the interface of the composite material after spark plasma sintering in Example 3 of the present application; Figure 3 (a) and (b) in the figure are a transmission electron microscope (TEM) and a high-resolution (HRTEM) image of the graphene bonding layer generated at the interface of the composite material in Example 3 of the present application. DETAILED DESCRIPTION

[0021] To enable those skilled in the art to understand the features and effects of the present application, the following is a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific words used herein have their usual meanings understood by those skilled in the art of the present application, and in case of conflict, the definition in the specification shall prevail.

[0022] Theories or mechanisms described and disclosed herein, whether correct or not, should not be used to limit the scope of the present application, i.e., the present application can be practiced without being limited by any particular theory or mechanism.

[0023] Herein, all features defined by a numerical range or a percentage range, such as numerical values, amounts, contents and concentrations, are merely for the sake of brevity and convenience. Accordingly, the description of a numerical range or a percentage range should be considered to have encompassed and specifically disclosed all possible sub-ranges and individual numerical values within the range (including integers and fractions).

[0024] Herein, unless otherwise specifically stated, "comprise", "include", "contain", "have" or similar terms, encompass both "consist of" and "consist essentially of", for example, "A comprises a" encompasses both "A comprises a and other" and "A consists of a".

[0025] Herein, for the sake of brevity, all possible combinations of the various technical features in the various embodiments or examples are not described. Therefore, the various technical features in the various embodiments or examples can be combined with each other as long as there is no contradiction, and all possible combinations should be considered as falling within the scope of the present specification.

[0026] The present application provides a method for preparing an interface of a carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite, comprising the following steps: 1) dispersing chopped carbon fibers into a glucose solution, then transferring to an autoclave for solvothermal reaction to deposit a PyC coating, and then washing, drying and pyrolyzing the product to obtain carbon fibers with a PyC coating; in step 1), the ratio of the amount of chopped carbon fibers to the amount of glucose solution is 1-2 g: 50-100 mL; the glucose solution is 50-100 mL, the carbon fiber content is 1-2 g, and the glucose content in the glucose solution is 5-10 wt%; the solvothermal reaction temperature is 160-200℃, and the reaction time is 6-12 h; the pyrolysis temperature is 800℃-1000℃, and the time is 1-2 h.

[0027] 2) mixing the carbon fibers with a PyC coating with a molten salt medium and a transition metal powder, and preparing a carbide coating on the surface of the carbon fibers by molten salt reaction to obtain carbon fibers coated with a carbide / PyC double coating; in step 2), the molten salt medium is an equimolar mixture of NaCl and KCl, the transition metal powder is one of Ta powder, Nb powder, Zr powder, Hf powder or Ti powder, and the molar ratio of the carbon fibers with a PyC coating to the transition metal powder and the molten salt medium is 1:0.1-0.5:5-10; the molten salt reaction temperature is 1000-1200℃, the reaction time is 1-2 h, and the protective atmosphere is argon.

[0028] 3) mixing the carbon fiber coated with carbide / PyC double coating layer and (TiZrHfNbTa)C high-entropy carbide powder, and preparing the carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material by a spark plasma sintering process; in step 3), the volume ratio of the carbon fiber coated with carbide / PyC double coating layer and (TiZrHfNbTa)C high-entropy carbide powder is 10-20 vol%:90-80 vol%, the sintering temperature is 1800-2000℃, the holding time is 10-20 min, the heating / cooling rate is 100℃ / min, the applied pressure is 40 MPa, and the protective atmosphere is argon.

[0029] As shown in FIG. 1, the carbon fiber coated with carbide / PyC double coating layer is shown; as shown in FIG. 2, the graphene adhesive layer generated in situ due to the diffusion of the TiC coating layer is shown; as shown in FIG. 3, the transmission electron microscope (TEM) shows that the graphene adhesive layer is composed of a graphene network intertwined with each other, and the HRTEM image shows the lattice fringes of the graphene. Figure 1 Figure 2 As shown in FIG. 1, the carbon fiber coated with carbide / PyC double coating layer is shown; as shown in FIG. 2, the graphene adhesive layer generated in situ due to the diffusion of the TiC coating layer is shown; as shown in FIG. 3, the transmission electron microscope (TEM) shows that the graphene adhesive layer is composed of a graphene network intertwined with each other, and the HRTEM image shows the lattice fringes of the graphene. Figure 3

[0030] In the above preparation process, in step 2), the PyC layer on the surface of the carbon fiber can not only protect the internal carbon fiber, but also serve as a carbon source to react with the transition metal powder to generate the carbide coating layer in situ; in step 3), during the spark plasma sintering, the carbide coating layer diffuses in two directions, part of which diffuses into the (TiZrHfNbTa)C high-entropy carbide ceramic matrix to form a solid solution, and the other part diffuses into the PyC coating layer and induces PyC catalytic graphitization to generate the graphene adhesive layer in situ; in addition, in step 3), the thickness of the graphene adhesive layer can be adjusted by adjusting the thickness of the carbide coating layer, that is, the interface structure is adjusted to enhance the interface bonding.

[0031] The application also provides a carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material with enhanced interface bonding obtained by the above synthesis method, which comprises carbon fibers and a ceramic matrix, and the carbon fibers and the ceramic matrix are wrapped by a graphene adhesive layer interface and a pyrolytic carbon layer interface from inside to outside.

[0032] The application also provides an application of the carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material in the field of thermal protection.

[0033] ​​The application will be further described in conjunction with specific examples. It should be understood that these examples are only used to illustrate the application and not used to limit the scope of the application. Furthermore, it should be understood that after reading the content of the present application, those skilled in the art can make various modifications or changes to the application, and these equivalent forms also fall within the scope defined by the appended claims.

[0034] The following examples use the instruments and equipment that are conventional in the art. The experimental methods in the following examples, unless otherwise specified, are generally carried out according to conventional conditions, or according to the conditions recommended by the manufacturer. Various raw materials are used in the following examples, unless otherwise specified, and conventional commercially available products are used, which are conventional specifications in the art. In the specification of the present application and in the following examples, unless otherwise specified, "%" means weight percent, "parts" means weight parts, and the ratio means weight ratio.

[0035] Example 1 The present example provides a method for preparing an interface control of a carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material, comprising the following steps: (1) 50 mL of glucose solution with a glucose content of 5 wt% is measured, 1 g of chopped carbon fiber is weighed and dispersed in the glucose solution, and then transferred to an autoclave for solvothermal reaction, the reaction temperature is 160℃, and the reaction time is 12 h. After the reaction is completed and cooled, the product is washed and dried, and after heat treatment at 800℃ for 2 h, carbon fiber with a PyC coating is obtained.

[0036] (2) NaCl, KCl, carbon fiber with a PyC coating, and metal Ta powder are mixed according to a molar ratio of 5:5:1:0.1, and then placed in an alumina crucible, and subjected to molten salt reaction at 1000℃ for 2 h under a flowing argon protective atmosphere. During this period, Ta can react with the PyC coating on the surface of the carbon fiber to form a TaC coating. After the reaction is completed, the furnace is cooled to room temperature, and then the powder mixture is dissolved in boiling water to dissolve NaCl and KCl, and filtered through a 300 mesh screen cloth to remove impurities, residual salt, and unreacted Ta powder, and finally obtain carbon fiber coated with TiC / PyC double coating on the surface.

[0037] (3) 20 vol% of carbon fiber coated with TaC / PyC double coating is mixed with 80 vol% of (TaNbTiZrHf)C high-entropy carbide ceramic powder, and through a spark plasma sintering process, a carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material is prepared by sintering at 1800℃ for 20 minutes (the heating rate is 100℃ / min, the applied pressure is 40 MPa, and the protective atmosphere is argon).

[0038] In the carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material prepared in this embodiment, the graphene adhesion layer generated by the diffusion reaction between the fiber and the matrix due to the TaC coating layer has a thickness of about 100 nm, the bending strength of the composite material is 523.45 MPa, and the fracture toughness is 6.54 MPa·m 1 / 2 .

[0039] Example 2 The embodiment provides a method for preparing an interface of a carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material, comprising the following steps: (1) 75 mL of glucose solution with a glucose content of 8 wt% is measured, 1.5 g of chopped carbon fiber is weighed and dispersed into the glucose solution, and then transferred into an autoclave for a solvothermal reaction, a reaction temperature is 180℃, and a reaction time is 10 h. After the reaction is completed and cooled, the product is washed and dried, and after heat treatment at 800℃ for 2 h, the carbon fiber with a PyC coating layer is obtained.

[0040] (2) NaCl, KCl, the carbon fiber with the PyC coating layer, and the metal Nb powder are mixed according to a molar ratio of 5:5:1:0.2, and then placed in an alumina crucible, and a molten salt reaction is performed at 1100℃ for 1 h under a flowing argon protection atmosphere. During this period, the Nb can react with the PyC coating layer on the surface of the carbon fiber to generate a NbC coating layer. After the reaction is completed, the furnace is cooled to room temperature, then the powder mixture is dissolved in boiling water to dissolve NaCl and KCl, and filtered through a 300 mesh sieve cloth to remove impurities, residual salt and unreacted Nb powder, and finally the carbon fiber coated with a NbC / PyC double coating layer on the surface is obtained.

[0041] (3) 20 vol% of the carbon fiber coated with the NbC / PyC double coating layer is mixed with 80 vol% of (TaNbTiZrHf)C high-entropy carbide ceramic powder, and a carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material is prepared by a spark plasma sintering process, sintered at 1800℃ for 20 minutes (the heating rate is 100℃ / min, the applied pressure is 40 MPa, and the protection atmosphere is argon).

[0042] In the carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material prepared in this embodiment, the graphene adhesion layer generated by the diffusion reaction between the fiber and the matrix due to the NbC coating layer has a thickness of about 150 nm, the bending strength of the composite material is 554.63 MPa, and the fracture toughness is 6.89 MPa·m 1 / 2 .

[0043] Example 3 The embodiment provides an interface regulation preparation method of a carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material, and comprises the following steps: (1) 100 mL of a glucose solution with a glucose content of 10 wt% is measured, 2 g of chopped carbon fibers are weighed and dispersed into the glucose solution, and then the glucose solution is transferred into an autoclave for a solvothermal reaction, a reaction temperature is 200 DEG C, and a reaction time is 6 h. After the reaction is completed and the product is cooled, the product is washed and dried, and after heat treatment at 900 DEG C for 1.5 h, the carbon fibers with a PyC coating are obtained.

[0044] (2) NaCl, KCl, the carbon fibers with the PyC coating and metal Ti powder are mixed according to a molar ratio of 10:10:1:0.3, and then are placed in an alumina crucible, and a molten salt reaction is carried out at 1000 DEG C for 1 h under a flowing argon protection atmosphere. During the reaction, Ti can react with the PyC coating on the surface of the carbon fibers to generate a TiC coating in situ. After the reaction is completed, the furnace is cooled to room temperature, then the powder mixture is dissolved in boiling water to dissolve NaCl and KCl, and is filtered through a 300-mesh sieve cloth to remove impurities, residual salt and unreacted Ti powder, and finally the carbon fibers with a TiC / PyC double coating on the surface are obtained.

[0045] (3) 15 vol% of the carbon fibers with the TiC / PyC double coating and 85 vol% of (TaNbTiZrHf)C high-entropy carbide ceramic powder are mixed, and a carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material is prepared by a spark plasma sintering process, sintering is carried out at 1900 DEG C for 15 min (a temperature rising rate is 100 DEG C / min, a pressure applied is 40 MPa, and a protective atmosphere is argon).

[0046] In the carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material prepared in the embodiment, the TiC coating diffusion induces catalytic graphitization of the PyC layer adjacent to the TiC coating between the fiber and the matrix, an in-situ generated graphene bonding layer has a thickness of about 320 nm, the bending strength of the composite material is 644.78 MPa, and the fracture toughness is 7.76 MPa·m 1 / 2 .

[0047] Embodiment 4 The embodiment provides an interface regulation preparation method of a carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material, and comprises the following steps: (1) 100mL of glucose solution with 10wt% glucose content was measured, 2g of short carbon fiber was weighed and dispersed into the glucose solution, and then transferred to an autoclave for solvothermal reaction, the reaction temperature was 200℃, and the reaction time was 6h. After the reaction was completed and cooled, the product was washed and dried, and after heat treatment at 1000℃ for 1h, carbon fiber with PyC coating was obtained.

[0048] (2) NaCl, KCl, carbon fiber with PyC coating and metal Ti powder were mixed according to the molar ratio of 5:5:1:0.5, and then placed in an alumina crucible, and then subjected to molten salt reaction at 1200℃ for 1h under the protection of flowing argon gas. During this period, Ti can react with the PyC coating on the surface of the carbon fiber to form a TiC coating. After the reaction was completed, the furnace was cooled to room temperature, and then the powder mixture was dissolved in boiling water to dissolve NaCl and KCl, and filtered through a 300 mesh screen cloth to remove impurities, residual salt and unreacted Ti powder, and finally obtain carbon fiber coated with TiC / PyC double coating.

[0049] (3) 10 vol% of carbon fiber coated with TiC / PyC double coating was mixed with 90 vol% of (TaNbTiZrHf)C high-entropy carbide ceramic powder, and then subjected to spark plasma sintering process at 2000℃ for 10 minutes (the heating rate was 100℃ / min, the applied pressure was 40 MPa, and the protective atmosphere was argon), to prepare a carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material.

[0050] In this embodiment, in the prepared carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material, the TiC coating layer between the fiber and the matrix diffuses and induces catalytic graphitization of the adjacent PyC layer, and the in-situ generated graphene bonding layer has a thickness of about 500nm. The bending strength of the composite material is 682.49MPa, and the fracture toughness is 6.47 MPa·m 1 / 2 .

[0051] The above is only to illustrate the technical idea of the present application, and cannot limit the protection scope of the present application. Any modification made according to the technical idea of the present application on the basis of the technical scheme falls within the protection scope of the claims of the present application.

Claims

1. A carbon fiber-reinforced (TiZrHfNbTa)C ceramic matrix composite, characterized in that, The carbon fiber and the ceramic matrix are wrapped with a pyrolytic carbon layer interface and a graphene adhesive layer interface in sequence from inside to outside.

2. The interface control method for carbon fiber-reinforced (TiZrHfNbTa)C ceramic matrix composite according to Claim 1, characterized by, The method comprises the following steps: 1) dispersing chopped carbon fibers into a glucose solution, performing a solvothermal reaction to deposit a PyC coating, and then sequentially performing cleaning, drying and pyrolysis to obtain carbon fibers with a PyC coating; 2) mixing the carbon fibers with a PyC coating with a molten salt medium and a transition metal powder, and preparing a carbide coating on the surface of the carbon fibers by a molten salt reaction to obtain carbon fibers coated with a carbide / PyC double coating; 3) mixing the carbon fibers coated with a carbide / PyC double coating with (TiZrHfNbTa)C high-entropy carbide powder, and preparing carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composites by a spark plasma sintering process.

3. The interfacial control method for carbon fiber-reinforced (TiZrHfNbTa)C ceramic matrix composite according to claim 2, characterized by, The ratio of the amount of the chopped carbon fibers to the glucose solution is 1-2 g: 50-100 mL; the glucose content in the glucose solution is 5-10 wt%.

4. The interfacial control method for carbon fiber-reinforced (TiZrHfNbTa)C ceramic matrix composite according to claim 2, characterized by, The temperature of the solvothermal reaction is 160-200℃, and the time is 6-12 h; the temperature of the pyrolysis is 800℃-1000℃, and the pyrolysis time is 1-2 h.

5. The interfacial control method for carbon fiber-reinforced (TiZrHfNbTa)C ceramic matrix composite according to claim 2, characterized by, The molten salt medium is an equimolar mixture of NaCl and KCl; the molar ratio of the carbon fibers with a PyC coating, the transition metal powder and the molten salt medium is 1:0.1-0.5:5-10.

6. The interfacial control method for carbon fiber-reinforced (TiZrHfNbTa)C ceramic matrix composite according to claim 2, characterized by, The transition metal powder is one of Ta powder, Nb powder, Zr powder, Hf powder or Ti powder.

7. The interfacial control method for carbon fiber-reinforced (TiZrHfNbTa)C ceramic matrix composite according to claim 2, characterized by, The temperature of the molten salt reaction is 1000-1200℃, the molten salt reaction time is 1-2 h, and the protective atmosphere is argon.

8. The interfacial control method for carbon fiber-reinforced (TiZrHfNbTa)C ceramic matrix composite according to claim 2, characterized by, The spark plasma sintering process is as follows: The sintering temperature is 1800-2000℃, the holding time is 10-20 min, the heating / cooling rate is 100℃ / min, the applied pressure is 40 MPa, and the protective atmosphere is argon.

9. The interfacial control method for the carbon fiber-reinforced (TiZrHfNbTa)C ceramic matrix composite according to claim 2, characterized by, The volume ratio of the carbon fibers coated with a carbide / PyC double coating to the (TiZrHfNbTa)C high-entropy carbide powder is 10-20 vol%: 90-80 vol%.

10. The use of the carbon fiber reinforced (TiZrHfNbTa)C ceramic matrix composite material of claim 1 in the field of thermal protection.

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