A method for preparing an ultra-high temperature ceramic matrix metal modified composite

Abstract

The application discloses a preparation method of an ultrahigh-temperature ceramic combined metal modified composite material and belongs to the field of ultrahigh-temperature ceramic-metal modified composite materials, and the specific method is as follows: a 2.5D preform is obtained by needling and weaving with PAN-based carbon fibers as a matrix; a 2.5D carbon / carbon composite material is obtained by depositing pyrolytic carbon on the surface of the preform through a chemical vapor infiltration method; a 2.5D carbon / carbon-silicon carbide composite material is obtained by continuously introducing a ceramic phase through a precursor impregnation and pyrolysis method; and finally, a 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material is prepared by high-temperature vacuum infiltration in zirconium copper metal powder through a reaction infiltration method. The three technologies are coupled and used, which not only ensures the uniform distribution of the silicon carbide and zirconium carbide components in the composite material, but also significantly shortens the preparation period, and greatly improves the ablation resistance and mechanical properties of the material.

Description

Technical Field

[0001] This invention belongs to the field of ultra-high temperature ceramic-metal modified composite materials technology, and particularly relates to a method for preparing ultra-high temperature ceramic-metal modified composite materials. Background Technology

[0002] In the ablation thermal protection material system of the aerospace field, carbon fiber reinforced carbon matrix (C / C) composites have become one of the core candidate materials due to their excellent comprehensive performance. This type of material uses carbon fiber and its fabric as the reinforcing phase and pyrolytic carbon (PyC) or graphite as the matrix phase, possessing several outstanding advantages: one of which is its low density, with the material density not exceeding 2.0 g / cm³. 3 Firstly, it can meet the lightweight design requirements of aerospace equipment while ensuring the performance of components. Secondly, it has excellent mechanical properties, combining lightweight and high strength, and can maintain good structural stability even in high-temperature environments. Thirdly, it has excellent friction and wear resistance, making it suitable for high-load friction conditions. Fourthly, it has outstanding ablation resistance, with an ablation tolerance temperature of over 3000℃, and its performance degradation is gradual and the ablation uniformity is good during short-term ablation. Since the successful development of pitch-based carbon fiber in the 1960s, C / C composite materials have been widely used in key aerospace components such as aircraft brake discs, missile nose cones, and rocket engine nozzle throat liners.

[0003] However, C / C composites suffer from significant oxidation defects, which has become a key constraint on their large-scale application. In oxygen-containing environments, the material undergoes significant oxidation at temperatures above 400°C, and the oxidation reaction intensifies dramatically above 600°C, easily causing structural damage and substantial performance degradation of components, severely limiting their long-term stable application in the aerospace field. Therefore, developing stable and reliable oxidation-resistant and ablation-resistant protection technologies for high-temperature environments is a core prerequisite for promoting the large-scale application of C / C composites as ablation thermal protection materials.

[0004] For the porous structure characteristics of C / C composites, existing anti-oxidation and ablation protection technologies mainly fall into two categories: one is to prepare an anti-oxidation coating on the material surface, and the other is to introduce ultra-high temperature ceramic (UHTCs) phases or metallic phases into the carbon matrix. Introducing UHTCs phases such as ZrC, ZrB2, HfC, and HfB2 into the carbon matrix, combined with metallic phases that exhibit a sweating cooling effect, is an effective technical approach to improve the overall performance of the material. Among existing UHTC ceramic systems, the ZrC-SiC binary system has been systematically studied due to its excellent ablation resistance. Further introducing a sweating metallic phase on this basis can significantly improve the composite material's adaptability to extreme service environments.

[0005] Currently, the mainstream preparation technologies for carbon / carbon-silicon carbide-zirconium carbide-copper composites mainly include chemical vapor infiltration / deposition (CVI / CVD), reactive infiltration (RMI), precursor impregnation pyrolysis (PIP), and slurry infiltration (SI). However, each single process has inherent defects that are difficult to avoid: CVI-prepared materials have uniform microstructure and excellent performance, cause little damage to carbon fibers, and have strong process controllability and designability, but its high preparation cost and long cycle are prominent problems; PIP-prepared ceramic matrices have uniform structures and good designability, and are suitable for the preparation of complex shaped parts, but they have two major shortcomings: firstly, the precursor conversion rate directly determines the quality of the ceramic matrix. Volume shrinkage during pyrolysis can easily lead to cracks in the matrix, which in turn affects the mechanical properties and oxidation resistance of the composite material. Secondly, multiple impregnation-pyrolysis cycles are required to achieve material densification. As the material density increases and the porosity decreases, the process efficiency will decrease significantly, ultimately leading to a longer preparation cycle and increased costs. The RMI method has the advantages of low cost, short cycle, fast densification speed, and net-size forming, making it suitable for the large-scale production of complex components. However, during the high-temperature melting and ceramicization process, the melt and carbon fiber are prone to violent interfacial reactions, causing damage to the fiber structure, resulting in a decrease in carbon fiber toughness and a deterioration in the mechanical properties of the composite material. At the same time, the uniformity of the generated ceramic phase is also difficult to guarantee effectively.

[0006] To overcome the inherent limitations of single-process preparation, the use of multi-process combined techniques to prepare ultra-high temperature ceramic-metal modified composite materials has become a research hotspot in the industry. Against this backdrop, developing an efficient and stable multi-process coupling technique to prepare high-performance carbon / carbon-silicon carbide-zirconium carbide-copper composite materials is of significant scientific importance and practical engineering value for promoting the technological development and engineering application of ultra-high temperature thermal protection materials in the aerospace field. Summary of the Invention

[0007] To address the aforementioned technical problems, this invention proposes a method for preparing ultra-high temperature ceramic-metal-modified composite materials.

[0008] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing an ultra-high temperature ceramic-bonded metal-modified composite material includes the following steps: (1) Needle-punching and weaving were performed using PAN (polyacrylonitrile) based carbon fiber as the matrix to obtain a density of 0.4 g / cm³. 3 2.5D prefabricated structure; (2) Pyrolytic carbon was deposited on the surface of the 2.5D preform by chemical vapor infiltration to obtain a 2.5D carbon / carbon composite material; (3) A ceramic phase was introduced into the 2.5D carbon / carbon composite material by using a precursor impregnation pyrolysis method to obtain a 2.5D carbon / carbon-silicon carbide composite material; (4) The 2.5D carbon / carbon-silicon carbide composite material was prepared by high-temperature vacuum melting in zirconium copper metal powder using the reactive melting method.

[0009] In this invention, pyrolytic carbon is deposited around carbon fibers using chemical vapor infiltration on a 2.5D preform, a ceramic phase is introduced using a precursor impregnation pyrolysis method, and an ultra-high temperature ceramic phase and a metal phase are introduced using a reactive melting infiltration method, ultimately preparing a 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material.

[0010] Furthermore, the specific operation steps of the chemical vapor infiltration method are as follows: a layer of annular pyrolytic carbon is deposited around the carbon fibers inside the 2.5D preform using methane gas (volume fraction of 85%) to obtain a 2.5D carbon / carbon composite material. The conditions for the chemical vapor infiltration process are as follows: the chemical vapor infiltration process is carried out at a controlled temperature of 1180-1190℃; a deposition cycle is 220-240 hours, and the density of the 2.5D preform increases by 0.3 g / cm³ in each cycle. 3 After two cycles of treatment, the density of the precast body reached 1 g / cm³. 3 .

[0011] Furthermore, the specific operation steps of the precursor impregnation pyrolysis method are as follows: the 2.5D carbon / carbon composite material is placed in the precursor solution and cyclically processed by vacuum pressure impregnation-drying-pyrolysis as a complete cycle to obtain the 2.5D carbon / carbon-silicon carbide composite material.

[0012] Furthermore, the specific process of vacuum pressure impregnation is as follows: the 2.5D carbon / carbon composite material is placed in a pressure vessel, a vacuum is drawn to reduce the pressure inside the vessel to -0.09MPa, and it is left to stand for 5 minutes; the feed inlet valve is opened to introduce the precursor solution, argon gas is introduced to raise the pressure inside the vessel to 7MPa, and this pressure is maintained for 30 minutes. The specific drying process is as follows: the temperature is 150-160℃, and the drying time is 1-2 hours; The specific pyrolysis process is as follows: the temperature is increased to 700-1300℃ at a heating rate of 10℃ / min, and then held at this temperature for pyrolysis for 30-60min.

[0013] Furthermore, the precursor solution is a mixture of polymethylsilane and xylene in a mass ratio of 1:1.

[0014] Furthermore, the specific operation steps of the reaction melting infiltration method are as follows: Under an argon protective atmosphere, a portion of zirconium copper metal powder is spread evenly on the bottom of a graphite crucible in a high-temperature carbonization furnace. The 2.5D carbon / carbon-silicon carbide composite material is placed on top of the zirconium copper metal powder in the crucible. The remaining zirconium copper metal powder is then completely covered on the 2.5D carbon / carbon-silicon carbide composite material. Under vacuum conditions, the high-temperature carbonization furnace is heated to 1150-1550℃ at a heating rate of 10℃ / min. After holding at this temperature for 1 hour, the furnace is allowed to cool naturally to room temperature to complete the melting infiltration treatment.

[0015] Furthermore, the method for preparing the zirconium-copper metal powder is as follows: zirconium powder and copper powder are used as raw materials and ball-milled under an argon atmosphere. Both the preparation and handling of the zirconium-copper metal powder are carried out under an argon atmosphere.

[0016] Further, the molar ratio of zirconium powder to copper powder is (1-4):(1-2); preferably 1:1, 2:1, 4:1 or 1:2. The ball milling time is 30-60 hours. Within the dosage ratio and ball milling time range specified in this invention, the prepared ball milled powder has excellent bonding properties and good stability, which can effectively improve the smoothness of subsequent melting and infiltration processes and ensure the molding quality and performance uniformity of the composite material.

[0017] The present invention also provides a 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material, which is prepared by the above preparation method.

[0018] This invention also provides the application of a 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material in the preparation of hypersonic vehicles.

[0019] Compared with the prior art, the present invention has the following advantages and technical effects: This invention achieves synergistic effects by combining three processes: traditional chemical vapor infiltration, precursor impregnation pyrolysis, and reactive melt infiltration. The chemical vapor infiltration process generates a ring-shaped pyrolytic carbon layer on the surface of the carbon fiber preform, effectively protecting the carbon fiber from damage in subsequent processes. The precursor impregnation pyrolysis process uniformly introduces the silicon carbide ceramic phase, ensuring the structural uniformity of the composite material. The reactive melt infiltration process efficiently introduces ultra-high temperature ceramic phases (zirconium carbide) and metallic phases (copper), optimizing the overall performance of the composite material, significantly shortening the preparation cycle, and improving the stability of product performance. Attached Figure Description

[0020] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings: Figure 1This is a schematic diagram of the preparation process of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material in an embodiment of the present invention; Figure 2 SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 1; Figure 3 SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 2; Figure 4 SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 3; Figure 5 SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 4; Figure 6 SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 5; Figure 7 EDS image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 5; Figure 8 SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 6; Figure 9 SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 7; Figure 10 SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 11; Figure 11 SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 12; Figure 12 SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 13; Figure 13 The images show the XRD patterns of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite materials prepared in Examples 1 and 5-7. Detailed Implementation

[0021] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0022] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0023] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0024] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0025] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0026] This invention provides a method for preparing ultra-high temperature ceramic-bonded metal-modified composite materials (see flowchart). Figure 1 ), including the following steps: (1) Preparation of 2.5D preforms: Using PAN-based carbon fiber as the matrix material, a density of 0.4 g / cm³ was prepared by needle punching and weaving process. 3 2.5D prefabricated structure; (2) Preparation of 2.5D carbon / carbon composite material: The 2.5D preform obtained in step (1) is placed in a CVI pyrolysis furnace, and methane with a volume fraction of 85% is used as the carbon source. The temperature is controlled at 1180-1190℃ (e.g., 1185℃) for chemical vapor infiltration process. A deposition cycle is 220-240h (e.g., 240h). The density of the 2.5D preform increases by 0.3g / cm³ in each cycle. 3 After two cycles of processing, a layer of annular pyrolytic carbon is deposited around the carbon fibers inside the preform, resulting in a density of 1 g / cm³. 3 2.5D carbon / carbon composite material; (3) Preparation of 2.5D carbon / carbon-silicon carbide composite materials: Polymethylsilane and xylene were mixed at a mass ratio of 1:1 to prepare a precursor solution. The 2.5D carbon / carbon composite material was placed in a pressure vessel, and the pressure inside the vessel was reduced to -0.09 MPa by evacuation and allowed to stand for 5 minutes. Then, the feed valve was opened to introduce the above precursor solution, and argon gas was introduced to raise the pressure inside the vessel to 7 MPa and maintain this pressure for 30 minutes to complete the vacuum pressure impregnation. The 2.5D carbon / carbon composite material, after vacuum pressure impregnation, is placed in an oven and dried at 150-160℃ (e.g., 150℃) for 1-2 hours (e.g., 1 hour). Then, it is placed in a tube furnace and heated to 700-1300℃ (e.g., 1300℃) at a rate of 10℃ / min, and held at this temperature for pyrolysis for 30-60 minutes (e.g., 60 minutes). This cycle of "vacuum pressure impregnation-drying-pyrolysis" is repeated multiple times until the composite material density reaches 1.2-1.5 g / cm³. 3 (e.g., 1.2g / cm) 3 1.3g / cm 3 1.4g / cm 3 Or 1.5g / cm 3 Preferred concentration: 1.5 g / cm³ 3 ), to obtain a 2.5D carbon / carbon-silicon carbide composite material; (4) Preparation of 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite materials: Zirconium and copper powders in a molar ratio of (1-4):(1-2) are ball-milled under an argon atmosphere for 30-60 hours to obtain zirconium-copper metal powder. The preparation and subsequent use of the zirconium-copper metal powder are carried out in an argon atmosphere. For example, the molar ratio of zirconium powder to copper powder is 1:1, 2:1, 4:1 or 1:2, preferably 1:1; the ball milling time can be 30 hours, 40 hours, 50 hours or 60 hours, preferably 30 hours. Under an argon protective atmosphere, a portion of the aforementioned zirconium-copper metal powder is spread evenly at the bottom of a graphite crucible in a high-temperature carbonization furnace. The 2.5D carbon / carbon-silicon carbide composite material is placed on top of the zirconium-copper metal powder in the crucible, and the remaining zirconium-copper metal powder is then completely covered on the surface of the 2.5D carbon / carbon-silicon carbide composite material. After the furnace is closed, a vacuum is drawn, and the high-temperature carbonization furnace is heated to 1150-1550℃ (such as 1150℃, 1350℃, 1450℃ or 1550℃, preferably 1350℃) at a heating rate of 10℃ / min. The material is held at this temperature for 1 hour for melting and infiltration. After the holding period, the furnace is allowed to cool naturally to room temperature to complete the melting and infiltration process, and the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material is finally obtained.

[0027] A 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material can be prepared using the above preparation method.

[0028] This 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material can be used to manufacture hypersonic vehicles. Its ablation resistance principle is as follows: Due to the high heat flux density and dynamic pressure during hypersonic vehicle flight, key thermal protection system components (such as the nose cone, leading edge, scramjet engine combustion chamber, and nozzle) are subjected to extreme aerodynamic heating. With increasing flight speed, aerodynamic heating intensifies, causing the surface temperature of components to rise rapidly to over 2000℃ in a short period. Under this extreme thermal environment, the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in this invention, with its excellent ablation resistance, can well adapt to extreme service environments. During the ablation process, the composite material mainly undergoes the following reactions: Cu(s) = Cu(l) Cu(l) = Cu(g) 4Cu(s) + O2(g) = 2Cu2O(l) 2Cu(s) + O2(g) = 2CuO(l) Cu₂O(s) = Cu₂O(l) Cu₂O(l) = Cu₂O(g) 4CuO(s) = 2Cu₂O(s) + O₂(g) 2C(s) + O2(g) = 2CO(g) C(s) + O2(g) = CO2(g) 2ZrC(s)+3O2(g)=2ZrO2(s)+2CO(g) ZrC(s) + 2O2(g) = ZrO2(s) + CO2(g) 2SiC(s)+3O2(g)=2SiO2(s)+2CO(g) SiC(s) + 2O2(g) = SiO2(s) + CO2(g) SiC(s) + O2(g) = SiO(g) + CO(g) 2SiC(s)+3O2(g)=2SiO(g)+2CO2(g) ZrO2(s) = ZrO2(l) SiO2(s) = SiO2(l) SiO2(l) = SiO2(g) CuxSiy(s) = CuxSiy(l) In the initial stage of ablation, the sample surface is gradually covered by oxides. At the ablation center, the large amount of oxide ceramics produced may cause volume expansion, while molten copper is carried away by high-speed gas flow. Thanks to the heat absorption and dissipation effects of copper during melting, the thermal response temperature at the ablation center is relatively low during the ablation process, and the molten copper can cover cracks and pores on the surface of the low-temperature zone, providing auxiliary protection. As the ablation time increases, the carbon fibers inside the composite material begin to be exposed, and ablation pits and copper residues will form due to the depletion of SiO2. In addition, a ZrO2 skeleton will be generated at the ablation center, and its pinning effect can reduce the loss of molten SiO2. A continuous Si-Zr-O region will also form beneath the surface of the composite material, which can effectively block the penetration of heat flux and oxygen, further improving the ablation resistance. At the ablation edge, the copper oxide layer can effectively protect the composite matrix; due to the lower temperature at the edge, the molten copper is retained and covers the surface, forming a good barrier against oxygen and heat flux. Meanwhile, since the wetting angle between copper and silicon exceeds 90°, excess liquid copper will aggregate into a spherical shape under the action of surface tension, preventing its disorderly flow from affecting the protective effect.

[0029] Compared with existing carbon / carbon-silicon carbide-zirconium carbide-copper composite material preparation processes, the technical solution of this invention provides a method for preparing 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite materials with superior performance. This provides in-depth theoretical support for future material design and applications, and offers important references and theoretical foundations for further design and optimization of carbon / carbon-zirconium carbide-silicon carbide-copper composite materials, thereby enhancing the diversity of composite material selection in high-temperature environments.

[0030] Unless otherwise specified, "room temperature" in this invention refers to 20-30℃.

[0031] All raw materials used in this invention are commercially available products and require no special preparation. The reagents and raw materials used in the following examples are: xylene (Sinopharm Chemical Reagent Co., Ltd.); PAN-based carbon fiber (purchased from Jiangsu Tianniao High-Tech Co., Ltd.). Furthermore, the needle-punching and weaving process used in the examples is a conventional technique in the field, and its specific operating procedures will not be elaborated here.

[0032] The technical solution of the present invention will be further illustrated by the following embodiments.

[0033] Example 1 A method for preparing an ultra-high temperature ceramic-bonded metal-modified composite material includes the following steps: (1) Preparation of 2.5D preforms: Using PAN-based carbon fiber as the matrix material, a density of 0.4 g / cm³ was prepared by needle punching and weaving process. 3 2.5D prefabricated structure; (2) Preparation of 2.5D carbon / carbon composite material: The 2.5D preform obtained in step (1) was placed in a CVI pyrolysis furnace, and the CVI process was carried out at a temperature of 1185℃ using methane with a volume fraction of 85% as the carbon source. Each deposition cycle lasted 240 hours, and the density of the 2.5D preform increased by 0.3 g / cm³ in each cycle. 3 After two cycles of processing, a layer of annular pyrolytic carbon is deposited around the carbon fibers inside the preform, resulting in a density of 1 g / cm³. 3 2.5D carbon / carbon composite material; (3) Preparation of precursor solution: Polymethylsilane (200g) and xylene (200g) were mixed at a mass ratio of 1:1 to prepare the precursor solution; (4) Preparation of 2.5D carbon / carbon-silicon carbide composite material: The 2.5D carbon / carbon composite material was placed in a pressure vessel, and the pressure inside the vessel was reduced to -0.09 MPa by vacuuming and allowed to stand for 5 min. Then, the feed valve was opened to introduce the above precursor solution, and argon gas was introduced to raise the pressure inside the vessel to 7 MPa and maintain this pressure for 30 min. Subsequently, the 2.5D carbon / carbon composite material after vacuum pressure impregnation was placed in an oven and dried at 150°C for 1 h. Then, it was placed in a tube furnace and heated to 1300°C at a heating rate of 10°C / min. It was then kept at this temperature for pyrolysis for 60 min. The process of "vacuum pressure impregnation-drying-pyrolysis" was repeated multiple times until a density of 1.5 g / cm³ was obtained. 3 2.5D carbon / carbon-silicon carbide composite material; (5) Preparation of zirconium copper metal powder: Under an argon atmosphere, zirconium powder (20.6g) and copper powder (14.4g) with a molar ratio of 1:1 were added to a ball mill jar, and tungsten carbide grinding balls were added at a ball-to-material ratio of 2:1. After the jar was closed, the pressure inside the jar was reduced to 10kPa. Then the ball mill jar was placed in a planetary ball mill and dry-milled at a speed of 500r / min for 30h. After the ball milling was completed, the powder was taken out under argon protection, which is zirconium copper metal powder. (6) Preparation of 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material: In a glove box under an argon atmosphere, some of the above-mentioned zirconium copper metal powder was spread on the bottom of a graphite crucible in a high-temperature carbonization furnace. The 2.5D carbon / carbon-silicon carbide composite material was placed on top of the zirconium copper metal powder in the crucible. The remaining zirconium copper metal powder was then completely covered on the surface of the 2.5D carbon / carbon-silicon carbide composite material. The crucible lid was tightened. The crucible was placed in a high-temperature carbonization furnace. After the furnace was closed, a vacuum was drawn. The high-temperature carbonization furnace was heated to 1350°C at a heating rate of 10°C / min. The furnace was held at this temperature for 1 hour for melting and infiltration. After the holding period, the furnace was allowed to cool naturally to room temperature to complete the melting and infiltration treatment. Finally, the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material was obtained.

[0034] Comparative Example 1 Similar to Example 1, the difference is that in step (4), by adjusting the number of cycles of "vacuum pressure impregnation-drying-pyrolysis", a density of 2.17 g / cm³ is obtained. 3 2.5D carbon / carbon-silicon carbide composite material.

[0035] Example 2 Similar to Example 1, the difference is that in step (4), by adjusting the number of cycles of "vacuum pressure impregnation-drying-pyrolysis", a density of 1.2 g / cm³ is obtained. 3 2.5D carbon / carbon-silicon carbide composite material.

[0036] Example 3 Similar to Example 1, the difference is that in step (4), by adjusting the number of cycles of "vacuum pressure impregnation-drying-pyrolysis", a density of 1.3 g / cm³ is obtained. 3 2.5D carbon / carbon-silicon carbide composite material.

[0037] Example 4 Similar to Example 1, the difference is that in step (4), by adjusting the number of cycles of "vacuum pressure impregnation-drying-pyrolysis", a density of 1.4 g / cm³ is obtained. 3 2.5D carbon / carbon-silicon carbide composite material.

[0038] Experimental results show that, after melt infiltration, the 2.5D carbon / carbon-silicon carbide composite materials of different densities obtained in Examples 1-4 and Comparative Example 1 have relatively small density differences, with the final 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material having the lowest density at 1.2 g / cm³. 3 When the C / C-SiC composite material is used as the matrix, the density is 2.17 g / cm³. 3 It has the lowest initial density, and its final density after melting and infiltration is close to that of the other three densities, thus yielding a value of 1.2 g / cm³. 3 The density has the best melting and infiltration efficiency.

[0039] Example 5 Same as Example 1, except that in step (5), the molar ratio of zirconium powder to copper powder is 2:1.

[0040] Example 6 Same as Example 1, except that in step (5), the molar ratio of zirconium powder to copper powder is 4:1.

[0041] Example 7 Same as Example 1, except that in step (5), the molar ratio of zirconium powder to copper powder is 1:2.

[0042] The composite materials prepared in Examples 1 and 5-7 with four different zirconium-copper molar ratios (1:1, 2:1, 4:1, 1:2) have densities of 2.15 g / cm³. 3 2.68g / cm 3 2.15g / cm 3 2.4g / cm 3 Comprehensive analysis of microstructure and melt infiltration uniformity shows that the composite material exhibits better density and uniformity when the zirconium-copper molar ratio is 1:1 and 2:1.

[0043] Example 8 Same as Example 1, except that in step (5), the ball milling time is 40h.

[0044] Example 9 Same as Example 1, except that in step (5), the ball milling time is 50h.

[0045] Example 10 Same as Example 1, except that in step (5), the ball milling time is 60h.

[0046] The composite materials prepared by four different ball milling times in Examples 1, 8-10, and 30h, 40h, 50h, and 60h had final melt penetration densities of 2.15 g / cm³, respectively. 3 2.28g / cm 3 2.03 g / cm 3 2.09 g / cm 3 However, because the samples prepared by the latter three ball milling times undergo secondary melting and infiltration, the efficiency is lower than that prepared by 30h. Therefore, based on comprehensive analysis, when the ball milling time is 30h, the bonding and flowability of the melt-infiltrated powder are optimal, and the corresponding melting and infiltration efficiency is optimal.

[0047] Example 11 Same as Example 1, except that in step (6), the melting temperature is set to 1150°C.

[0048] Example 12 Same as Example 1, except that in step (6), the melting temperature is set to 1450°C.

[0049] Example 13 Same as Example 1, except that in step (6), the melting temperature is set to 1550°C.

[0050] The composite materials prepared at four different melting temperatures in Examples 1 and 11-13 had melting densities of 2.24 g / cm³ for samples prepared at 1150℃, 1350℃, 1450℃, and 1550℃, respectively. 3 2.15g / cm3 2.2g / cm 3 2.08 g / cm 3 Comprehensive analysis of the microstructure shows that the melting and infiltration effect is optimal when the melting and infiltration temperature is 1350℃, and the damage to the carbon fibers inside the composite material is minimal. This maximizes the preservation of the reinforcing effect of the carbon fibers and ensures the overall performance of the composite material.

[0051] Figure 2 The image shows a SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 1. As can be seen from the image, the SiC particles introduced by the precursor impregnation pyrolysis method are uniformly distributed inside the composite material and fill the spaces between the fiber bundles. At the same time, the ZrC and Cu introduced by the reaction melting process synergistically fill the gaps between the fiber bundles with SiC, effectively improving the densification degree of the composite material.

[0052] Figure 3 The image shows a SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 2. As can be seen from the image, the fibers are wrapped by zirconium carbide and there are a few pores. Cu and SiC are distributed around the fibers to fill the pores.

[0053] Figure 4 The image shows a SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 3. As can be seen from the image, small particles of SiC, Cu, and ZrC surround the fibers, but there are many pores inside.

[0054] Figure 5 The image shows a SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 4. As can be seen from the image, the fibers are surrounded by ZrC, SiC and Cu in a synergistic manner, with a small number of pores.

[0055] Figure 6 The image shows a SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 5. As can be seen from the image, the fibers are wrapped with large blocks of ZrC, and there are SiC and Cu connections between the ZrC. The pores are few and the density is good.

[0056] Figure 7 The image shows the EDS diagram of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 5; it can be clearly seen from the image that the bulk particles are ZrC.

[0057] Figure 8The image shows a SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 6. As can be seen from the image, ZrC is wrapped around the fibers, but the particle size of ZrC is reduced, and the amount of fine granular ZrC around the fibers is increased. This is because the zirconium content is higher compared with other samples.

[0058] Figure 9 The image shows a SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 7. As can be seen from the image, for the sample prepared from metal powder with less zirconium and more copper, a large number of fine Cu and SiC particles are distributed around the fibers, while ZrC is less compared to the other three.

[0059] Figure 10 The image shows a SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 11. As can be seen from the image, there is a layer of ring-shaped ZrC protecting the fibers, and there are a large number of irregular ZrC, SiC and Cu composites between the fibers.

[0060] Figure 11 The image shows a SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 12. As can be seen from the image, the granular ZrC particles are interconnected and cover the fibers, exhibiting good density, which indicates that the viscosity increases at 1450℃.

[0061] Figure 12 The image shows a SEM image of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material prepared in Example 13. As can be seen from the image, there is a layer of ZrC at the bottom of the fiber, and a large number of small ZrC particles are formed by combining with each other at high temperature.

[0062] Figure 13 The XRD patterns of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite materials prepared in Examples 1 and 5-7 are shown in the figures. The formation of ZrC and SiC, as well as the infiltration of Cu, can be seen from the figures.

[0063] Table 1 shows the mass ablation rate and linear ablation rate results for different samples.

[0064] Table 1 As can be seen from the data in Table 1, the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite materials prepared in Examples 1-13 of this invention have better density and ablation performance than Comparative Example 1. By introducing ultra-high temperature ceramics and metals into the carbon matrix, it is possible to... Enhancing the ablation properties of 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composites provides an option for adapting to more demanding aircraft service environments.

[0065] Compared with existing carbon / carbon-zirconium carbide-silicon carbide-copper composite material preparation processes, the technical solution of this invention not only shortens the composite material preparation cycle, but also provides a method for preparing 2.5D carbon / carbon-zirconium carbide-zirconium carbide-copper composite materials with superior performance. This provides in-depth theoretical support for future material design and applications, and offers important references and theoretical foundations for further design and optimization of carbon / carbon-zirconium carbide-silicon carbide-copper composite materials, thereby enhancing the diversity of composite material selection in high-temperature environments.

[0066] Note that the above description is merely a preferred embodiment of the present invention and the technical principles employed. Those skilled in the art will understand that the present invention is not limited to the specific embodiments described herein, and various obvious changes, readjustments, and substitutions can be made without departing from the scope of protection of the present invention. Therefore, although the present invention has been described in detail through the above embodiments, the present invention is not limited to the above embodiments, and may include many other equivalent embodiments without departing from the concept of the present invention, the scope of which is determined by the scope of the appended claims.

Claims

1. A method for preparing an ultra-high temperature ceramic-bonded metal-modified composite material, characterized in that, Includes the following steps: (1) Needle-punching and weaving were performed using PAN-based carbon fiber as the matrix to obtain a 2.5D preform; (2) Pyrolytic carbon was deposited on the surface of the 2.5D preform by chemical vapor infiltration to obtain a 2.5D carbon / carbon composite material; (3) A ceramic phase was introduced into the 2.5D carbon / carbon composite material by using a precursor impregnation pyrolysis method to obtain a 2.5D carbon / carbon-silicon carbide composite material; (4) The 2.5D carbon / carbon-silicon carbide composite material was prepared by high-temperature vacuum melting in zirconium copper metal powder using the reactive melting method.

2. The preparation method according to claim 1, characterized in that, The specific operation steps of the chemical vapor infiltration method are as follows: a layer of annular pyrolytic carbon is deposited around the carbon fibers inside the 2.5D preform using methane gas to obtain a 2.5D carbon / carbon composite material. The conditions for the chemical vapor infiltration process are as follows: the chemical vapor infiltration process is carried out at a controlled temperature of 1180-1190℃; a deposition cycle is 220-240 hours, and the density of the 2.5D preform increases by 0.3 g / cm³ in each cycle. 3 After two cycles of treatment, the density of the precast body reached 1 g / cm³. 3 .

3. The preparation method according to claim 1, characterized in that, The specific operation steps of the precursor impregnation pyrolysis method are as follows: the 2.5D carbon / carbon composite material is placed in the precursor solution and cyclically processed by vacuum pressure impregnation-drying-pyrolysis as a complete cycle to obtain the 2.5D carbon / carbon-silicon carbide composite material.

4. The preparation method according to claim 3, characterized in that, The specific process of vacuum pressure impregnation is as follows: 2.5D carbon / carbon composite material is placed in a pressure vessel, vacuum is drawn to reduce the pressure inside the vessel to -0.09MPa, and it is left to stand for 5 minutes; a precursor solution is introduced, argon gas is introduced to raise the pressure inside the vessel to 7MPa, and this pressure is maintained for 30 minutes. The specific drying process is as follows: the temperature is 150-160℃, and the drying time is 1-2 hours; The specific pyrolysis process is as follows: the temperature is increased to 700-1300℃ at a heating rate of 10℃ / min, and then held at this temperature for pyrolysis for 30-60min.

5. The preparation method according to claim 4, characterized in that, The precursor solution is a mixture of polymethylsilane and xylene in a mass ratio of 1:

1.

6. The preparation method according to claim 1, characterized in that, The specific operation steps of the reaction melting infiltration method are as follows: Under the protective atmosphere of argon, a portion of zirconium copper metal powder is spread evenly on the bottom of a graphite crucible. The 2.5D carbon / carbon-silicon carbide composite material is placed on top of the zirconium copper metal powder in the crucible. The remaining zirconium copper metal powder is then completely covered on the 2.5D carbon / carbon-silicon carbide composite material. The high-temperature carbonization furnace is heated to 1150-1550℃ at a heating rate of 10℃ / min. After holding at this temperature for 1 hour, the furnace is allowed to cool naturally to room temperature to complete the melting infiltration treatment.

7. The preparation method according to claim 6, characterized in that, The zirconium-copper metal powder is prepared by ball milling zirconium powder and copper powder as raw materials under an argon atmosphere.

8. The preparation method according to claim 7, characterized in that, The molar ratio of zirconium powder to copper powder is (1-4):(1-2); the ball milling time is 30-60 h.

9. A 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material, characterized in that, It is prepared using the preparation method described in any one of claims 1-8.

10. The application of the 2.5D carbon / carbon-silicon carbide-zirconium carbide-copper composite material as described in claim 9 in the preparation of hypersonic vehicles.

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