Preparation method of anti-ablation copper infiltration phase change sweating ceramic solid solution modified C / C material

Abstract

The invention relates to the technical field of C / C composite ceramic material forming, and discloses a preparation method of an anti-ablation copper infiltration phase change sweating ceramic solid solution modified C / C material, which comprises the following steps: preparing a low-density C / C composite material preform through isothermal chemical vapor deposition; constructing a titanium-zirconium-hafnium-silicon ceramic solid solution matrix in the low-density C / C composite material preform by adopting a process of combining slurry impregnation with precursor impregnation-cracking; the titanium-zirconium-hafnium-silicon ceramic solid solution matrix is subjected to copper infiltration under high-temperature and high-pressure conditions through a hot isostatic pressing technology. According to the preparation method of the anti-ablation copper infiltration phase change sweating ceramic solid solution modified C / C material, the zirconium-hafnium-silicon ceramic solid solution matrix is adopted, good high-temperature anti-ablation capacity is achieved, distribution is uniform, the diameter of formed pores is controllable, and a guarantee is provided for controllability of the infiltration depth and the infiltration amount of elemental copper in the copper infiltration process.

Description

Technical Field

[0001] This invention relates to the field of C / C composite ceramic material forming technology, specifically to a method for preparing C / C material modified with ablation-resistant copper-infiltrating phase transformation and sweating ceramic solid solution. Background Technology

[0002] With the development of solid rocket motors, the working environment of throat liners is becoming increasingly harsh. Studies have shown that the combustion chamber has reached tens of megapascals, with the highest temperature reaching 2700℃, while the erosion velocity of alumina particles exceeds Mach 1. Such stringent service conditions place extremely high demands on the high-temperature resistance and ablation resistance of throat liner materials. Traditional C / C composite materials cannot meet these requirements, thus there is an urgent need to find a new type of throat liner material that is resistant to high temperatures and ablation.

[0003] The copper-infiltrated phase transformation sweating ceramic solid solution modified C / C composite material with ablation resistance uses carbon fiber as the reinforcing fiber and titanium-zirconium-hafnium silicon ceramic solid solution as the matrix. Copper metal is infiltrated into the pores of the matrix. Under high-temperature service conditions, copper will undergo a vaporization phase transformation to carry away heat and reduce the surface temperature of the material, thereby improving the high-temperature resistance and ablation resistance of the throat liner.

[0004] The material is prepared by using puncture-structured carbon fiber fabric as a preform and through processes such as isothermal chemical vapor deposition, slurry impregnation, precursor impregnation-pyrolysis, high-temperature sintering, and hot isostatic pressing copper infiltration. Among these processes, slurry impregnation, precursor impregnation-pyrolysis, and high-temperature sintering are the key steps in the preparation of this material.

[0005] Common copper-infiltrating evaporative phase change materials typically use a single silicon carbide or zirconium carbide ceramic matrix to improve the wettability between the ceramic matrix and elemental copper. Very rarely, a composite ceramic matrix of silicon carbide / zirconium carbide / hafnium carbide is used. However, a single ceramic matrix exhibits poor resistance to high-temperature ablation after the copper has completely evaporated, while using a composite ceramic matrix can result in uneven composition distribution, leading to localized areas of lower resistance to high-temperature ablation.

[0006] This invention solves the aforementioned technical bottlenecks by designing a titanium-zirconium-hafnium-silicon ceramic solid solution matrix combined with a controllable copper infiltration process. Summary of the Invention

[0007] The purpose of this invention is to address the shortcomings of the above-mentioned technologies by providing a method for preparing a copper-resistant copper-infiltrating phase transformation sweating ceramic solid solution modified C / C material. The method uses a zirconium-hafnium silicon ceramic solid solution matrix, which has good high-temperature ablation resistance, uniform distribution, and controllable pore diameter, thus ensuring the controllability of the penetration depth and amount of copper element in the copper infiltrating process.

[0008] To achieve the above objectives, the preparation method of the anti-ablation copper-infiltrating phase transformation sweating ceramic solid solution modified C / C material designed in this invention includes the following steps: A) Preparation of low-density C / C composite preforms by isothermal chemical vapor deposition; B) A titanium-zirconium-hafnium silicon ceramic solid solution matrix was constructed in a low-density C / C composite preform using a slurry impregnation combined with a precursor impregnation-pyrolysis process. C) Copper infiltration is performed on a titanium-zirconium-hafnium ceramic solid solution matrix under high temperature and high pressure conditions using hot isostatic pressing (HIP).

[0009] Preferably, step A) includes the following steps: A1) Place the carbon fiber braided body into the deposition chamber, close the furnace door, and evacuate to below 180~200Pa; A2) Introduce N2 gas until the vacuum degree is greater than 95~100 kPa, close the gas filling valve, and evacuate again to below 180~200 Pa. Repeat this process at least 3 times. A3) Start heating, raise the temperature to 400-420℃ in 180-200 minutes, raise the temperature to 950-960℃ in 240-260 minutes, and raise the temperature to 978-982℃ in 60-70 minutes; A4) After the furnace temperature reaches 978~982℃ and is held for 120~140min, C3H6 and N2 with a volume ratio of 1:(1~1.1) are continuously introduced, and the furnace pressure is maintained at 1000~1100Pa. The temperature is then maintained for 9600±60min. After the temperature is maintained, the introduction of C3H6 is stopped, and N2 is introduced. The furnace is cooled to 140~150℃, and the furnace is opened to remove the material, thus obtaining a low-density C / C composite material preform.

[0010] Preferably, in step B), the slurry is prepared as follows: nano-sized titanium carbide powder, nano-sized zirconium carbide powder, nano-sized hafnium carbide powder, and xylene are placed in a mortar and ground in a mass ratio of (1~1.1):(1~1.1):(1~1.1):(0.2~0.25) until a slurry is formed. The slurry is then removed and placed in a ball mill jar. Zirconia grinding balls are added, with a ball-to-material ratio of (3~4):1. The mixture is then ball-milled in a planetary ball mill at a speed of 280~300 r / min for 24~25 hours. After ball milling, an equal mass of xylene is added to the product and stirred to form a slurry.

[0011] Preferably, in step B), when impregnating with slurry, the low-density C / C composite preform is completely immersed in the slurry and placed in a vacuum drying oven to be evacuated to 200~220Pa and maintained for 30~40 minutes. Then, the low-density C / C composite preform is taken out and placed in a forced-air drying oven and dried at 180~200℃ for 24~30 hours.

[0012] Preferably, in step B), the precursor impregnation-pyrolysis process includes dissolving polyzirconium carbosilane in polymethylsilane at a mass ratio of (1~1.1):1, completely immersing the low-density C / C composite preform that has undergone slurry impregnation in the solution, placing it in a vacuum drying oven and evacuating it to 200~220 Pa for 30~40 minutes, then removing it and placing it in a forced-air drying oven, introducing N2 and holding it at 250~260℃ for 6~8 hours, then placing it in a vacuum pyrolysis furnace and holding it at 1000~1200 Pa and 1300~1400℃ for 2~3 hours. This step is repeated multiple times until the density reaches 1.55 g / cm³. 3 The above materials are placed in a high-temperature heat treatment furnace and held at 100~120 Pa and 2200~2300℃ for 4~5 hours to sinter and prepare a titanium-zirconium-hafnium silicon ceramic solid solution matrix.

[0013] Preferably, in step C), the prepared titanium-zirconium-hafnium silicon ceramic solid solution matrix is ​​placed in a sleeve, coated with copper powder, and placed in a hot isostatic pressing furnace. N2 is introduced until the vacuum degree is greater than 95~100 kPa. The gas charging valve is closed, and the vacuum is evacuated again to below 450~500 Pa. Then, the temperature is increased according to the following steps: room temperature → 280~290℃ (heating time 120~150 min) → holding (holding time 180~240 min) → 320~360℃ (heating time 30~45 min) → holding (holding time 30~45 min). → 650~700℃ (heating time 500~600min) → Hold (holding time 120~150min) → 1300~1400℃ (heating time 240~270min) → Hold (holding time 60~90min) → Stop heating and control the temperature. After heating to 280~290℃ and holding, introduce N2 and pressurize to 40~50MPa. Stop introducing N2. Continue heating to 650~700℃, introduce N2 and maintain the pressure at 95~100MPa until the end.

[0014] Preferably, when the temperature is raised to 650~700℃, N2 is introduced and the pressure is maintained at 95~100MPa. When the temperature continues to rise, the pressure is maintained by a pressure relief valve.

[0015] Compared with the prior art, the present invention has the following advantages: 1. By combining slurry impregnation process and precursor impregnation-pyrolysis process, a variety of high-temperature resistant ceramics were introduced into the C / C composite matrix; 2. Solve the problem of high-temperature ablation resistance of C / C composite materials. In a high-temperature oxygen environment, elemental copper absorbs heat and undergoes a phase change, transforming into a liquid or even a gaseous state. The phase change process "sweats" and sublimates, carrying away heat and reducing the temperature near the material. 3. By utilizing the mechanism that elements in the same group easily form solid solutions, a titanium-zirconium-hafnium silicon ceramic solid solution is formed in the matrix, which further improves the ablation resistance of the material; 4. The problem of uniform distribution of multi-component ceramic matrix was solved by utilizing high-temperature diffusion to ensure that the titanium-zirconium-hafnium-silicon ceramic solid solution is uniformly distributed inside the matrix. 5. By controlling the diameter of pores in the matrix through high-temperature sintering process, the penetration depth and amount of elemental copper can be controlled. Detailed Implementation

[0016] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0017] A method for preparing an ablation-resistant, copper-infiltrating phase transformation, sweating ceramic solid solution modified C / C material includes the following steps: A) Preparation of low-density C / C composite preforms by isothermal chemical vapor deposition; B) A titanium-zirconium-hafnium silicon ceramic solid solution matrix was constructed in a low-density C / C composite preform using a slurry impregnation combined with a precursor impregnation-pyrolysis process. C) Copper infiltration is performed on a titanium-zirconium-hafnium ceramic solid solution matrix under high temperature and high pressure conditions using hot isostatic pressing (HIP).

[0018] Example 1 A method for preparing an ablation-resistant, copper-infiltrating phase transformation, sweating ceramic solid solution modified C / C material includes the following steps: A) Preparation of low-density C / C composite preforms by isothermal chemical vapor deposition, specifically including the following steps: A1) Place the carbon fiber braided body into the deposition chamber, close the furnace door, and evacuate to below 200 Pa; A2) Introduce N2 gas until the vacuum degree is greater than 95 kPa, close the gas filling valve, and evacuate the vacuum again to below 200 Pa. Repeat this process 3 times. A3) Start heating, heat to 400℃ in 180 minutes, heat to 950℃ in 240 minutes, and heat to 980℃ in 60 minutes; A4) After the furnace temperature reaches 980℃ and is held for 120 minutes, C3H6 and N2 with a volume ratio of 1:1 are continuously introduced, the furnace pressure is maintained at 1000Pa, and the holding time is continued for 9600 minutes. After the holding time is completed, the introduction of C3H6 is stopped, and N2 is continued to be introduced. The furnace is cooled to 150℃, the furnace is opened and the material is taken out to obtain a low-density C / C composite material preform. B) Constructing a titanium-zirconium-hafnium ceramic solid solution matrix in a low-density C / C composite preform using a slurry impregnation combined with a precursor impregnation-pyrolysis process: The preparation method of the slurry is as follows: Nano-sized titanium carbide powder, nano-sized zirconium carbide powder, nano-sized hafnium carbide powder and xylene are put into a mortar and ground in a mass ratio of 1:1:1:0.2 until they become a slurry. The slurry is then removed and placed in a ball mill jar. Zirconia grinding balls are added at a ball-to-material ratio of 3:1. The mixture is then ball-milled in a planetary ball mill at a speed of 280 r / min for 24 hours. After ball milling, an equal mass of xylene is added to the product and the mixture is stirred to form a slurry. When impregnating with slurry, the low-density C / C composite preform is completely immersed in the slurry and placed in a vacuum drying oven to be evacuated to 200Pa for 30 minutes. Then, the low-density C / C composite preform is taken out and placed in a forced-air drying oven to be dried at 180℃ for 24 hours. The precursor impregnation-pyrolysis process involves dissolving polyzirconium carbosilane in polymethylsilane at a 1:1 mass ratio, completely immersing the pre-impregnated low-density C / C composite material into the solution, placing it in a vacuum drying oven, evacuating it to 200 Pa, maintaining this temperature for 30 minutes, then removing it and placing it in a forced-air drying oven, purging it with N2, and holding it at 250°C for 6 hours. Next, it is placed in a vacuum pyrolysis furnace and held at 1000 Pa and 1300°C for 2 hours. This process is repeated multiple times until the density reaches 1.55 g / cm³. 3 The above materials were placed in a high-temperature heat treatment furnace and held at 100 Pa and 2300 °C for 4 hours to sinter and prepare a titanium-zirconium-hafnium silicon ceramic solid solution matrix. C) Copper infiltration is performed on the titanium-zirconium-hafnium silicon ceramic solid solution matrix under high temperature and high pressure conditions using hot isostatic pressing (HIP). The specific method is as follows: The prepared titanium-zirconium-hafnium silicon ceramic solid solution matrix was placed in a sleeve and coated with copper powder. It was then placed in a hot isostatic pressing furnace, and N2 was introduced until the vacuum level exceeded 95 kPa. The gas filling valve was closed, and the vacuum was evacuated again to below 500 Pa. The furnace was then heated according to the following sequence: room temperature → 280℃ (heating time 120 min) → hold (holding time 180 min) → 320℃ (heating time 30 min) → hold (holding time 30 min) → 650℃ (heating time 500 min) → hold (holding time 500 min). (120 min) → 1300℃ (heating time 240 min) → heat preservation (heat preservation time 60 min) → stop heating and control the temperature. Among them, after heating to 280℃ and heat preservation is completed, N2 is introduced to pressurize to 40MPa, N2 is stopped, and when heating continues to 650℃, N2 is introduced and the pressure is maintained at 95MPa until the end. Among them, when heating to 650℃, N2 is introduced and the pressure is maintained at 95MPa. When the temperature continues to rise, the pressure is maintained through the pressure relief valve.

[0019] Example 2 A method for preparing an ablation-resistant, copper-infiltrating phase transformation, sweating ceramic solid solution modified C / C material includes the following steps: A) Preparation of low-density C / C composite preforms by isothermal chemical vapor deposition, specifically including the following steps: A1) Place the carbon fiber braided body into the deposition chamber, close the furnace door, and evacuate to below 180 Pa; A2) Introduce N2 gas until the vacuum degree is greater than 95 kPa, close the gas filling valve, and evacuate the vacuum again to below 180 Pa. Repeat this process 4 times. A3) Start heating, heat to 400℃ in 180 minutes, heat to 950℃ in 240 minutes, and heat to 978℃ in 60 minutes; A4) After the furnace temperature reaches 978℃ and is held for 120 minutes, C3H6 and N2 with a volume ratio of 1:1 are continuously introduced, the furnace pressure is maintained at 1000Pa, and the holding time is continued for 9540 minutes. After the holding time is completed, the introduction of C3H6 is stopped, and N2 is continued to be introduced. The furnace is cooled to 140℃, the furnace is opened and the material is taken out to obtain a low-density C / C composite material preform. B) Constructing a titanium-zirconium-hafnium ceramic solid solution matrix in a low-density C / C composite preform using a slurry impregnation combined with a precursor impregnation-pyrolysis process: The preparation method of the slurry is as follows: Nano-sized titanium carbide powder, nano-sized zirconium carbide powder, nano-sized hafnium carbide powder and xylene are put into a mortar and ground in a mass ratio of 1:1:1:0.2 until they become a slurry. The slurry is then removed and placed in a ball mill jar. Zirconia grinding balls are added at a ball-to-material ratio of 3:1. The mixture is then ball-milled in a planetary ball mill at a speed of 280 r / min for 24 hours. After ball milling, an equal mass of xylene is added to the product and the mixture is stirred to form a slurry. When impregnating with slurry, the low-density C / C composite preform is completely immersed in the slurry and placed in a vacuum drying oven to be evacuated to 200Pa for 30 minutes. Then, the low-density C / C composite preform is taken out and placed in a forced-air drying oven to be dried at 180℃ for 24 hours. The precursor impregnation-pyrolysis process involves dissolving polyzirconium carbosilane in polymethylsilane at a 1:1 mass ratio, completely immersing the pre-impregnated low-density C / C composite material into the solution, placing it in a vacuum drying oven, evacuating it to 200 Pa, maintaining this temperature for 30 minutes, then removing it and placing it in a forced-air drying oven, purging it with N2, and holding it at 250°C for 6 hours. Next, it is placed in a vacuum pyrolysis furnace and held at 1000 Pa and 1300°C for 2 hours. This process is repeated multiple times until the density reaches 1.55 g / cm³. 3 The above materials were placed in a high-temperature heat treatment furnace and held at 100 Pa and 2200 °C for 4 hours to sinter and prepare a titanium-zirconium-hafnium silicon ceramic solid solution matrix. C) Copper infiltration is performed on the titanium-zirconium-hafnium silicon ceramic solid solution matrix under high temperature and high pressure conditions using hot isostatic pressing (HIP). The specific method is as follows: The prepared titanium-zirconium-hafnium silicon ceramic solid solution matrix was placed in a sleeve and coated with copper powder. It was then placed in a hot isostatic pressing furnace, and N2 was introduced until the vacuum level exceeded 95 kPa. The gas filling valve was closed, and the vacuum was evacuated again to below 450 Pa. The furnace was then heated according to the following sequence: room temperature → 280℃ (heating time 120 min) → hold (holding time 180 min) → 320℃ (heating time 30 min) → hold (holding time 30 min) → 650℃ (heating time 500 min) → hold (holding time 500 min). (120 min) → 1300℃ (heating time 240 min) → heat preservation (heat preservation time 60 min) → stop heating and control the temperature. Among them, after heating to 280℃ and heat preservation is completed, N2 is introduced to pressurize to 40MPa, N2 is stopped, and when heating continues to 650℃, N2 is introduced and the pressure is maintained at 95MPa until the end. Among them, when heating to 650℃, N2 is introduced and the pressure is maintained at 95MPa. When the temperature continues to rise, the pressure is maintained through the pressure relief valve.

[0020] Example 3 A method for preparing an ablation-resistant, copper-infiltrating phase transformation, sweating ceramic solid solution modified C / C material includes the following steps: A) Preparation of low-density C / C composite preforms by isothermal chemical vapor deposition, specifically including the following steps: A1) Place the carbon fiber braided body into the deposition chamber, close the furnace door, and evacuate to below 200 Pa; A2) Introduce N2 gas until the vacuum degree is greater than 100 kPa, close the gas filling valve, and evacuate the vacuum again to below 200 Pa. Repeat this process 5 times. A3) Start heating, heat to 420℃ in 200 minutes, heat to 960℃ in 260 minutes, and heat to 982℃ in 60 minutes; A4) After the furnace temperature reaches 982℃ and is held for 140 min, C3H6 and N2 with a volume ratio of 1:1.1 are continuously introduced, the furnace pressure is maintained at 1100 Pa, and the holding time is continued for 9660 min. After the holding time is completed, the introduction of C3H6 is stopped, and N2 is continued to be introduced. The furnace is cooled to 150℃, the furnace is opened and the material is taken out to obtain a low-density C / C composite material preform. B) Constructing a titanium-zirconium-hafnium ceramic solid solution matrix in a low-density C / C composite preform using a slurry impregnation combined with a precursor impregnation-pyrolysis process: The slurry is prepared as follows: Nano-sized titanium carbide powder, nano-sized zirconium carbide powder, nano-sized hafnium carbide powder, and xylene are ground in a mortar in a mass ratio of 1.1:1.1:1.1:0.25 until they become a slurry. The slurry is then removed and placed in a ball mill jar. Zirconia grinding balls are added at a ball-to-material ratio of 4:1. The mixture is then ball-milled in a planetary ball mill at a speed of 300 r / min for 25 hours. After ball milling, an equal mass of xylene is added to the product and the mixture is stirred to form a slurry. When impregnating with slurry, the low-density C / C composite preform is completely immersed in the slurry and placed in a vacuum drying oven to be evacuated to 220Pa for 40 minutes. Then, the low-density C / C composite preform is taken out and placed in a forced-air drying oven to be dried at 200℃ for 30 hours. The precursor impregnation-pyrolysis process involves dissolving polyzirconium carbosilane in polymethylsilane at a mass ratio of 1.1:1, completely immersing the low-density C / C composite preform (which has undergone slurry impregnation) in the solution, placing it in a vacuum drying oven, evacuating it to 220 Pa, and maintaining this temperature for 40 minutes. Then, it is removed and placed in a forced-air drying oven, where N2 is introduced and the temperature is maintained at 260°C for 8 hours. Finally, it is placed in a vacuum pyrolysis furnace and maintained at 1200 Pa and 1400°C for 3 hours. This process is repeated multiple times until the density reaches 1.55 g / cm³. 3 The above materials were placed in a high-temperature heat treatment furnace and held at 120 Pa and 2300 °C for 5 hours to sinter and prepare a titanium-zirconium-hafnium silicon ceramic solid solution matrix. C) Copper infiltration is performed on the titanium-zirconium-hafnium silicon ceramic solid solution matrix under high temperature and high pressure conditions using hot isostatic pressing (HIP). The specific method is as follows: The prepared titanium-zirconium-hafnium silicon ceramic solid solution matrix was placed in a sleeve and coated with copper powder. It was then placed in a hot isostatic pressing furnace, and N2 was introduced until the vacuum level exceeded 100 kPa. The gas filling valve was closed, and the vacuum was evacuated again to below 500 Pa. The furnace was then heated according to the following sequence: room temperature → 290℃ (heating time 150 min) → hold (holding time 240 min) → 360℃ (heating time 45 min) → hold (holding time 45 min) → 700℃ (heating time 600 min) → hold (holding time 600 min). (150 min) → 1400℃ (heating time 270 min) → heat preservation (heat preservation time 90 min) → stop heating and control the temperature. Among them, after heating to 290℃ and heat preservation is completed, N2 is introduced to pressurize to 50 MPa, then N2 is stopped. When heating continues to 700℃, N2 is introduced and the pressure is maintained at 100 MPa until the end. When heating to 700℃, N2 is introduced and the pressure is maintained at 100 MPa. When the temperature continues to rise, the pressure is maintained through the pressure relief valve.

[0021] Example 4 A method for preparing an ablation-resistant, copper-infiltrating phase transformation, sweating ceramic solid solution modified C / C material includes the following steps: A) Preparation of low-density C / C composite preforms by isothermal chemical vapor deposition, specifically including the following steps: A1) Place the carbon fiber braided body into the deposition chamber, close the furnace door, and evacuate to below 190 Pa; A2) Introduce N2 gas until the vacuum degree is greater than 95 kPa, close the gas filling valve, and evacuate the vacuum again to below 180 Pa. Repeat this process 3 times. A3) Start heating, heat to 410℃ in 190 minutes, heat to 960℃ in 250 minutes, and heat to 980℃ in 70 minutes; A4) After the furnace temperature reaches 980℃ and is held for 130 min, C3H6 and N2 with a volume ratio of 1:1.06 are continuously introduced, the furnace pressure is maintained at 1050 Pa, and the holding time is continued for 9620 min. After the holding time is completed, the introduction of C3H6 is stopped, and N2 is continued to be introduced. The furnace is cooled to 145℃, the furnace is opened and the material is taken out to obtain a low-density C / C composite material preform. B) Constructing a titanium-zirconium-hafnium ceramic solid solution matrix in a low-density C / C composite preform using a slurry impregnation combined with a precursor impregnation-pyrolysis process: The slurry is prepared as follows: Nano-sized titanium carbide powder, nano-sized zirconium carbide powder, nano-sized hafnium carbide powder, and xylene are ground in a mortar in a mass ratio of 1.1:1.08:1.02:0.22 until they become a slurry. The slurry is then removed and placed in a ball mill jar. Zirconia grinding balls are added at a ball-to-material ratio of 3.5:1. The mixture is then ball-milled in a planetary ball mill at a speed of 290 r / min for 24 hours. After ball milling, an equal mass of xylene is added to the product and the mixture is stirred to form a slurry. When impregnating with slurry, the low-density C / C composite preform is completely immersed in the slurry and placed in a vacuum drying oven to be evacuated to 210 Pa for 35 minutes. Then, the low-density C / C composite preform is taken out and placed in a forced-air drying oven to be dried at 190°C for 28 hours. The precursor impregnation-pyrolysis process involves dissolving polyzirconium carbosilane in polymethylsilane at a mass ratio of 1.08:1, completely immersing the pre-impregnated low-density C / C composite material into the solution, and placing it in a vacuum drying oven at 210 Pa for 35 minutes. It is then removed and placed in a forced-air drying oven, where N2 is introduced and the temperature is maintained at 250°C for 7 hours. Next, it is placed in a vacuum pyrolysis furnace and held at 110 Pa and 1350°C for 2.5 hours. This process is repeated multiple times until the density reaches 1.55 g / cm³. 3 The above-mentioned materials were placed in a high-temperature heat treatment furnace and held at 110 Pa and 2250 °C for 4.5 hours to sinter and prepare a titanium-zirconium-hafnium silicon ceramic solid solution matrix. C) Copper infiltration is performed on the titanium-zirconium-hafnium silicon ceramic solid solution matrix under high temperature and high pressure conditions using hot isostatic pressing (HIP). The specific method is as follows: The prepared titanium-zirconium-hafnium silicon ceramic solid solution matrix was placed in a sleeve and coated with copper powder. It was then placed in a hot isostatic pressing furnace, and N2 was introduced until the vacuum level exceeded 98 kPa. The gas filling valve was closed, and the vacuum was evacuated again to below 480 Pa. The furnace was then heated according to the following sequence: room temperature → 285℃ (heating time 130 min) → hold (holding time 200 min) → 340℃ (heating time 40 min) → hold (holding time 40 min) → 675℃ (heating time 550 min) → hold (holding time 550 min). (140 min) → 1350℃ (heating time 250 min) → heat preservation (heat preservation time 75 min) → stop heating and control the temperature. Among them, after heating to 285℃ and heat preservation is completed, N2 is introduced to pressurize to 45 MPa, N2 is stopped, and when heating continues to 675℃, N2 is introduced and the pressure is maintained at 98 MPa until the end. Among them, when heating to 675℃, N2 is introduced and the pressure is maintained at 98 MPa. When the temperature continues to rise, the pressure is maintained through the pressure relief valve.

[0022] The copper-infiltrated copper phase change sweating ceramic solid solution modified C / C material prepared in the above embodiments has a copper infiltration mass fraction of 10% and a plasma ablation rate of less than 0.005 mm / s within 40 seconds. Compared with the plasma ablation rate of 0.06-0.08 mm / s of traditional carbon-carbon composite materials, this represents a significant decrease. In particular, the ablation resistance temperature can reach up to 2600 degrees Celsius, while the highest ablation resistance temperature of traditional carbon-carbon composite materials is 2200 to 2300 degrees Celsius. Although the highest ablation resistance temperature of silicon carbide materials can reach 2500 degrees Celsius, their plasma ablation rate is 0.1 mm / s, which is much higher than that of the copper-infiltrated copper phase change sweating ceramic solid solution modified C / C material prepared in this invention.

[0023] This invention discloses a method for preparing copper-modified C / C materials with copper phase change and sweating ceramic solid solution resistance. By combining a slurry impregnation process and a precursor impregnation-pyrolysis process, various high-temperature resistant ceramics are introduced into the C / C composite matrix. This addresses the high-temperature ablation resistance issue of C / C composites. In a high-temperature, oxygen-rich environment, elemental copper absorbs heat and undergoes a phase change, transforming into a liquid or even gaseous state. The phase change process, known as "sweat," sublimates and carries away heat, lowering the temperature near the material. Utilizing the mechanism that elements in the same group readily form solid solutions, a titanium-zirconium-hafnium-silicon ceramic solid solution is formed in the matrix, further improving the material's ablation resistance. The method also solves the problem of uniform distribution in multi-component ceramic matrices by utilizing high-temperature diffusion to ensure a uniform distribution of the titanium-zirconium-hafnium-silicon ceramic solid solution within the matrix. Furthermore, the high-temperature sintering process controls the diameter of pores in the matrix, thereby achieving controllable penetration depth and amount of elemental copper.

[0024] It should be noted that the above description of the technical solutions is exemplary, and this specification may be embodied in different forms and should not be construed as limiting it to the technical solutions set forth herein. Rather, providing these descriptions will ensure that the disclosure of this invention is thorough and complete, and will fully convey the scope of this specification to those skilled in the art. Furthermore, the technical solutions of this invention are defined only by the scope of the claims. Features of various embodiments of this invention may be combined or spliced ​​together in part or in whole, and may be implemented in various different configurations as will be fully understood by those skilled in the art. Embodiments of this invention may be implemented independently of each other or may be implemented together in an interdependent relationship.

[0025] For those skilled in the art, several simple deductions or substitutions can be made without departing from the concept of the present invention, and the above structures should all be considered to fall within the protection scope of the present invention.

Claims

1. A method for preparing a C / C material modified with a solid solution of copper-infiltrating phase transformation ceramic that resists ablation and sweating, characterized in that: Includes the following steps: A) Preparation of low-density C / C composite preforms by isothermal chemical vapor deposition; B) A titanium-zirconium-hafnium silicon ceramic solid solution matrix was constructed in a low-density C / C composite preform using a slurry impregnation combined with a precursor impregnation-pyrolysis process. C) Copper infiltration is performed on the titanium-zirconium-hafnium ceramic solid solution matrix under high temperature and high pressure conditions using hot isostatic pressing (HIP).

2. The preparation method of the ablation-resistant copper-infiltrating phase transformation sweating ceramic solid solution modified C / C material as described in claim 1, characterized in that: Step A) includes the following steps: A1) Place the carbon fiber woven body into the deposition chamber, close the furnace door, and evacuate to below 180~200Pa; A2) Introduce N2 gas until the vacuum degree is greater than 95~100 kPa, close the gas filling valve, and evacuate again to below 180~200 Pa. Repeat this process at least 3 times. A3) Start heating, raise the temperature to 400-420℃ in 180-200 minutes, raise the temperature to 950-960℃ in 240-260 minutes, and raise the temperature to 978-982℃ in 60-70 minutes; A4) After the furnace temperature reaches 978~982℃ and is held for 120~140min, C3H6 and N2 with a volume ratio of 1:(1~1.1) are continuously introduced, and the furnace pressure is maintained at 1000~1100Pa. The temperature is then maintained for 9600±60min. After the temperature is maintained, the introduction of C3H6 is stopped, and N2 is introduced. The furnace is cooled to 140~150℃, and the furnace is opened to remove the material, thus obtaining a low-density C / C composite material preform.

3. The preparation method of the ablation-resistant copper-infiltrating phase transformation sweating ceramic solid solution modified C / C material as described in claim 1, characterized in that: In step B), the slurry is prepared as follows: Nano-sized titanium carbide powder, nano-sized zirconium carbide powder, nano-sized hafnium carbide powder, and xylene are placed in a mortar and ground in a mass ratio of (1~1.1):(1~1.1):(1~1.1):(0.2~0.25) until a slurry is formed. The slurry is then removed and placed in a ball mill jar. Zirconia grinding balls are added at a ball-to-material ratio of (3~4):

1. The mixture is then ball-milled in a planetary ball mill at a speed of 280~300 r / min for 24~25 hours. After ball milling, an equal mass of xylene is added to the product and stirred to form a slurry.

4. The preparation method of the ablation-resistant copper-infiltrating phase transformation sweating ceramic solid solution modified C / C material as described in claim 1, characterized in that: In step B), when impregnating with slurry, the low-density C / C composite preform is completely immersed in the slurry and placed in a vacuum drying oven to be evacuated to 200~220Pa and maintained for 30~40 minutes. Then, the low-density C / C composite preform is taken out and placed in a forced-air drying oven and dried at 180~200℃ for 24~30 hours.

5. The preparation method of the ablation-resistant copper-infiltrating phase transformation sweating ceramic solid solution modified C / C material as described in claim 1, characterized in that: In step B), the precursor impregnation-pyrolysis process includes dissolving polyzirconium carbosilane in polymethylsilane at a mass ratio of (1~1.1):1, completely immersing the low-density C / C composite preform that has undergone slurry impregnation in the solution, placing it in a vacuum drying oven and evacuating it to 200~220 Pa for 30~40 minutes, then removing it and placing it in a forced-air drying oven, introducing N2 and holding it at 250~260℃ for 6~8 hours, then placing it in a vacuum pyrolysis furnace and holding it at 1000~1200 Pa and 1300~1400℃ for 2~3 hours. This step is repeated multiple times until the density reaches 1.55 g / cm³. 3 The above materials are placed in a high-temperature heat treatment furnace and held at 100~120 Pa and 2200~2300℃ for 4~5 hours to sinter and prepare a titanium-zirconium-hafnium silicon ceramic solid solution matrix.

6. The preparation method of the ablation-resistant copper-infiltrating phase transformation sweating ceramic solid solution modified C / C material as described in claim 1, characterized in that: In step C), the prepared titanium-zirconium-hafnium silicon ceramic solid solution matrix is ​​placed in a sleeve, coated with copper powder, and placed in a hot isostatic pressing furnace. N2 is introduced until the vacuum level is greater than 95-100 kPa. The gas filling valve is closed, and the vacuum is evacuated again to below 450-500 Pa. Then, the temperature is increased according to the following steps: room temperature → 280-290℃ (heating time 120-150 min) → holding (holding time 180-240 min) → 320-360℃ (heating time 30-45 min) → holding (holding time 30-45 min) → 650~700℃ (heating time 500~600min) → Hold (holding time 120~150min) → 1300~1400℃ (heating time 240~270min) → Hold (holding time 60~90min) → Stop heating and control the temperature. After heating to 280~290℃ and holding, introduce N2 and pressurize to 40~50MPa. Stop introducing N2. Continue heating to 650~700℃, introduce N2 and maintain the pressure at 95~100MPa until the process ends.

7. The preparation method of the ablation-resistant copper-infiltrating phase transformation sweating ceramic solid solution modified C / C material as described in claim 6, characterized in that: When the temperature rises to 650~700℃, N2 is introduced and the pressure is maintained at 95~100MPa. When the temperature continues to rise, the pressure is maintained through the pressure relief valve.