Rapid preparation method of ultrahigh-temperature ceramic-based composite material of high-thermal-conductivity tire net
By combining the preform and multiple processes, the problems of high thermal conductivity and rapid densification in the preparation of existing ultra-high temperature ceramic matrix composites have been solved, realizing the rapid preparation of ceramic matrix composites with high thermal conductivity and high flexural strength, thus meeting the manufacturing requirements of hypersonic aircraft.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-24
- Publication Date
- 2026-03-27
Smart Images
Figure CN121735666A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of ceramic matrix composite material preparation, in particular to a rapid preparation method of high-thermal-conductivity preform super-high-temperature ceramic matrix composite material. BACKGROUND
[0002] The preform (carbon fiber preform), also known as preform, is a kind of non-woven fabric material formed by randomly interweaving short carbon fibers through mechanical carding or air laying technology. Due to its unique structure and performance, it has been widely used in composite materials, industrial manufacturing and special fields.
[0003] During service, the instantaneous surface temperature of the nose cone, leading edge and other key parts of a hypersonic vehicle can exceed 2000 ℃. However, although the existing ultra-high-temperature ceramic (UHTC) matrix composite material has high temperature resistance, it generally has the limitations of large intrinsic brittleness, low thermal conductivity and long preparation period. At the same time, the new generation of thermal protection systems is developing towards the direction of integrating heat protection, load bearing and thermal conductivity into one, thus there is an urgent need to develop a new type of ultra-high-temperature ceramic matrix composite material that can rapidly conduct local heat, suppress cracking caused by thermal stress, and achieve low cost and high efficiency densification in extreme thermal environments. Although sintering technologies such as hot-pressing sintering, reactive sintering and spark plasma sintering can produce high-performance ultra-high-temperature ceramics, they are expensive and difficult to apply to the preparation of large-size components. In another type of densification technology, the chemical vapor infiltration (CVI) process often takes tens to hundreds of hours, which is difficult to meet the requirements of rapid and low-cost manufacturing of large-size complex components; and the polymer precursor impregnation and pyrolysis (PIP) process requires up to 10-15 cycles to achieve densification. Therefore, developing a new type of ultra-high-temperature ceramic matrix composite material preparation route with high thermal conductivity, low cost and rapid densification has become an urgent need to break through the bottleneck of extreme thermal protection and support the development of hypersonic vehicles. SUMMARY
[0004] To solve the above technical problems, the purpose of the present application is to provide a rapid preparation method of high-thermal-conductivity preform super-high-temperature ceramic matrix composite material, to solve the problem that the existing ultra-high-temperature ceramic matrix composite material preparation process cannot have high thermal conductivity, low cost and rapid densification.
[0005] The technical solution of the present application to solve the above technical problems is as follows: a rapid preparation method of high-thermal-conductivity preform super-high-temperature ceramic matrix composite material is provided, which comprises the following steps in sequence: (1) shaping and interface deposition: flatten the preform body using a mold, shape it, then perform interface deposition to obtain a first preform; (2) Impregnation with the first slurry: Mix ultra-high temperature powder and water to prepare the first slurry. Impregnate the first mesh with the first slurry and dry it at 50-300℃ for 8-12 hours to obtain the second mesh. (3) PIP phenolic resin: Under vacuum conditions, the second mesh is immersed in phenolic resin for 10-45 min, and then under pressure conditions, it is continued to be immersed for 10-45 min, and then dried at 25-100℃ to obtain the third mesh. (4) Hot pressing curing and pyrolysis: The third mesh is hot-pressed and pyrolyzed to obtain the fourth mesh; (5) PIP toughening / ultra-high temperature particles + resin: Phenolic resin and toughening / ultra-high temperature particles are mixed to prepare a second slurry. Under vacuum conditions, the fourth mesh is immersed in the second slurry for 10-45 minutes. Then, under pressure conditions, it is immersed for another 10-45 minutes, and then cured and pyrolyzed to obtain the fifth mesh. (6) RMI: The fifth mesh is impregnated with silicon or silicon-zirconium alloy using RMI to obtain a high thermal conductivity mesh ultra-high temperature ceramic matrix composite material.
[0006] Based on the above technical solution, the present invention can be further improved as follows: Furthermore, in step (1), the conditions for interface deposition are: propylene flow rate of 0.1-20 L / min, argon flow rate of 0.5-21 L / min, deposition time of 10-80 h, temperature of 400-1100 ℃, and 2-8 batches of deposition.
[0007] Furthermore, in step (2), the ultra-high temperature powder is ZrB2, HfB2, NbB2, TaB2, ZrC, NbC, TaC or HfC.
[0008] Furthermore, in step (2), the volume fraction of ultra-high temperature powder in the first slurry is 2-30%. Furthermore, in step (3), the pressure condition is 0.2-1.5 MPa.
[0009] Furthermore, in step (3), the product is dried for 0.5-15 hours.
[0010] Furthermore, in step (4), the material is hot-pressed and cured for 2-20 hours under conditions of 0.5-5 MPa and 30-200℃.
[0011] Furthermore, in step (4), the sample is vacuum pyrolyzed at 700-1600℃ for 0.5-5h.
[0012] Furthermore, in step (5), the toughening / ultra-high temperature powder is ZrB2, HfB2, NbB2, TaB2, ZrC, NbC, TaC or HfC.
[0013] Furthermore, in step (5), the mass ratio of phenolic resin to toughening / ultra-high temperature particles is (10-100): (0.5-10).
[0014] Furthermore, in step (5), the pressure condition is 0.2-1.5 MPa.
[0015] Further, in step (5), the product is cured at 30-100℃ for 2-20 hours, and then cured at 150-200℃ for 2-20 hours to complete the curing process.
[0016] Furthermore, in step (5), the pyrolysis is carried out at 500-1500℃ for 0.5-5h.
[0017] The present invention has the following beneficial effects: 1. This invention uses a preformed tire mesh and combines hot pressing curing, slurry impregnation, PIP and RMI processes to prepare a high thermal conductivity tire mesh ultra-high temperature ceramic matrix composite material.
[0018] 2. This invention introduces an ultra-high temperature phase by using a slurry impregnation method, which solves the problem of low CVI deposition efficiency and effectively improves the preparation efficiency of C / SiC ceramic matrix composites.
[0019] 3. This invention uses resin-coated toughened / ultra-high temperature particles for PIP. The resin carbon layer effectively separates the particles, protecting the toughened / ultra-high temperature particles from erosion by the high temperature melt during the subsequent RMI process, which could lead to particle damage or agglomeration. It can also significantly improve the wetting behavior of the particles, increase the dispersion of the particles in the matrix, improve the uniformity of material density, and thus improve the thermal conductivity of the material.
[0020] 4. This invention combines multiple processes such as hot-press curing, slurry impregnation, PIP, and RMI, which can fully leverage the advantages of each process, overcome the shortcomings of a single process, and improve the material performance and preparation efficiency. For example, slurry impregnation can quickly introduce the ultra-high temperature phase and the particles can divide the pores. Then, hot-press curing is used to improve the densification rate of the composite material. Next, the PIP process is used to fill the large-sized pores between fiber bundles. Finally, the RMI process is used for densification treatment. The resulting ceramic matrix composite material has a more uniform microstructure and better thermal conductivity.
[0021] 5. The final bending strength of the tire mesh plate obtained by the present invention is greater than or equal to 90 MPa, and the thermal conductivity is ≥90 W / (m·K). Attached Figure Description
[0022] Figure 1 For process flow diagram; Figure 2 The image shows the microstructure of the composite material obtained in Example 1 using SEM. Detailed Implementation
[0023] The principles and features of the present invention are described below with reference to the accompanying drawings. The examples given are for illustrative purposes only and are not intended to limit the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer should be followed. Reagents or instruments whose manufacturers are not specified are all commercially available products.
[0024] Example 1: A rapid preparation method for a high thermal conductivity tire mesh ultra-high temperature ceramic matrix composite material includes the following steps: (process flow is available in [link to process flow]). Figure 1 ) (1) Shaping and interface deposition: The woven preform is flattened by a mold to shape it and prevent it from deforming during the deposition process. Then, interface deposition is carried out. The interface deposition conditions are: propylene flow rate of 10L / min, argon flow rate of 10L / min, deposition time of 50h, temperature of 800℃, and 6 furnaces of deposition to obtain the first preform. (2) Impregnation with the first slurry: Mix ultra-high temperature powder (ZrB2) and water to prepare the first slurry (volume fraction of 15%). Impregnate the first mesh with the first slurry and dry it at 200℃ for 10h to obtain the second mesh. (3) PIP phenolic resin: The second mesh is suspended above the phenolic resin without being immersed, and vacuumed for 25 minutes; then, under vacuum conditions, the second mesh is immersed in the phenolic resin for 25 minutes; then it is transferred to a pressure tank and immersed for another 25 minutes under pressure (1 MPa); finally, it is dried in an oven at 50°C for 8 hours to obtain the third mesh. (4) Hot pressing curing and pyrolysis: The third tire mesh is placed in a vulcanizing machine and hot-pressed for 10 hours at 3 MPa and 100°C. Then it is vacuum pyrolyzed for 3 hours at 1100°C to obtain the fourth tire mesh. (5) PIP toughening / ultra-high temperature particles + resin: Phenolic resin and toughening / ultra-high temperature particles (ZrB2) were mixed at a mass ratio of 50:6 to prepare the second slurry; the fourth mesh was suspended above the second slurry without being immersed, and vacuumed for 25 minutes; then, under vacuum conditions, the fourth mesh was immersed in the second slurry for 25 minutes; then it was transferred to a pressure tank and immersed for another 25 minutes under pressure (1MPa); finally, it was cured at 50°C for 10 hours, and then cured at 180°C for 10 hours to complete the curing process; and then it was pyrolyzed at 900°C for 3 hours to obtain the fifth mesh. (6) RMI: The fifth mesh is impregnated with silicon using RMI. Specifically, the mixture is weighed and placed into a crucible lined with graphite paper and leveled. It is first roughly pressed, then compacted with a pressure feeder, then leveled with a scraper, and finally compacted with a pressure feeder. The fifth mesh is placed into the crucible containing the mixture. The powder thickness under the fifth mesh is 15 mm. The mixture is then added above the fifth mesh and compacted with a pressure feeder. RMI is then performed to obtain a high thermal conductivity mesh ultra-high temperature ceramic matrix composite material (see Figure 2 ).
[0025] Example 2: A rapid preparation method for a high thermal conductivity tire mesh ultra-high temperature ceramic matrix composite material includes the following steps: (1) Shaping and interface deposition: The woven preform is flattened with a mold to shape it and prevent it from deforming during the deposition process. Then, interface deposition is carried out. The interface deposition conditions are: propylene flow rate of 0.1L / min, argon flow rate of 0.5L / min, deposition time of 80h, temperature of 400℃, and 8 furnaces of deposition to obtain the first preform. (2) Impregnation with the first slurry: Mix ultra-high temperature powder (HfB2) and water to prepare the first slurry (volume fraction of 2%). Impregnate the first mesh with the first slurry and dry it at 50°C for 12 hours to obtain the second mesh. (3) PIP phenolic resin: The second mesh is suspended above the phenolic resin without being immersed, and vacuumed for 10 minutes; then, under vacuum conditions, the second mesh is immersed in the phenolic resin for 10 minutes; then it is transferred to a pressure tank and immersed for another 10 minutes under pressure (0.2 MPa); finally, it is dried in an oven at 25°C for 15 hours to obtain the third mesh. (4) Hot pressing curing and pyrolysis: The third tire mesh is placed in a vulcanizing machine and hot-pressed for 20 hours at 0.5 MPa and 30°C, and then vacuum pyrolyzed for 5 hours at 700°C to obtain the fourth tire mesh; (5) PIP toughening / ultra-high temperature particles + resin: Phenolic resin and toughening / ultra-high temperature particles (HfB2) were mixed at a mass ratio of 10:0.5 to prepare the second slurry; the fourth mesh was suspended above the second slurry without being immersed, and vacuumed for 10 minutes; then, under vacuum conditions, the fourth mesh was immersed in the second slurry for 10 minutes; then it was transferred to a pressure tank and immersed for another 10 minutes under pressure (0.2MPa); finally, it was cured at 30°C for 2 hours, and then cured at 150°C for 20 hours to complete the curing process; and then it was pyrolyzed at 500°C for 5 hours to obtain the fifth mesh. (6) RMI: The fifth mesh is impregnated with silicon by RMI. Specifically, the mixture is weighed and placed into a crucible lined with graphite paper and leveled. It is first roughly pressed, then compacted with a pressure feeder, then leveled with a scraper, and finally compacted with a pressure feeder. The fifth mesh is placed into the crucible containing the mixture. The thickness of the powder under the fifth mesh is 15mm. The mixture is then added above the fifth mesh and compacted with a pressure feeder. RMI is performed to obtain a high thermal conductivity mesh ultra-high temperature ceramic matrix composite material.
[0026] Example 3: A rapid preparation method for a high thermal conductivity tire mesh ultra-high temperature ceramic matrix composite material includes the following steps: (1) Shaping and interface deposition: The woven preform is flattened with a mold to shape it and prevent it from deforming during the deposition process. Then, interface deposition is carried out. The interface deposition conditions are: propylene flow rate of 20L / min, argon flow rate of 21L / min, deposition time of 10h, temperature of 1100℃, and deposition is carried out in 2 batches to obtain the first preform. (2) Impregnation with the first slurry: The ultra-high temperature powder (ZrC) and water are mixed to prepare the first slurry (volume fraction of 30%). The first mesh is impregnated with the first slurry and then dried at 300℃ for 8 hours to obtain the second mesh. (3) PIP phenolic resin: The second mesh is suspended above the phenolic resin without being immersed, and vacuumed for 45 min; then, under vacuum conditions, the second mesh is immersed in the phenolic resin for 45 min; then it is transferred to a pressure tank and immersed for another 45 min under pressure (1.5 MPa); finally, it is dried in an oven at 100°C for 0.5 h to obtain the third mesh. (4) Hot pressing curing and pyrolysis: The third tire mesh is placed in a vulcanizing machine and hot-pressed for 2 hours at 5 MPa and 200℃, and then vacuum pyrolyzed for 0.5 hours at 1600℃ to obtain the fourth tire mesh; (5) PIP toughening / ultra-high temperature particles + resin: Phenolic resin and toughening / ultra-high temperature particles (HfC) were mixed at a mass ratio of 100:10 to prepare the second slurry; the fourth mesh was suspended above the second slurry without being immersed, and vacuumed for 45 min; then, under vacuum conditions, the fourth mesh was immersed in the second slurry for 45 min; then transferred to a pressure tank and immersed for another 45 min under pressure (1.5 MPa); finally, it was cured at 100℃ for 2 h, and then cured at 200℃ for 2 h to complete the curing process; and then pyrolyzed at 1500℃ for 0.5 h to obtain the fifth mesh. (6) RMI: The fifth mesh is impregnated with silicon or silicon-zirconium alloy by RMI. Specifically, the mixture is weighed and placed into a crucible with graphite paper and leveled. It is first roughly pressed, then compacted with a pressure feeder, then leveled with a scraper, and finally compacted with a pressure feeder. The fifth mesh is placed into the crucible containing the mixture. The thickness of the powder under the fifth mesh is 15mm. The mixture is then added above the fifth mesh and compacted with a pressure feeder. RMI is performed to obtain a high thermal conductivity mesh ultra-high temperature ceramic matrix composite material.
[0027] Test case I. The microstructure of the composite material obtained in Example 1 was examined by SEM. The results are shown in the figure. Figure 2 ( Figure 2 In the image, a is the SEM image of the cross-section, and b is the SEM image of the fiber bundle in the cross-section.
[0028] Depend on Figure 2 It can be seen that the ultra-high temperature particles are uniformly dispersed inside the matrix, and the material pores are completely filled by the matrix, with virtually no visible pores. In addition, the fibers are intact and have not been eroded by the RMI melt, which is an important factor in improving the material's performance.
[0029] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A rapid preparation method for a high thermal conductivity ultra-high temperature ceramic matrix composite material, characterized in that, The steps are as follows: (1) Shaping and interface deposition: The preform of the tire mesh is flattened by a mold and shaped, and then interface deposition is performed to obtain the first tire mesh; (2) Impregnation with the first slurry: Mix ultra-high temperature powder and water to prepare the first slurry. Impregnate the first mesh with the first slurry and dry it at 50-300℃ for 8-12 hours to obtain the second mesh. (3) PIP phenolic resin: Under vacuum conditions, the second mesh is immersed in phenolic resin for 10-45 min, and then under pressure conditions, it is continued to be immersed for 10-45 min, and then dried at 25-100℃ to obtain the third mesh. (4) Hot pressing and curing, pyrolysis: The third mesh is hot-pressed and cured and vacuum pyrolyzed to obtain the fourth mesh; (5) PIP toughening / ultra-high temperature particles + resin: Phenolic resin and toughening / ultra-high temperature particles are mixed to prepare a second slurry. Under vacuum conditions, the fourth mesh is immersed in the second slurry for 10-45 minutes. Then, under pressure conditions, it is immersed for another 10-45 minutes, and then cured and pyrolyzed to obtain the fifth mesh. (6) RMI: The fifth mesh is impregnated with silicon or silicon-zirconium alloy to obtain a high thermal conductivity mesh ultra-high temperature ceramic matrix composite material.
2. The rapid preparation method of the high thermal conductivity tire mesh ultra-high temperature ceramic matrix composite material according to claim 1, characterized in that, In step (1), the conditions for interface deposition are: propylene flow rate of 0.1-20 L / min, argon flow rate of 0.5-21 L / min, deposition time of 10-80 h, temperature of 400-1100 ℃, and 2-8 batches of deposition.
3. The rapid preparation method of the high thermal conductivity tire mesh ultra-high temperature ceramic matrix composite material according to claim 1, characterized in that, In step (2), the ultra-high temperature powder is ZrB2, HfB2, NbB2, TaB2, ZrC, NbC, TaC or HfC.
4. The rapid preparation method of the high thermal conductivity ultra-high temperature ceramic matrix composite material according to claim 1, characterized in that, In step (2), the volume fraction of ultra-high temperature powder in the first slurry is 2-30%.
5. The rapid preparation method of the high thermal conductivity tire mesh ultra-high temperature ceramic matrix composite material according to claim 1, characterized in that, In step (4), the product is hot-pressed and cured for 2-20 hours at 0.5-5 MPa and 30-200℃.
6. The rapid preparation method of the high thermal conductivity ultra-high temperature ceramic matrix composite material according to claim 1, characterized in that, In step (4), the sample is vacuum pyrolyzed at 700-1600℃ for 0.5-5h.
7. The rapid preparation method of the high thermal conductivity ultra-high temperature ceramic matrix composite material according to claim 1, characterized in that, In step (5), the toughening / ultra-high temperature particles are ZrB2, HfB2, NbB2, TaB2, ZrC, NbC, TaC or HfC.
8. The rapid preparation method of the high thermal conductivity ultra-high temperature ceramic matrix composite material according to claim 1, characterized in that, In step (5), the product is cured at 30-100℃ for 2-20 hours, and then cured at 150-200℃ for 2-20 hours to complete the curing process.
9. The rapid preparation method of the high thermal conductivity tire mesh ultra-high temperature ceramic matrix composite material according to claim 1, characterized in that, In step (5), the pyrolysis is carried out at 500-1500℃ for 0.5-5h.
10. The high thermal conductivity tire mesh ultra-high temperature ceramic matrix composite material prepared by the rapid preparation method according to any one of claims 1-9.