An ultra-high temperature ceramic matrix composite ceramic coating and a method of making the same

Abstract

The application relates to an ultrahigh-temperature ceramic matrix composite ceramic coating and a preparation method thereof; the method comprises the following steps: cleaning and sand blasting treatment of a ceramic matrix composite substrate; ceramic coating powder containing ultrahigh-temperature ceramic powder and silicon carbide powder is sprayed onto the surface of the cleaned and sand blasted ceramic matrix composite substrate by a plasma spraying process to form a coating; the surface of the ceramic matrix composite substrate with the coating is scanned, melted and solidified by using a laser beam irradiation process, and then high-temperature heat treatment is carried out in a vacuum environment, so that an ultrahigh-temperature ceramic matrix composite ceramic coating is prepared on the ceramic matrix composite substrate. The application can improve the high-temperature stability, sintering degree and ablation resistance of the prepared ultrahigh-temperature ceramic matrix composite ceramic coating, can make the ultrahigh-temperature ceramic matrix composite have excellent high-temperature resistance, oxidation resistance and ablation resistance, and can be used for net forming of high-performance complex structural parts.

Description

Technical Field

[0001] This invention belongs to the field of aerospace materials technology, and particularly relates to an ultra-high temperature ceramic matrix composite material ceramic coating and its preparation method. Background Technology

[0002] Structural components in aerospace vehicles place high demands on the high-temperature resistance and mechanical properties of ceramic matrix composites. Traditional ultra-high temperature ceramic matrix composites, relying solely on the matrix, are insufficient to meet these requirements. Water and oxygen corrosion in the environment easily leads to failure of the matrix and interface layers, as well as fiber damage. In contrast, ultra-high temperature ceramics such as ZrC, HfC, and TaC have high melting points, excellent high-temperature resistance, and certain oxidation resistance. Preparing ultra-high temperature ceramic coatings on the surface of ultra-high temperature ceramic matrix composites holds promise for meeting the requirements of aerospace vehicle structural components.

[0003] However, the traditional precursor impregnation pyrolysis process and chemical vapor impregnation process are difficult to prepare uniform and dense multi-component composite coatings quickly. In addition, there are also problems that the high-temperature mechanical properties and high-temperature ablation resistance of ceramic matrix composites need to be further improved. Therefore, it is urgent to develop an efficient method for preparing ultra-high temperature ceramic matrix composite ceramic coatings. Summary of the Invention

[0004] To address one or more technical problems existing in the prior art, this invention provides an ultra-high temperature ceramic matrix composite material ceramic coating and its preparation method. This invention can efficiently prepare a uniform and dense ultra-high temperature ceramic matrix composite material ceramic coating, improving the high-temperature stability, sintering degree, and ablation resistance of the prepared coating. It enables the ultra-high temperature ceramic matrix composite material to possess excellent high-temperature resistance, mechanical properties, oxidation resistance, and ablation resistance, and can be used for the net-shape forming of high-performance complex structural components.

[0005] The present invention provides a method for preparing a ceramic coating on an ultra-high temperature ceramic matrix composite material in a first aspect, the method comprising the following steps:

[0006] (1) Cleaning and sandblasting the ceramic matrix composite material matrix;

[0007] (2) A ceramic coating powder containing ultra-high temperature ceramic powder and silicon carbide powder is sprayed onto the surface of a cleaned and sandblasted ceramic matrix composite material matrix by plasma spraying process to form a coating.

[0008] (3) The surface of the coated ceramic matrix is ​​scanned, melted and solidified by laser beam irradiation process, and then subjected to high temperature heat treatment in a vacuum environment to obtain an ultra-high temperature ceramic matrix composite ceramic coating on the ceramic matrix.

[0009] Preferably, the ceramic matrix composite material matrix is ​​a C / ZrC-SiC ultra-high temperature ceramic matrix composite material matrix.

[0010] Preferably, the ultra-high temperature ceramic powder is one or more of zirconium carbide powder, hafnium carbide powder, and tantalum carbide powder. More preferably, the particle size of the zirconium carbide powder, hafnium carbide powder, and tantalum carbide powder is 200 nm to 1 μm; the particle size of the silicon carbide powder is 200 nm to 1 μm; and / or the volume ratio of the ultra-high temperature ceramic powder to the silicon carbide powder is (4 to 6): 1.

[0011] Preferably, the plasma spraying process is a low-pressure plasma spraying process, and the parameters for the low-pressure plasma spraying process are: current 650-750A, voltage 55-80V, argon flow rate 25-45L / min, hydrogen flow rate 2-4L / min, powder feed rate 35-60g / min, vacuum chamber pressure 100kPa, and spraying distance 150-200mm.

[0012] Preferably, in the laser beam irradiation process, an Nd:YAG laser with a wavelength of 1064nm is used; during the irradiation process, the laser power is 100-200W, the spot diameter is 1.0-1.2mm, the scanning speed is 10-15mm / s, the pulse width is 2-4ms, the frequency is 15-30Hz, and the overlap rate is 30-50%.

[0013] Preferably, the high-temperature heat treatment is performed in a vacuum environment with a pressure of 50 to 150 kPa; and / or the temperature of the high-temperature heat treatment is 1300 to 1700 °C, and the time of the high-temperature heat treatment is 0.5 to 2.0 h.

[0014] Preferably, before cleaning and sandblasting the ceramic matrix composite matrix, the surface of the ceramic matrix composite matrix is ​​first etched using a laser.

[0015] Preferably, a laser is used to etch the surface of the ceramic matrix composite matrix to uniformly form multiple microgrooves on the surface of the ceramic matrix composite matrix. The cross-sectional profile of the microgrooves is V-shaped, the depth of the microgrooves is 5 to 10 μm, and the spacing between two adjacent microgrooves is 10 to 20 μm.

[0016] Preferably, the ceramic coating powder further comprises Yb2Si2O7 powder, and the volume fraction of Yb2Si2O7 powder in the ceramic coating powder is 5-10%; more preferably, the particle size of the Yb2Si2O7 powder is 200nm-1μm.

[0017] In a second aspect, the present invention provides an ultra-high temperature ceramic matrix composite ceramic coating, which is prepared using the preparation method described in the first aspect of the present invention.

[0018] Compared with the prior art, the present invention has at least the following beneficial effects:

[0019] (1) This invention uses plasma spraying to spray ultra-high temperature ceramic powder and SiC powder, mixed in a certain proportion, onto the surface of a ceramic matrix composite substrate. Subsequently, laser beam irradiation is used to scan, melt, and solidify the substrate surface. This allows the coating material and the substrate surface to melt simultaneously, forming a high-bonding coating during natural cooling. This enables the coating to form a dense microstructure at high temperatures, enhancing its strength and temperature resistance. The powder in the coating can melt and bond more fully, forming a more uniform structure. The uniform and dense coating reduces the penetration path of the ablation medium, effectively improving the coating's ablation resistance and... The high-temperature mechanical properties of the coating are improved by performing high-temperature heat treatment on the coating in a vacuum environment, which is beneficial to improving the high-temperature stability, sintering degree and ablation resistance of the coating. Compared with traditional precursor impregnation pyrolysis and chemical vapor deposition processes, the plasma spraying, laser beam irradiation and vacuum heat treatment processes used in this invention can provide higher deposition rates, more uniform coating quality and better high-temperature stability and ablation resistance when preparing ultra-high temperature ceramic matrix composite ceramic coatings. This can efficiently prepare uniform and dense coatings and significantly improve the mechanical properties and ablation resistance of ultra-high temperature ceramic matrix composites under extreme high temperature conditions.

[0020] (2) This invention rapidly prepares an ultra-high temperature ceramic coating on the surface of a substrate using a plasma spraying process, achieving ultra-high temperature, oxidation resistance, and ablation resistance protection on the surface of the ceramic matrix composite substrate. This invention combines laser beam irradiation and vacuum annealing (vacuum heat treatment) to rapidly strengthen the bonding between the substrate and the coating, as well as the sintering of the ultra-high temperature ceramic phase inside the coating, effectively improving the erosion resistance, high temperature stability, sintering degree, and ablation resistance of the ultra-high temperature ceramic matrix composite ceramic coating. The method of this invention enables the ultra-high temperature ceramic matrix composite material containing the ultra-high temperature ceramic matrix composite ceramic coating to possess excellent high temperature resistance, excellent high temperature mechanical properties, and excellent high temperature ablation resistance.

[0021] (3) In some preferred embodiments of the present invention, a laser is used to etch the surface of the ceramic matrix composite material matrix to uniformly form multiple microgrooves on the surface of the ceramic matrix composite material matrix, and the cross-sectional profile of the microgrooves is V-shaped, the depth of the microgrooves is 5-10 μm, and the spacing between two adjacent microgrooves is 10-20 μm. The present invention found that the design of the V-shaped microgrooves, combined with laser beam irradiation scanning melting and solidification treatment and high-temperature heat treatment, jointly improves the high-temperature mechanical properties and high-temperature ablation resistance of the ultra-high temperature ceramic matrix composite material. The V-shaped microgroove structure can provide effective mechanical locking and enhance the adhesion between the coating and the substrate. This suitable surface microstructure can significantly increase the contact area between the coating and the substrate, thereby improving the adhesion strength of the coating. The high temperature of the laser beam can melt the interface material between the coating and the substrate surface, and then naturally cool and solidify, further enhancing the adhesion between the coating and the substrate. The bonding force of the substrate is conducive to the formation of a dense and uniform bonding layer. This invention has found that the microgrooves can help disperse the stress generated by the coating under high temperature conditions, reduce local stress concentration, reduce thermal stress and crack formation. In addition, under high temperature conditions, the microgrooves can alleviate the temperature gradient between the coating surface and the substrate, thereby reducing the stress caused by thermal expansion. Laser high-temperature irradiation can release the residual stress in the coating material. At the same time, due to the solidification process and heat treatment process, a dense and uniform structure is formed, which is conducive to improving the high-temperature strength of the coating. Furthermore, the microgrooves can reduce the erosion of the coating by changing the flow pattern of the ablation medium. At the same time, the guidance of the microgrooves can help reduce the peeling of ablation products, which is conducive to improving the high-temperature ablation resistance. The high temperature of laser beam irradiation can melt and re-solidify the coating surface, sealing the surface micropores and cracks. This can effectively block the intrusion of high-temperature gases and improve the ablation resistance.

[0022] (4) In some preferred embodiments of the present invention, the ceramic coating powder further comprises Yb2Si2O7, and the volume fraction of Yb2Si2O7 powder in the ceramic coating powder is 5-10%. The present invention has found that adding Yb2Si2O7 to the ceramic coating powder of ultra-high temperature ceramic matrix composites not only improves the density of the coating, but also optimizes the thermophysical properties and ablation resistance of the coating. This enables the coating to maintain stable mechanical properties and ablation resistance under extreme high temperature environments, thereby further improving the service life and reliability of the material. The possible reason is that adding appropriate Yb2Si2O7 to the ceramic coating powder can make Yb2Si2O7 more stable. At high temperatures, Yb₂Si₂O₇ melts and fills microcracks and defects within the coating. When microcracks appear in the coating due to thermal or mechanical stress, Yb₂Si₂O₇ can melt at high temperatures, filling these cracks and defects and preventing their propagation. This helps to effectively maintain the integrity and density of the coating and effectively block the penetration of oxidizing media in high-temperature oxidizing environments, thereby improving the coating's oxidation resistance and ablation resistance. In addition, under extreme high-temperature environments, some Yb₂Si₂O₇ may react with other components of the coating or external media to form a new dense oxide protective layer, which can also enhance the coating's ablation resistance and prevent the material from undergoing severe ablation under the impact of high-temperature airflow. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0024] The present invention provides a method for preparing a ceramic coating on an ultra-high temperature ceramic matrix composite material in a first aspect, the method comprising the following steps:

[0025] (1) Cleaning and sandblasting the ceramic matrix composite material matrix; the present invention does not specifically limit the cleaning and sandblasting process, which is a conventional technique in the field; specifically, for example, before spraying, acetone is used to clean the surface of the ceramic matrix composite material matrix, and sandblasting is performed (sand particle size 16-64 mesh, sandblasting pressure 0.4-0.6MPa), and then dry compressed air is used to clean the residual sand particles on the surface of the matrix.

[0026] (2) A ceramic coating powder containing ultra-high temperature ceramic powder and silicon carbide powder is sprayed onto the surface of a cleaned and sandblasted ceramic matrix composite material substrate by plasma spraying process to form a coating; in this invention, the thickness of the coating is preferably 50μm to 300μm.

[0027] (3) The surface of the coated ceramic matrix composite substrate is scanned, melted and solidified using a laser beam irradiation process, and then subjected to high-temperature heat treatment in a vacuum environment to obtain an ultra-high temperature ceramic matrix composite ceramic coating (abbreviated as ceramic coating) on ​​the ceramic matrix composite substrate; In this invention, the laser beam irradiation process is, for example, a high-energy laser beam irradiation process; The scanning melting and solidification in this invention is to scan and melt the surface of the coated ceramic matrix composite substrate using a laser beam irradiation process, so that the coating material and the substrate surface melt simultaneously, and solidify during natural cooling to form a coating with high bonding strength; In this invention, the surface of the coating after laser beam irradiation is subjected to high-temperature heat treatment (annealing) in a vacuum environment to improve the high-temperature stability, sintering degree and ablation resistance of the coating.

[0028] This invention utilizes plasma spraying to coat a ceramic matrix composite substrate with a mixture of ultra-high temperature ceramic powder and SiC powder in a specific ratio. Subsequently, laser beam irradiation is used to scan, melt, and solidify the substrate surface. This allows both the coating material and the substrate surface to melt simultaneously, forming a high-bonding coating during natural cooling. This enables the coating to form a dense microstructure at high temperatures, enhancing its strength and temperature resistance. The powder in the coating melts and bonds more fully, resulting in a more uniform structure. This uniform and dense coating reduces the penetration path of ablation media, effectively improving the coating's resistance to ablation and high-temperature performance. The mechanical properties of the coating are improved by performing high-temperature heat treatment in a vacuum environment, which enhances the high-temperature stability, sintering degree, and ablation resistance of the coating. Compared with traditional precursor impregnation pyrolysis and chemical vapor deposition processes, the plasma spraying, laser beam irradiation, and vacuum heat treatment processes used in this invention can provide higher deposition rates, more uniform coating quality, and better high-temperature stability and ablation resistance when preparing ultra-high temperature ceramic matrix composite ceramic coatings. This enables the efficient preparation of uniform and dense coatings and significantly improves the mechanical properties and ablation resistance of ultra-high temperature ceramic matrix composites under extreme high-temperature conditions. This invention rapidly prepares an ultra-high temperature ceramic coating on the surface of a substrate using a plasma spraying process, achieving ultra-high temperature, oxidation resistance, and ablation resistance protection on the surface of the ceramic matrix composite substrate. This invention combines laser beam irradiation and vacuum annealing processes to rapidly strengthen the bond between the substrate and the coating, as well as the sintering of the ultra-high temperature ceramic phase within the coating. This effectively improves the erosion resistance, high-temperature stability, sintering degree, and ablation resistance of the ultra-high temperature ceramic matrix composite coating. The method of this invention enables ultra-high temperature ceramic matrix composites containing the aforementioned ultra-high temperature ceramic matrix composite coating to possess excellent high-temperature resistance, excellent high-temperature mechanical properties, and excellent high-temperature ablation resistance.

[0029] According to some preferred embodiments, the ceramic matrix composite material matrix is ​​a C / ZrC-SiC ultra-high temperature ceramic matrix composite material matrix (also referred to as carbon fiber reinforced zirconium carbide-silicon carbide ultra-high temperature ceramic matrix composite material matrix); the present invention does not specifically limit the C / ZrC-SiC ultra-high temperature ceramic matrix composite material matrix, etc., and can use products that can be purchased directly or products prepared by existing methods.

[0030] According to some preferred embodiments, the ultra-high temperature ceramic powder is one or more of zirconium carbide powder (ZrC powder), hafnium carbide powder (HfC powder), and tantalum carbide powder (TaC powder); in this invention, preferably, the particle size of the ceramic coating powder is 200 nm to 1 μm, specifically, preferably, the particle size of zirconium carbide powder, hafnium carbide powder, and tantalum carbide powder is all 200 nm to 1 μm; the particle size of the silicon carbide powder is 200 nm to... 1μm, that is, in this invention, preferably, the particle size of ZrC powder is 200nm to 1μm, the particle size of HfC powder is 200nm to 1μm, the particle size of TaC powder is 200nm to 1μm, and the particle size of SiC powder is 200nm to 1μm; and / or the volume ratio of the ultra-high temperature ceramic powder to the silicon carbide powder is (4 to 6):1 (e.g., 4:1, 4.5:1, 5:1, 5.5:1 or 6:1), preferably 5:1.

[0031] According to some preferred embodiments, the plasma spraying process is a low-pressure plasma spraying process. The parameters for the low-pressure plasma spraying process are: current 650-750A, voltage 55-80V, argon flow rate 25-45L / min, hydrogen flow rate 2-4L / min, powder feed rate 35-60g / min, vacuum chamber pressure 100kPa, and spraying distance 150-200mm. The present invention does not specify the plasma spraying time, as long as the preset coating thickness can be obtained.

[0032] According to some preferred embodiments, an Nd:YAG laser with a wavelength of 1064 nm is used in the laser beam irradiation process. In this invention, during the scanning and melting process of the coated ceramic matrix composite substrate, an Nd:YAG laser with a wavelength of 1064 nm is used to control the laser to scan the surface with a certain overlap rate, uniformly irradiating the entire coating surface. During the irradiation process, the laser power is 100-200 W, the spot diameter is 1.0-1.2 mm, the scanning speed is 10-15 mm / s, the pulse width is 2-4 ms, the frequency is 15-30 Hz, and the overlap rate is 30-50%. In this invention, the selection of these laser beam irradiation process parameters can precisely control the melting process, which not only ensures a good bond between the coating material and the substrate, but also helps to improve the uniformity, density, and high-temperature stability of the coating. This significantly improves the high-temperature mechanical properties and high-temperature ablation resistance of the ultra-high temperature ceramic matrix composite material, enabling it to perform excellently in extreme working environments.

[0033] According to some preferred embodiments, high-temperature heat treatment is performed in a vacuum environment with a pressure of 50–150 kPa; and / or the temperature of the high-temperature heat treatment (annealing) is 1300–1700°C (e.g., 1300°C, 1400°C, 1500°C, 1600°C, or 1700°C), and the time of the high-temperature heat treatment is 0.5–2.0 h (e.g., 0.5, 1, 1.5, or 2 h); in this invention, it is preferred that the temperature of the high-temperature heat treatment is 1300–1700°C and the time is 0.5–2.0 h, followed by natural cooling to room temperature. Suitable high-temperature heat treatment conditions promote the bonding between powder particles, which is beneficial to optimizing the microstructure of the material and improving the density and uniformity of the coating.

[0034] According to some preferred embodiments, the surface of the ceramic matrix composite matrix is ​​first etched using a laser before cleaning and sandblasting.

[0035] According to some preferred embodiments, a laser is used to etch the surface of a ceramic matrix composite matrix to uniformly form multiple microgrooves on the surface of the ceramic matrix composite matrix. The cross-sectional profile of the microgrooves is V-shaped, the depth of the microgrooves is 5-10 μm, and the spacing between two adjacent microgrooves is 10-20 μm. In this invention, this spacing refers to the distance between the centers of two adjacent microgrooves. In this invention, the apex angle of the microgrooves is 20°. This invention has found that the design of this V-shaped microgrooves, combined with laser beam irradiation scanning melting and solidification treatment and high-temperature heat treatment, jointly improves the high-temperature mechanical properties and high-temperature ablation resistance of ultra-high temperature ceramic matrix composites. The V-shaped microgroove structure can provide effective mechanical locking and enhance the adhesion between the coating and the substrate. This suitable surface microstructure can significantly increase the contact area between the coating and the substrate, thereby improving the adhesion strength of the coating. The high temperature of the laser beam can melt the interface material between the coating and the substrate surface. After cooling and solidification, the coating is further strengthened by the natural cooling process, which enhances the adhesion between the coating and the substrate and facilitates the formation of a dense and uniform bonding layer. This invention reveals that the microgrooves help disperse the stress generated in the coating under high-temperature conditions, reducing localized stress concentration, thermal stress, and crack formation. Furthermore, in high-temperature environments, the microgrooves can alleviate the temperature gradient between the coating surface and the substrate, thereby reducing stress caused by thermal expansion. High-temperature laser irradiation can release residual stress in the coating material. Simultaneously, the solidification and heat treatment processes create a dense and uniform structure, which is beneficial for improving the high-temperature strength of the coating. In addition, the microgrooves can reduce the erosion of the coating by altering the flow pattern of the ablation medium. The guidance provided by the microgrooves also helps reduce the peeling of ablation products, improving high-temperature ablation resistance. The high temperature of the laser beam irradiation can melt and re-solidify the coating surface, sealing surface micropores and cracks, effectively preventing the intrusion of high-temperature gases and enhancing ablation resistance.

[0036] In this invention, the microgrooves formed on the surface of the ultra-high temperature ceramic matrix composite material matrix help to better seal the surface of the ceramic matrix composite material matrix and reduce the penetration of oxidizing media. This is very important for improving the oxidation resistance under high temperature environment. However, if the microgrooves are formed on the coating surface, this still cannot effectively improve the bonding and adhesion between the matrix material and the coating structure. On the contrary, the microgrooves structure may be easily damaged or worn during use, resulting in a decrease in coating performance. While the microgrooves formed on the surface of ultra-high temperature ceramic matrix composite (UHT) substrates help to better seal the substrate surface, thereby improving the high-temperature mechanical properties and high-temperature ablation resistance of UHT ceramic matrix composites, this is inseparable from the auxiliary role of laser beam irradiation scanning melting and solidification treatment. If laser beam irradiation scanning melting and solidification treatment is not performed after plasma spraying, although ceramic coating powder can be sprayed onto the substrate surface with microgrooves through plasma spraying, without the assistance of laser beam irradiation, the density and interfacial bonding strength of the coating may be insufficient. This is because laser beam irradiation provides the opportunity for melting and solidification, which helps to fully fill the microgrooves, eliminate defects, and enhance the density and adhesion of the coating. Without the assistance of laser beam irradiation melting, the filling of microgrooves may not be uniform and tight enough, and the coating may have lower strength at the interfacial bonding, especially under high temperature and high stress environments, which may make it more prone to interfacial delamination and coating cracking.

[0037] According to some preferred embodiments, the ceramic coating powder further comprises Yb₂Si₂O₇ powder, wherein the volume fraction of Yb₂Si₂O₇ powder in the ceramic coating powder is 5-10% (e.g., 5%, 6%, 7%, 8%, 9%, or 10%); in this invention, preferably, the particle size of the Yb₂Si₂O₇ powder is 200 nm to 1 μm; this invention has found that adding Yb₂Si₂O₇ to the ceramic coating powder of ultra-high temperature ceramic matrix composites not only improves the density of the coating but also optimizes the thermophysical properties and ablation resistance of the coating. This enables the coating to maintain stable mechanical properties and ablation resistance under extreme high temperature environments, thereby further improving the service life and reliability of the material; the possible reason is that in ceramic coatings... Adding appropriate amounts of Yb₂Si₂O₇ to the coating powder allows Yb₂Si₂O₇ to melt at high temperatures and fill microcracks and defects within the coating. When microcracks appear in the coating due to thermal or mechanical stress, Yb₂Si₂O₇ can melt at high temperatures, filling these cracks and defects and preventing their propagation. This helps to effectively maintain the integrity and density of the coating and effectively block the penetration of oxidizing media in high-temperature oxidizing environments, thereby improving the coating's oxidation resistance and ablation resistance. In addition, under extreme high-temperature environments, some Yb₂Si₂O₇ may react with other components of the coating or external media to form a new dense oxide protective layer, which can also enhance the coating's ablation resistance and prevent the material from undergoing severe ablation under the impact of high-temperature airflow.

[0038] In this invention, it is preferred that the volume fraction of Yb2Si2O7 powder in the ceramic coating powder is 5-10%. This invention has found that although adding Yb2Si2O7 to the ceramic coating filler is beneficial for further improving the high-temperature mechanical properties and high-temperature ablation resistance of ultra-high temperature ceramic matrix composites, the control of the Yb2Si2O7 content is crucial. This is likely because an appropriate amount of Yb2Si2O7 can melt and flow at high temperatures, filling cracks. This helps maintain the integrity and stability of the coating under high-temperature conditions, reducing crack propagation and structural damage, and promoting the densification and stabilization of the coating structure. However, if the Yb2Si2O7 content is too low, the coating cannot effectively fill cracks at high temperatures and will not achieve an effective effect. Conversely, if the Yb2Si2O7 content is too high, it will increase the brittleness of the coating, making it more prone to cracking under high-temperature mechanical stress. Furthermore, if the content is too high, the presence of the molten phase will significantly reduce the upper temperature limit of the coating, affecting the overall high-temperature stability of the coating.

[0039] In a second aspect, the present invention provides an ultra-high temperature ceramic matrix composite ceramic coating, which is prepared using the preparation method described in the first aspect of the present invention.

[0040] The present invention will be further described below by way of examples, but the scope of protection of the present invention is not limited to these embodiments. The present invention may have many other embodiments, and those skilled in the art can make various corresponding changes and modifications based on the present invention without departing from its spirit and essence; however, all such corresponding changes and modifications should fall within the scope of protection of the appended claims.

[0041] Example 1

[0042] ① Powder preparation: ZrC powder, HfC powder, TaC powder, and SiC powder are mixed in a certain proportion to form a mixed powder (ceramic coating powder); wherein, the average particle size of ZrC powder is 500nm, the average particle size of HfC powder is 500nm, the average particle size of TaC powder is 500nm, the average particle size of SiC powder is 500nm, and the volume ratio of ZrC powder, HfC powder, TaC powder, and SiC powder in the ceramic coating powder is 2:2.5:0.5:1.

[0043] ② Substrate surface treatment: Before spraying, use acetone to clean the surface of the ceramic matrix composite matrix (C / ZrC-SiC ceramic matrix composite matrix), and then sandblast the surface of the C / ZrC-SiC ceramic matrix composite matrix (substrate) (sand particle size 64 mesh, sandblasting pressure 0.5MPa). Use dry compressed air to clean the residual sand particles on the substrate surface.

[0044] ③ Plasma spraying: The ceramic coating powder obtained in step ① is sprayed onto the surface of the C / ZrC-SiC ceramic matrix composite substrate treated in step ② to form a coating (coating thickness 100μm). The low-pressure plasma spraying process parameters are: current 700A, voltage 70V, argon flow rate 30L / min, hydrogen flow rate 3L / min, powder feed rate 45g / min, vacuum chamber pressure 100kPa, and spraying distance 180mm.

[0045] ④ Laser beam irradiation: The surface of the C / ZrC-SiC ceramic matrix composite substrate with the coating formed in step ③ is scanned, melted and solidified using a laser beam irradiation process. During the scanning and melting process, an Nd:YAG laser with a wavelength of 1064nm is used to control the laser to scan the surface with a certain overlap rate, uniformly irradiating the entire coating surface. During the irradiation process, the laser power is 150W, the spot diameter is 1.1mm, the scanning speed is 10mm / s, the pulse width is 3ms, the frequency is 20Hz, and the overlap rate is 40%.

[0046] ⑤ Vacuum annealing: The coating surface after laser beam irradiation in step ④ is annealed in a vacuum environment (pressure 100 kPa) at a temperature of 1500℃ for 1.0 h and then naturally cooled to room temperature to obtain an ultra-high temperature ceramic matrix composite ceramic coating on a C / ZrC-SiC ceramic matrix composite substrate.

[0047] The C / ZrC-SiC ceramic matrix composite material with an ultra-high temperature ceramic matrix composite ceramic coating prepared in this embodiment was tested. The tensile strength at 1800℃ was 192 MPa, the flexural strength at 1800℃ was 244 MPa, and the average linear ablation rate in the 2100℃ / 4000s oxyacetylene ablation test was 4.6 × 10⁻⁶. -4 mm / s.

[0048] Example 2

[0049] ① Powder preparation: ZrC powder, TaC powder, and SiC powder are mixed in a certain proportion to form a mixed powder (ceramic coating powder); wherein, the average particle size of ZrC powder is 500nm, the average particle size of TaC powder is 500nm, the average particle size of SiC powder is 500nm, and the volume ratio of ZrC powder, TaC powder, and SiC powder in the ceramic coating powder is 3.5:1.5:1.

[0050] ② Substrate surface treatment: Before spraying, use acetone to clean the surface of the ceramic matrix composite matrix (C / ZrC-SiC ceramic matrix composite matrix), and then sandblast the surface of the C / ZrC-SiC ceramic matrix composite matrix (substrate) (sand particle size 64 mesh, sandblasting pressure 0.5MPa). Use dry compressed air to clean the residual sand particles on the substrate surface.

[0051] ③ Plasma spraying: The ceramic coating powder obtained in step ① is sprayed onto the surface of the C / ZrC-SiC ceramic matrix composite substrate treated in step ② to form a coating (coating thickness 100μm). The low-pressure plasma spraying process parameters are: current 700A, voltage 70V, argon flow rate 30L / min, hydrogen flow rate 3L / min, powder feed rate 45g / min, vacuum chamber pressure 100kPa, and spraying distance 180mm.

[0052] ④ Laser beam irradiation: The surface of the C / ZrC-SiC ceramic matrix composite substrate with the coating formed in step ③ is scanned, melted and solidified using a laser beam irradiation process. During the scanning and melting process, an Nd:YAG laser with a wavelength of 1064nm is used to control the laser to scan the surface with a certain overlap rate, uniformly irradiating the entire coating surface. During the irradiation process, the laser power is 150W, the spot diameter is 1.1mm, the scanning speed is 10mm / s, the pulse width is 3ms, the frequency is 20Hz, and the overlap rate is 40%.

[0053] ⑤ Vacuum annealing: The coating surface after laser beam irradiation in step ④ is annealed in a vacuum environment (pressure 100 kPa) at a temperature of 1500℃ for 1.0 h and then naturally cooled to room temperature to obtain an ultra-high temperature ceramic matrix composite ceramic coating on a C / ZrC-SiC ceramic matrix composite substrate.

[0054] The C / ZrC-SiC ceramic matrix composite material with an ultra-high temperature ceramic matrix composite ceramic coating prepared in this embodiment was tested. The tensile strength at 1800℃ was 155 MPa, the flexural strength at 1800℃ was 237 MPa, and the average linear ablation rate in the 2100℃ / 4000s oxyacetylene ablation test was 6.1 × 10⁻⁶. -4 mm / s.

[0055] Example 3

[0056] ① Powder preparation: HfC powder and SiC powder are prepared into mixed powder (ceramic coating powder) in a certain proportion; wherein, the average particle size of HfC powder is 500nm, the average particle size of SiC powder is 500nm, and the volume ratio of HfC powder to SiC powder in the ceramic coating powder is 5:1.

[0057] ② Substrate surface treatment: Before spraying, use acetone to clean the surface of the ceramic matrix composite matrix (C / ZrC-SiC ceramic matrix composite matrix), and then sandblast the surface of the C / ZrC-SiC ceramic matrix composite matrix (substrate) (sand particle size 64 mesh, sandblasting pressure 0.5MPa). Use dry compressed air to clean the residual sand particles on the substrate surface.

[0058] ③ Plasma spraying: The ceramic coating powder obtained in step ① is sprayed onto the surface of the C / ZrC-SiC ceramic matrix composite substrate treated in step ② to form a coating (coating thickness 100μm). The low-pressure plasma spraying process parameters are: current 700A, voltage 70V, argon flow rate 30L / min, hydrogen flow rate 3L / min, powder feed rate 45g / min, vacuum chamber pressure 100kPa, and spraying distance 180mm.

[0059] ④ Laser beam irradiation: The surface of the C / ZrC-SiC ceramic matrix composite substrate with the coating formed in step ③ is scanned, melted and solidified using a laser beam irradiation process. During the scanning and melting process, an Nd:YAG laser with a wavelength of 1064nm is used to control the laser to scan the surface with a certain overlap rate, uniformly irradiating the entire coating surface. During the irradiation process, the laser power is 150W, the spot diameter is 1.1mm, the scanning speed is 10mm / s, the pulse width is 3ms, the frequency is 20Hz, and the overlap rate is 40%.

[0060] ⑤ Vacuum annealing: The coating surface after laser beam irradiation in step ④ is annealed in a vacuum environment (pressure 100 kPa) at a temperature of 1500℃ for 1.0 h and then naturally cooled to room temperature to obtain an ultra-high temperature ceramic matrix composite ceramic coating on a C / ZrC-SiC ceramic matrix composite substrate.

[0061] The C / ZrC-SiC ceramic matrix composite material with an ultra-high temperature ceramic matrix composite ceramic coating prepared in this embodiment was tested. The tensile strength at 1800℃ was 163 MPa, the flexural strength at 1800℃ was 242 MPa, and the average linear ablation rate in the 2100℃ / 4000s oxyacetylene ablation test was 5.8 × 10⁻⁶. -4 mm / s.

[0062] Example 4

[0063] Example 4 is basically the same as Example 1, except that:

[0064] ② Substrate surface treatment: The surface of the ceramic matrix composite matrix (C / ZrC-SiC ceramic matrix composite matrix) is etched using a laser to uniformly form multiple microgrooves on the surface of the ceramic matrix composite matrix. The cross-sectional profile of the microgrooves is V-shaped, the depth of the microgrooves is 6μm, and the spacing between two adjacent microgrooves is 15μm. Before spraying, the surface of the etched ceramic matrix composite matrix (C / ZrC-SiC ceramic matrix composite matrix) is cleaned with acetone, and the surface of the etched C / ZrC-SiC ceramic matrix composite matrix (substrate) is sandblasted (sand particle size 64 mesh, sandblasting pressure 0.5MPa). Dry compressed air is used to clean the residual sand particles on the surface of the substrate.

[0065] The C / ZrC-SiC ceramic matrix composite material with an ultra-high temperature ceramic matrix composite ceramic coating prepared in this embodiment was tested. The tensile strength at 1800℃ was 205 MPa, the flexural strength at 1800℃ was 261 MPa, and the average linear ablation rate in the 2100℃ / 4000s oxyacetylene ablation test was 2.8 × 10⁻⁶. -4 mm / s.

[0066] Example 5

[0067] Example 5 is basically the same as Example 1, except that:

[0068] ① Powder preparation: ZrC powder, HfC powder, TaC powder, SiC powder, and Yb2Si2O7 powder are mixed in a certain proportion to form a ceramic coating powder; wherein, the average particle size of ZrC powder, HfC powder, TaC powder, SiC powder, and Yb2Si2O7 powder is 500nm, the volume ratio of ZrC powder, HfC powder, TaC powder, and SiC powder in the ceramic coating powder is 2:2.5:0.5:1, and the volume fraction of Yb2Si2O7 in the ceramic coating powder is 6%.

[0069] ② Substrate surface treatment: The surface of the ceramic matrix composite matrix (C / ZrC-SiC ceramic matrix composite matrix) is etched using a laser to uniformly form multiple microgrooves on the surface of the ceramic matrix composite matrix. The cross-sectional profile of the microgrooves is V-shaped, the depth of the microgrooves is 6μm, and the spacing between two adjacent microgrooves is 15μm. Before spraying, the surface of the etched ceramic matrix composite matrix (C / ZrC-SiC ceramic matrix composite matrix) is cleaned with acetone, and the surface of the etched C / ZrC-SiC ceramic matrix composite matrix (substrate) is sandblasted (sand particle size 64 mesh, sandblasting pressure 0.5MPa). Dry compressed air is used to clean the residual sand particles on the surface of the substrate.

[0070] The C / ZrC-SiC ceramic matrix composite material with an ultra-high temperature ceramic matrix composite ceramic coating prepared in this embodiment was tested. The tensile strength at 1800℃ was 215 MPa, the flexural strength at 1800℃ was 273 MPa, and the average linear ablation rate in the 2100℃ / 4000s oxyacetylene ablation test was 1.3 × 10⁻⁶. -4 mm / s.

[0071] Example 6

[0072] Example 6 is basically the same as Example 5, except that:

[0073] ① Powder preparation: ZrC powder, HfC powder, TaC powder, SiC powder, and Yb2Si2O7 powder are mixed in a certain proportion to form a mixed powder (ceramic coating powder); wherein, the average particle size of ZrC powder, HfC powder, TaC powder, SiC powder, and Yb2Si2O7 powder is 500nm, the volume ratio of ZrC powder, HfC powder, TaC powder, and SiC powder in the ceramic coating powder is 2:2.5:0.5:1, and the volume fraction of Yb2Si2O7 in the ceramic coating powder is 15%.

[0074] The C / ZrC-SiC ceramic matrix composite material with an ultra-high temperature ceramic matrix composite ceramic coating prepared in this embodiment was tested. The tensile strength at 1800℃ was 197 MPa, the flexural strength at 1800℃ was 256 MPa, and the average linear ablation rate in the 2100℃ / 4000s oxyacetylene ablation test was 3.3 × 10⁻⁶. -4 mm / s.

[0075] Example 7

[0076] Example 7 is basically the same as Example 1, except that:

[0077] ⑤ Vacuum annealing: The coating surface after laser beam irradiation in step ④ is annealed in a vacuum environment (pressure 100 kPa) at a temperature of 600℃ for 4 hours and then naturally cooled to room temperature to obtain an ultra-high temperature ceramic matrix composite ceramic coating on a C / ZrC-SiC ceramic matrix composite substrate.

[0078] The C / ZrC-SiC ceramic matrix composite material with an ultra-high temperature ceramic matrix composite ceramic coating prepared in this embodiment was tested. The tensile strength at 1800℃ was 186 MPa, the flexural strength at 1800℃ was 231 MPa, and the average linear ablation rate in the 2100℃ / 4000s oxyacetylene ablation test was 6.6 × 10⁻⁶. -4 mm / s.

[0079] Comparative Example 1

[0080] ① Powder preparation: ZrC powder, HfC powder, TaC powder, and SiC powder are mixed in a certain proportion to form a mixed powder (ceramic coating powder); wherein, the average particle size of ZrC powder is 1500nm, the average particle size of HfC powder is 1500nm, the average particle size of TaC powder is 1500nm, the average particle size of SiC powder is 1500nm, and the volume ratio of ZrC powder, HfC powder, TaC powder, and SiC powder in the ceramic coating powder is 2:2.5:0.5:1.

[0081] ② Substrate surface treatment: Before spraying, use acetone to clean the surface of the ceramic matrix composite matrix (C / ZrC-SiC ceramic matrix composite matrix), and then sandblast the surface of the C / ZrC-SiC ceramic matrix composite matrix (substrate) (sand particle size 64 mesh, sandblasting pressure 0.5MPa). Use dry compressed air to clean the residual sand particles on the substrate surface.

[0082] ③ Plasma spraying: The ceramic coating powder obtained in step ① is sprayed onto the surface of the C / ZrC-SiC ceramic matrix composite substrate treated in step ② to form a coating (coating thickness 100μm). The low-pressure plasma spraying process parameters are: current 700A, voltage 70V, argon flow rate 30L / min, hydrogen flow rate 3L / min, powder feed rate 45g / min, vacuum chamber pressure 100kPa, and spraying distance 180mm.

[0083] ④ Laser beam irradiation: The surface of the C / ZrC-SiC ceramic matrix composite substrate with the coating formed in step ③ is scanned, melted and solidified using a laser beam irradiation process. During the scanning and melting process, an Nd:YAG laser with a wavelength of 1064nm is used to control the laser to scan the surface with a certain overlap rate, uniformly irradiating the entire coating surface. During the irradiation process, the laser power is 150W, the spot diameter is 1.1mm, the scanning speed is 10mm / s, the pulse width is 3ms, the frequency is 20Hz, and the overlap rate is 40%.

[0084] ⑤ Vacuum annealing: The coating surface after laser beam irradiation in step ④ is annealed in a vacuum environment (pressure 100 kPa) at a temperature of 1500℃ for 1.0 h and then naturally cooled to room temperature to obtain a ceramic coating on the C / ZrC-SiC ceramic matrix composite substrate.

[0085] The C / ZrC-SiC ceramic matrix composite material with ceramic coating prepared in this comparative example was tested. The tensile strength at 1800℃ was 127 MPa, the flexural strength at 1800℃ was 217 MPa, and the average linear ablation rate in the 2100℃ / 4000s oxyacetylene ablation test was 1.2 × 10⁻⁶. -3 mm / s.

[0086] Comparative Example 2

[0087] ① Powder preparation: ZrC powder, TaC powder, and SiC powder are mixed in a certain proportion to form a mixed powder (ceramic coating powder); wherein, the average particle size of ZrC powder is 500nm, the average particle size of TaC powder is 500nm, the average particle size of SiC powder is 500nm, and the volume ratio of ZrC powder, TaC powder, and SiC powder in the ceramic coating powder is 3.5:1.5:1.

[0088] ② Substrate surface treatment: Before spraying, use acetone to clean the surface of the ceramic matrix composite matrix (C / ZrC-SiC ceramic matrix composite matrix), and then sandblast the surface of the C / ZrC-SiC ceramic matrix composite matrix (substrate) (sand particle size 64 mesh, sandblasting pressure 0.5MPa). Use dry compressed air to clean the residual sand particles on the substrate surface.

[0089] ③ Plasma spraying: The ceramic coating powder obtained in step ① is sprayed onto the surface of the C / ZrC-SiC ceramic matrix composite substrate treated in step ② to form a coating (coating thickness 100μm). The low-pressure plasma spraying process parameters are: current 700A, voltage 70V, argon flow rate 30L / min, hydrogen flow rate 3L / min, powder feed rate 45g / min, vacuum chamber pressure 100kPa, and spraying distance 180mm.

[0090] ④ Vacuum annealing: The surface of the coating after plasma spraying in step ③ is annealed in a vacuum environment (pressure 100kPa) at a temperature of 1500℃ for 1.0h and then naturally cooled to room temperature to obtain a ceramic coating on the C / ZrC-SiC ceramic matrix composite substrate.

[0091] The C / ZrC-SiC ceramic matrix composite material with ceramic coating prepared in this comparative example was tested. The tensile strength at 1800℃ was 117 MPa, the flexural strength at 1800℃ was 205 MPa, and the average linear ablation rate in the 2100℃ / 4000s oxyacetylene ablation test was 2.1 × 10⁻⁶. -3 mm / s.

[0092] Comparative Example 3

[0093] ① Powder preparation: HfC powder and SiC powder are prepared into mixed powder (ceramic coating powder) in a certain proportion; wherein, the average particle size of HfC powder is 500nm, the average particle size of SiC powder is 500nm, and the volume ratio of HfC powder to SiC powder in the ceramic coating powder is 5:1.

[0094] ② Substrate surface treatment: Before spraying, use acetone to clean the surface of the ceramic matrix composite matrix (C / ZrC-SiC ceramic matrix composite matrix), and then sandblast the surface of the C / ZrC-SiC ceramic matrix composite matrix (substrate) (sand particle size 64 mesh, sandblasting pressure 0.5MPa). Use dry compressed air to clean the residual sand particles on the substrate surface.

[0095] ③ Plasma spraying: The ceramic coating powder obtained in step ① is sprayed onto the surface of the C / ZrC-SiC ceramic matrix composite substrate treated in step ② to form a coating (coating thickness 100μm). The low-pressure plasma spraying process parameters are: current 700A, voltage 70V, argon flow rate 30L / min, hydrogen flow rate 3L / min, powder feed rate 45g / min, vacuum chamber pressure 100kPa, and spraying distance 180mm.

[0096] ④ Laser beam irradiation: The surface of the C / ZrC-SiC ceramic matrix composite substrate with the coating formed in step ③ is scanned, melted and solidified using a laser beam irradiation process. During the scanning and melting process, an Nd:YAG laser with a wavelength of 1064nm is used to control the laser to scan the surface with a certain overlap rate, uniformly irradiating the entire coating surface. During the irradiation process, the laser power is 150W, the spot diameter is 1.1mm, the scanning speed is 10mm / s, the pulse width is 3ms, the frequency is 20Hz, and the overlap rate is 40%, thus obtaining a ceramic coating on the C / ZrC-SiC ceramic matrix composite substrate.

[0097] The C / ZrC-SiC ceramic matrix composite material with ceramic coating prepared in this comparative example was tested. The tensile strength at 1800℃ was 144 MPa, the flexural strength at 1800℃ was 231 MPa, and the average linear ablation rate in the 2100℃ / 4000s oxyacetylene ablation test was 8.7 × 10⁻⁶. -4 mm / s.

[0098] Comparative Example 4

[0099] ① Powder preparation: ZrC powder, HfC powder, TaC powder, and SiC powder are mixed in a certain proportion to form a mixed powder (ceramic coating powder); wherein, the average particle size of ZrC powder is 500nm, the average particle size of HfC powder is 500nm, the average particle size of TaC powder is 500nm, the average particle size of SiC powder is 500nm, and the volume ratio of ZrC powder, HfC powder, TaC powder, and SiC powder in the ceramic coating powder is 2:2.5:0.5:1.

[0100] ② Substrate surface treatment: The surface of the ceramic matrix composite matrix (C / ZrC-SiC ceramic matrix composite matrix) is etched using a laser to uniformly form multiple microgrooves on the surface of the ceramic matrix composite matrix. The cross-sectional profile of the microgrooves is V-shaped, the depth of the microgrooves is 6μm, and the spacing between two adjacent microgrooves is 15μm. Before spraying, the surface of the etched ceramic matrix composite matrix (C / ZrC-SiC ceramic matrix composite matrix) is cleaned with acetone, and the surface of the etched C / ZrC-SiC ceramic matrix composite matrix (substrate) is sandblasted (sand particle size 64 mesh, sandblasting pressure 0.5MPa). Dry compressed air is used to clean the residual sand particles on the surface of the substrate.

[0101] ③ Plasma spraying: The ceramic coating powder obtained in step ① is sprayed onto the surface of the C / ZrC-SiC ceramic matrix composite substrate treated in step ② to form a coating (coating thickness 100μm). The low-pressure plasma spraying process parameters are: current 700A, voltage 70V, argon flow rate 30L / min, hydrogen flow rate 3L / min, powder feed rate 45g / min, vacuum chamber pressure 100kPa, and spraying distance 180mm.

[0102] ④ Vacuum annealing: The surface of the coating after plasma spraying in step ③ is annealed in a vacuum environment (pressure 100kPa) at a temperature of 1500℃ for 1.0h and then naturally cooled to room temperature to obtain a ceramic coating on the C / ZrC-SiC ceramic matrix composite substrate.

[0103] The C / ZrC-SiC ceramic matrix composite material with ceramic coating prepared in this comparative example was tested. The tensile strength at 1800℃ was 106 MPa, the flexural strength at 1800℃ was 181 MPa, and the average linear ablation rate in the 2100℃ / 4000s oxyacetylene ablation test was 3.4 × 10⁻⁶ MPa. -3 mm / s.

[0104] Comparative Example 5

[0105] ① High-temperature treatment: C / ZrC-SiC ceramic matrix composite material was selected as the matrix material. Acetone was used to clean the surface of the ceramic matrix composite material matrix (C / ZrC-SiC ceramic matrix composite material matrix), and the surface of the C / ZrC-SiC ceramic matrix composite material matrix (substrate) was sandblasted (64-mesh abrasive, 0.5 MPa sandblasting pressure). Dry compressed air was used to remove residual abrasive particles from the substrate surface. Then, the substrate was placed in a cavity, and the cavity was evacuated until the pressure reached 5 × 10⁻⁶ MPa. -8 Torr, then H2 is introduced into the cavity until the pressure reaches 1×10 -3 Torr was used to treat C / ZrC-SiC ceramic matrix composites in a vacuum chamber at 1150℃ for 15 minutes in an H2 atmosphere to obtain high-temperature treated C / SiC ceramic matrix composites.

[0106] ② Pulsed laser deposition: Ultra-high temperature ceramic ZrC is used as the target material and transported to a designated position in the deposition chamber. Before pulsed laser deposition of the ZrC layer, C2H2 gas is introduced into the deposition chamber to create a vacuum environment at a pressure of 6 × 10⁻⁶. -3The process involves simultaneous pulsed laser deposition and high-temperature annealing to deposit a ZrC layer on the surface of the high-temperature treated C / ZrC-SiC ceramic matrix composite. Then, an ultra-high temperature ceramic (TaC) is used as the target and transported to a designated location in the deposition chamber. Before pulsed laser deposition of the TaC layer, C2H2 gas is introduced into the deposition chamber to create a vacuum environment at a pressure of 6 × 10⁻⁶. -3 Torr, then simultaneously pulsed laser deposition and high-temperature annealing, depositing a TaC layer on top of the ZrC layer; then using ultra-high temperature ceramic HfC as the target material, transported to the designated position in the deposition chamber, and before pulsed laser deposition of the HfC layer, C2H2 gas is introduced into the deposition chamber to a vacuum environment pressure of 6×10. -3 Torr, followed by simultaneous pulsed laser deposition and high-temperature annealing, depositing an HfC layer on top of the TaC layer, thereby obtaining an ultra-high temperature ceramic protective layer consisting of ZrC, TaC, and HfC layers sequentially on the surface of the high-temperature treated C / ZrC-SiC ceramic matrix composite material, resulting in a C / ZrC-SiC ceramic matrix composite material containing an ultra-high temperature ceramic protective layer; the parameters are the same during the pulsed laser deposition of the ZrC layer, TaC layer, and HfC layer, specifically: the output wavelength of the pulsed Nd:YAG laser is 355nm, and the laser energy density is 5J / cm². 2 The pulse width is 10 ns and the frequency is 10 Hz. The pulsed Nd:YAG laser is focused on the target surface at an incident angle of 45°. During deposition, the temperature of the high-temperature treated C / ZrC-SiC ceramic matrix composite material is raised to 1350°C. The distance between the target and the high-temperature treated C / ZrC-SiC ceramic matrix composite material is 60 mm. The rotation speed of the target and the high-temperature treated C / SiC ceramic matrix composite material is 30° / min. When preparing the ZrC layer, TaC layer and HfC layer, the laser pulse deposition temperature and high-temperature annealing time are both 1350°C and 3 h.

[0107] The C / ZrC-SiC ceramic matrix composite material with an ultra-high temperature ceramic protective layer prepared in this comparative example was tested. The tensile strength at 1800℃ was 96 MPa, the flexural strength at 1800℃ was 165 MPa, and the average linear ablation rate in the 2100℃ / 4000s oxyacetylene ablation test was 5.1 × 10⁻⁶. -3 mm / s.

[0108] In this invention, the performance test results of the materials finally obtained in each embodiment and each comparative example are shown in Table 1.

[0109] Table 1. Performance test results of the materials finally obtained in each embodiment and comparative example.

[0110]

[0111]

[0112] The parts of this invention not described in detail are techniques known to those skilled in the art.

[0113] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a ceramic coating for an ultra-high temperature ceramic matrix composite material, characterized in that, The method includes the following steps: (1) Cleaning and sandblasting the ceramic matrix composite material matrix; (2) A ceramic coating powder containing ultra-high temperature ceramic powder and silicon carbide powder is sprayed onto the surface of a cleaned and sandblasted ceramic matrix composite material substrate by plasma spraying process to form a coating; the ultra-high temperature ceramic powder is one or more of zirconium carbide powder, hafnium carbide powder, and tantalum carbide powder, and the particle size of zirconium carbide powder, hafnium carbide powder, and tantalum carbide powder is 200nm~1μm; the particle size of silicon carbide powder is 200nm~1μm; (3) The surface of the coated ceramic matrix is ​​scanned, melted and solidified by laser beam irradiation process, and then subjected to high temperature heat treatment in a vacuum environment to obtain an ultra-high temperature ceramic matrix composite ceramic coating on the ceramic matrix.

2. The preparation method according to claim 1, characterized in that: The ceramic matrix composite material matrix is ​​a C / ZrC-SiC ultra-high temperature ceramic matrix composite material matrix.

3. The preparation method according to claim 1, characterized in that: The volume ratio of the ultra-high temperature ceramic powder to the silicon carbide powder is (4~6):

1.

4. The preparation method according to claim 1, characterized in that: The plasma spraying process is a low-pressure plasma spraying process. The parameters for the low-pressure plasma spraying process are: current 650~750A, voltage 55~80V, argon flow rate 25~45L / min, hydrogen flow rate 2~4L / min, powder feed rate 35~60g / min, vacuum chamber pressure 100kPa, and spraying distance 150~200mm.

5. The preparation method according to claim 1, characterized in that: In the laser beam irradiation process, an Nd:YAG laser with a wavelength of 1064nm is used; During irradiation, the laser power is 100~200W, the spot diameter is 1.0~1.2mm, the scanning speed is 10~15mm / s, the pulse width is 2~4ms, the frequency is 15~30Hz, and the overlap rate is 30~50%.

6. The preparation method according to claim 1, characterized in that: High-temperature heat treatment under vacuum conditions with a pressure of 50~150 kPa; and / or The high-temperature heat treatment is performed at a temperature of 1300~1700℃ for a duration of 0.5~2.0h.

7. The preparation method according to claim 1, characterized in that: Before cleaning and sandblasting the ceramic matrix composite matrix, the surface of the ceramic matrix composite matrix is ​​first etched using a laser.

8. The preparation method according to claim 7, characterized in that: Laser etching is used to uniformly form multiple microgrooves on the surface of a ceramic matrix composite matrix. The cross-sectional profile of the microgrooves is V-shaped, the depth of the microgrooves is 5~10μm, and the spacing between two adjacent microgrooves is 10~20μm.

9. The preparation method according to claim 1, characterized in that: The ceramic coating powder also contains Yb2Si2O7 powder, and the volume fraction of Yb2Si2O7 powder in the ceramic coating powder is 5~10%.

10. The preparation method according to claim 9, characterized in that: The particle size of the Yb2Si2O7 powder is 200nm~1μm.

11. A ceramic coating for an ultra-high temperature ceramic matrix composite material, characterized in that: It is prepared by any one of the preparation methods according to claims 1 to 10.

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