A method of additive manufacturing of ultra-high temperature ceramic matrix composites

Abstract

The application belongs to the field of additive manufacturing, and specifically discloses an additive manufacturing method for ultrahigh-temperature ceramic matrix composites, which comprises the following steps: S1: a continuous fiber composite blank is prepared by using a continuous fiber additive manufacturing technology, and carbonization treatment is performed to obtain a carbonized preform ceramic; S2: ceramic post-treatment is performed on the carbonized preform ceramic to regulate the carbon density and form an interface layer on the surface of the continuous fibers in the carbonized preform ceramic; and S3: the carbonized preform ceramic after the ceramic post-treatment is infiltrated with zirconium metal and / or hafnium metal at high temperature to obtain an ultrahigh-temperature ceramic matrix composite. Through the design, the continuous fiber reinforced ceramic matrix composite can stably serve in an ultrahigh-temperature environment, and when a complex structure part is formed, cracking and volume shrinkage can be inhibited, toughness can be improved, complex structure forming and high densification can be realized.

Description

Technical Field

[0001] This application belongs to the field of additive manufacturing, and more specifically, relates to an additive manufacturing method for ultra-high temperature ceramic matrix composite materials. Background Technology

[0002] Ultra-high temperature ceramics, with their extreme heat resistance exceeding 2000℃, have become key structural materials for thermal protection systems in aerospace and hypersonic vehicles. However, most of the components used in these applications (such as wing leading edges and furnace tubes) are complex and irregularly shaped, making them difficult to fabricate using traditional powder metallurgy techniques. This has led to additive manufacturing technology demonstrating significant advantages in the fabrication of such components.

[0003] In related technologies, laser additive manufacturing is used to process zirconium diboride and Ta4HfC5 ultra-high temperature ceramics. However, due to the high melting point of ceramics, laser processing is difficult, and parts are prone to cracking. Currently, only simple experimental samples can be prepared, and it is impossible to obtain complex three-dimensional structural parts without cracks. Based on this, researchers have developed indirect additive manufacturing technologies. For example, using ink direct writing technology combined with pressureless sintering, porous structures of hafnium diboride and zirconium diboride lattice have been successfully prepared; alumina ceramics have been prepared using photopolymerization technology combined with pressureless sintering, and zirconium carbide and zirconium diboride ceramics with porous complex structures have been further prepared by introducing a boron / carbothermal reduction process. Although the above-mentioned indirect additive manufacturing technologies have achieved the forming of complex structures, the large volume shrinkage during sintering makes it easy to generate internal defects and cracks, making it difficult to meet the requirements of high density and high reliability.

[0004] To address the aforementioned issues, methane gas has been introduced into the laser forming and high-temperature sintering processes of ultra-high temperature ceramics, effectively improving the volume shrinkage and stress problems in additive manufacturing of ultra-high temperature ceramics. However, the low toughness of ultra-high temperature ceramics remains unresolved. Therefore, short-cut silicon carbide fibers have been used in ink direct writing technology to improve the toughness of zirconium diboride ultra-high temperature ceramics. However, the toughening effect of short fibers is limited, and the improvement in fracture toughness still cannot meet the requirements of extreme working conditions.

[0005] Continuous fibers offer superior toughening compared to chopped fibers. Existing technologies have proposed methods for preparing continuous fiber-reinforced ceramic matrix composites using direct ink writing technology. This approach enhances the fracture toughness of the material by increasing the continuous fiber content and controls production costs. However, it cannot meet the heat resistance requirements of materials in ultra-high temperature environments (>2000℃). Summary of the Invention

[0006] To address the shortcomings of existing technologies, this application provides an additive manufacturing method for ultra-high temperature ceramic matrix composites, aiming to solve the problems that existing continuous fiber reinforced ceramic matrix composites cannot be stably used in ultra-high temperature environments, and that existing ultra-high temperature ceramic additive manufacturing technologies are prone to cracking, large volume shrinkage, and insufficient toughness when forming complex structures.

[0007] This application provides an additive manufacturing method for ultra-high temperature ceramic matrix composite materials, which specifically includes the following steps: S1: Continuous fiber composite material preforms are prepared using continuous fiber additive manufacturing technology and then carbonized to obtain carbonized preform ceramics; S2: Perform ceramic post-treatment on the carbonized preform ceramic to regulate its carbon density and form an interface layer on the surface of the continuous fibers in the carbonized preform ceramic. S3: The carbonized preform ceramic that has undergone ceramic post-treatment is infiltrated with zirconium metal and / or hafnium metal at high temperature to obtain an ultra-high temperature ceramic matrix composite material.

[0008] Compared with the prior art, the above-conceptual technical solution conceived in this application uses continuous fiber additive manufacturing technology to construct the preform. After carbonization treatment, the preform forms a stable carbon skeleton for ultra-high temperature ceramics. The carbon density is then controlled through ceramic post-processing, and an interface layer is formed on the surface of the continuous fibers to protect them. Finally, zirconium metal and / or hafnium metal are infiltrated and reacted in situ to generate an ultra-high temperature ceramic phase. This enables the continuous fiber reinforced ceramic matrix composite material to serve stably in ultra-high temperature environments. Furthermore, when forming complex structural parts, it can suppress cracking and volume shrinkage, improve toughness, and achieve complex structural forming and high density.

[0009] As a further preferred embodiment, the continuous fiber additive manufacturing technology adopts any one of the following: continuous fiber ink direct writing technology, continuous fiber composite filament fused deposition modeling technology, or continuous fiber composite filament laser additive manufacturing technology.

[0010] As a further preferred embodiment, the volume fraction of continuous fibers in the continuous fiber composite preform is 20%-50%.

[0011] As a further preferred embodiment, the continuous fiber is high-purity carbon fiber with a purity of not less than 98.5%.

[0012] As a further preferred embodiment, the continuous fibers are coated with a resin, which is a thermosetting resin or a thermoplastic resin.

[0013] As a further preferred embodiment, when the continuous fibers are coated with thermoplastic resin, the continuous fiber composite preform is subjected to a shaping treatment before carbonization.

[0014] As a further preferred embodiment, the method for shaping the continuous fiber composite material preform is as follows: a thermosetting resin layer is coated on the outside of the continuous fiber composite material preform, and the continuous fiber composite material preform is carbonized after the thermosetting resin layer is cured.

[0015] As a further preferred embodiment, in step S2, the ceramic post-treatment includes precursor impregnation pyrolysis and chemical vapor infiltration. Precursor impregnation pyrolysis is used to control the carbon density of the carbonized preform ceramic, and chemical vapor infiltration is used to form an interface layer on the surface of the continuous fibers in the carbonized preform ceramic.

[0016] As a further preferred embodiment, in step S3, the method for infiltrating zirconium metal and / or hafnium metal into the carbide preform ceramic is as follows: the carbide preform ceramic that has undergone ceramic post-treatment is embedded in one or more of pure zirconium powder, pure hafnium powder, zirconium-hafnium alloy powder, silicon-hafnium alloy powder, or silicon-zirconium alloy powder, and heated to 1800℃~2200℃ under a protective atmosphere to infiltrate zirconium metal and / or hafnium metal into the carbide preform ceramic.

[0017] As a further preferred embodiment, the infiltration of zirconium metal and / or hafnium metal into the carbide preform ceramic is carried out in an atmosphere furnace. The atmosphere furnace is first evacuated, and then high-purity argon gas is introduced to atmospheric pressure. The evacuation and argon gas introduction steps are repeated at least twice.

[0018] The ultra-high temperature ceramic matrix composite material provided in this application is prepared by the above method.

[0019] In summary, compared with the prior art, the technical solutions conceived in this application have the following main technical advantages: 1. The ultra-high temperature ceramic matrix composite material prepared by the additive manufacturing method of this application has a stable carbon skeleton, and the carbon density is controlled by ceramic post-treatment. An interface layer is formed on the fiber surface, and zirconium metal and / or hafnium metal are infiltrated and reacted in situ to generate an ultra-high temperature ceramic phase. It can achieve the beneficial effects of ultra-high temperature service, suppression of cracking and volume shrinkage, improvement of toughness, realization of complex structure forming and high density.

[0020] 2. In this application, when the resin coating of the continuous fiber is a thermoplastic resin, effective shaping can be achieved by coating the continuous fiber composite preform with a thermosetting resin layer and then performing carbonization treatment, thus preventing preform deformation.

[0021] 3. In this application, a post-processed carbonized preform ceramic is embedded in one or more of pure zirconium powder, pure hafnium powder, zirconium-hafnium alloy powder, silicon-hafnium alloy powder, or silicon-zirconium alloy powder. The preform is heated at high temperature under a protective atmosphere. Before infiltration, the atmosphere furnace is evacuated and then purged with high-purity argon gas to atmospheric pressure. This operation is repeated at least twice. This ensures that zirconium metal and / or hafnium metal are efficiently and uniformly infiltrated into the carbonized preform ceramic, promoting in-situ reaction to generate the required ultra-high temperature ceramic phase. Attached Figure Description

[0022] Figure 1 This is a flowchart of the method provided in the embodiments of this application; Figure 2 This is an elemental distribution diagram of the interface of the ultra-high temperature ceramic matrix composite material prepared by the additive manufacturing method of this application. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0024] In traditional ultra-high temperature ceramic materials, the significant difference in thermal expansion coefficients between the matrix and the reinforcing phase (or between different components) leads to thermal mismatch, resulting in enormous thermal stress within the material. This thermal stress cannot be effectively released through mechanisms such as plastic deformation and tends to concentrate highly at inherent defects such as micropores and inclusions within the material, thereby inducing microcracks. Under thermal shock or rapid heating and cooling environments, these microcracks will rapidly, unstablely, and propagate through the material, ultimately leading to brittle fracture or even disintegration of the entire material. Therefore, traditional ultra-high temperature ceramics have almost no buffering capacity against thermal shock.

[0025] This application discloses an additive manufacturing method for ultra-high temperature ceramic matrix composites. A preform is constructed using continuous fiber additive manufacturing technology, followed by carbonization to form a stable carbon skeleton for ultra-high temperature ceramics. The carbon density is then controlled through ceramic post-treatment, and an interface layer is formed on the surface of the continuous fibers to protect them. Finally, zirconium and / or hafnium metals are infiltrated, reacting in situ to generate an ultra-high temperature ceramic phase. This method enables the rapid preparation of complex ultra-high temperature ceramic materials, which possess excellent resistance to extreme thermal shock, high-temperature oxidation resistance, and corrosion resistance. Furthermore, this method significantly improves the upper temperature limit and high-temperature mechanical properties of continuous fiber reinforced ceramic matrix composites, thereby overcoming the technical defects of existing additive manufacturing technologies, such as low fracture toughness, weak thermal shock resistance, and poor high-temperature mechanical properties in ultra-high temperature ceramics. When thermal shock-induced cracks propagate to the fiber / matrix interface of the component in this application, energy dissipation mechanisms such as interface debonding, fiber bridging, and fiber pull-out are triggered. These behaviors can consume a large amount of crack propagation energy, forcibly preventing crack penetration into the matrix, thereby effectively suppressing thermal shock damage at the mechanistic level.

[0026] Reference Figure 1 The additive manufacturing method for ultra-high temperature ceramic matrix composite materials disclosed in this application includes the following steps: S1: This application employs continuous fiber additive manufacturing technology to prepare continuous fiber composite material preforms, which are then carbonized to obtain carbonized preform ceramics. The continuous fiber additive manufacturing technology utilizes any one of the following: continuous fiber ink direct writing technology, continuous fiber composite filament fused deposition modeling technology, or continuous fiber composite filament laser additive manufacturing technology. These technologies are commonly used in additive manufacturing. Continuous fiber ink direct writing technology is suitable for the preparation of small-sized precision parts, while continuous fiber composite filament fused deposition modeling technology and continuous fiber composite filament laser additive manufacturing technology are suitable for the preparation of medium to large-sized structural parts. The appropriate technology can be selected based on actual needs, and will not be specifically described here. The volume fraction of continuous fibers in the continuous fiber composite material preform is 20%-50% to balance the structural strength of the preform with the fiber content of the final part, thereby achieving excellent resistance to extreme thermal shock. The continuous fiber is high-purity carbon fiber with a purity of not less than 98.5%. This high purity carbon fiber improves the fracture toughness of the ultra-high temperature ceramic, achieving a fracture toughness higher than 10 MPa·m. 1 / 2 It is far superior to the fracture toughness of traditional ultra-high temperature ceramics by 4 MPa·m. 1 / 2 Carbonization converts the polymer in the continuous fiber composite preform into pyrolytic carbon, thereby facilitating the stability of the preform shape in subsequent processing.

[0027] When continuous fibers are formed, they need to be coated with resin. The resin's forming properties allow the continuous fibers to solidify into a specific shape. Therefore, the continuous fiber composite preform contains a resin matrix. In practice, the resin can be a thermosetting resin or a thermoplastic resin. When the resin is a thermosetting resin, the continuous fiber composite preform can be directly placed in an atmosphere furnace for high-temperature carbonization. When the resin is a thermoplastic resin, because thermoplastic resins soften and flow at high temperatures, the continuous fiber composite preform needs to be shaped before carbonization. In this embodiment, the method for shaped treatment of the continuous fiber composite preform is as follows: first, a layer of thermosetting resin is coated on the outside of the continuous fiber composite preform to constrain the shape of the preform and prevent deformation during high-temperature heat treatment, ensuring the stability of the shape during high-temperature heat treatment. After the thermosetting resin layer on the outside of the continuous fiber composite preform has cured, it is then carbonized, i.e., placed in an atmosphere furnace for burial. During burial, the thermosetting resin layer volatilizes and does not affect the continuous fiber composite preform.

[0028] S2: Post-treatment of the carbide preform ceramic aims to control its carbon density and form an interface layer on the surface of the continuous fibers in the carbide preform ceramic. Preferably, the carbon density of the carbide preform ceramic is controlled to 0.8 g / cm³. 3 -0.9g / cm 3 To ensure that the strength of the processed sample is moderate, if the carbon density is too low, the toughness of the processed sample will be low after high-temperature metal infiltration; if the carbon density is too high, the strength of the processed sample will be low after high-temperature metal infiltration. The ceramic post-treatment includes precursor impregnation pyrolysis and chemical vapor infiltration. Precursor impregnation pyrolysis is used to control the carbon density of the carbide preform ceramic, and chemical vapor infiltration is used to form an interface layer on the surface of the continuous fibers in the carbide preform ceramic. Precursor impregnation pyrolysis and chemical vapor infiltration are both commonly used techniques in this field and will not be specifically described here. After ceramic post-treatment, the surface of the carbide preform ceramic forms a porous structure to facilitate subsequent infiltration of zirconium metal and / or hafnium metal. In this embodiment, the carbide preform ceramic undergoes chemical vapor infiltration to form an interface layer on the surface of the continuous fibers, which effectively protects the continuous fibers. In this application, the difference between the mass of the ceramic in the post-treated carbide preform ceramic and the mass of the continuous fibers in step S1 is the carbon mass in the carbide preform ceramic. The carbon mass consists of two parts: one part comes from the pyrolytic carbon mass formed by carbonization of the continuous fiber composite material preform in step S1, and the other part comes from the carbon-adding mass during the ceramic post-processing in step S2.

[0029] S3: A high-temperature ceramic matrix composite material is prepared by infiltrating zirconium and / or hafnium metal into a post-ceramic treated carbonized preform ceramic at high temperature. In practical applications, titanium and other metals can also be infiltrated as needed. The method for infiltrating zirconium and / or hafnium metal into the carbonized preform ceramic is as follows: The post-ceramic treated carbonized preform ceramic is embedded in one or more of pure zirconium powder, pure hafnium powder, zirconium-hafnium alloy powder, silicon-hafnium alloy powder, or silicon-zirconium alloy powder. The mixture is heated to 1800℃~2200℃ under a protective atmosphere to allow the zirconium and / or hafnium metal to infiltrate into the carbonized preform ceramic. The infiltration of zirconium and / or hafnium metal into the carbonized preform ceramic is carried out in an atmosphere furnace. First, the atmosphere furnace is evacuated, then high-purity argon gas is introduced to atmospheric pressure. This evacuation and argon introduction process is repeated at least twice. In this application, since one carbon atom reacts with one hafnium atom or one zirconium atom, the required mass of zirconium metal and / or hafnium metal to be incorporated can be calculated based on the molar mass ratio. Therefore, it is necessary to ensure that the metal powder used for embedding provides sufficient zirconium and / or hafnium to meet the stoichiometric ratio requirement. Figure 2 As shown, this figure is an elemental distribution diagram of the interface of an ultra-high temperature ceramic matrix composite material component prepared using the additive manufacturing method of this application. The figure shows that continuous fibers are arranged in the carbon element distribution area, thereby improving the density and strength of the material.

[0030] The ultra-high temperature ceramic prepared by the additive manufacturing method of the ultra-high temperature ceramic matrix composite material of this application can have an service temperature of over 2000℃ in an oxygen-containing environment, which is significantly better than the oxygen-containing service temperature of 1200℃ of traditional high temperature ceramics. This shows that the method of this application effectively improves the ultra-high temperature service performance of the material.

[0031] The method of this application will be described below through specific embodiments: Example 1: In this embodiment, high-purity carbon fiber with a purity of not less than 98.5% is used as the continuous fiber, which is externally coated with thermoplastic resins such as polylactic acid (PLA) and PETG to prepare a continuous fiber composite filament. The preform is formed using either fused deposition modeling (FDM) or laser additive manufacturing (LAD) technology for continuous fiber composite filaments. By adjusting the process parameters, the volume fraction of continuous fibers in the formed continuous fiber composite preform is controlled within the range of 20% to 50% to ensure sufficient structural strength of the preform while ensuring that the fiber content in the final part meets the requirements for thermal shock resistance.

[0032] The formed continuous fiber composite preform was subjected to carbonization treatment. First, the preform was vacuum impregnated in a phenolic resin solution, then removed and cured in an oven at 150°C for 2 hours, forming a thermosetting resin coating layer on the outer surface of the preform to maintain its shape stability during high-temperature treatment. Subsequently, the cured preform was embedded with SiC powder with a particle size of 50~90 μm, placed in an atmosphere furnace with a protective atmosphere, and heated to 1000°C at a heating rate of 5°C / min, and held at that temperature for 2 hours for carbonization treatment. During carbonization, the polymer matrix inside the preform and the phenolic resin layer on the outside are converted into pyrolytic carbon, resulting in a carbonized preform ceramic.

[0033] The aforementioned carbonized preform ceramic underwent ceramic post-treatment. A SiC interface layer was deposited on the surface of the continuous fibers using chemical vapor deposition (CVD). This interface layer can induce toughening mechanisms such as interface debonding, fiber bridging, and fiber pull-out during subsequent thermal shock, effectively protecting the continuous fibers. Simultaneously, in this embodiment, precursor impregnation pyrolysis technology was used to control the carbon density of the carbonized preform ceramic. Specifically, phenolic resin was dissolved in anhydrous ethanol to prepare an impregnation solution with a mass fraction of 50-60 wt.%, and 2-5 wt.% of a curing accelerator was added. The carbonized preform ceramic was placed in a vacuum chamber, and after evacuating to below 1 kPa and maintaining the vacuum for 30-60 minutes, the impregnation solution was injected. Subsequently, a nitrogen pressure of 0.3-0.6 MPa was applied and maintained for 2-4 hours to promote the resin's full penetration into the pores. After removing the preform, it was cured in stages at 80℃ / 2h, 120℃ / 2h, and 150℃ / 2h, with the heating rate controlled at 1℃ / min. Within n, after curing, the temperature is raised to 600℃ at 2℃ / min and held for 1 hour under nitrogen protection, and then raised to 1000℃ at 5℃ / min and held for 2 hours for pyrolysis. After each pyrolysis, the carbon density increases by about 0.10~0.15g / cm³. After 2~3 impregnation-pyrolysis cycles, the carbon density of the carbonized preform ceramic is precisely controlled at 0.8g / cm³, while maintaining an open porosity of 35~45 vol.%, providing a matrix with both certain strength and good melt permeability for subsequent high-temperature metal infiltration.

[0034] The carbonized preform ceramic, after ceramic post-treatment, undergoes high-temperature metal infiltration. Specifically, the carbonized preform ceramic is embedded in silicon-hafnium alloy powder and placed in an atmosphere furnace. The atmosphere furnace is first evacuated, then high-purity argon gas is introduced to atmospheric pressure. This evacuation-argon gas introduction process is repeated at least twice to completely remove residual oxygen from the furnace. Subsequently, the atmosphere furnace is heated to 1800℃~2200℃ under a protective atmosphere and held for 2~4 hours, allowing hafnium and silicon elements to infiltrate into the interior of the carbonized preform ceramic, ultimately yielding an ultra-high temperature ceramic matrix composite material.

[0035] Testing showed that the fracture toughness of the ultra-high temperature ceramic matrix composite material prepared in this embodiment is higher than 10 MPa·m. 1 / 2It is far higher than that of traditional ultra-high temperature ceramics by about 4 MPa·m 1 / 2 It exhibits superior fracture toughness; its service temperature in an oxygen-rich environment exceeds 2000℃, while that of traditional high-temperature ceramics is only 1200℃; at the same time, this material has excellent thermal shock resistance. When thermal shock-induced cracks propagate to the fiber / matrix interface, a large amount of crack propagation energy is dissipated through interface debonding, fiber bridging, and fiber pull-out, forcibly preventing cracks from penetrating the matrix, thus inhibiting thermal shock damage from a mechanistic perspective.

[0036] Example 2: In this embodiment, high-purity carbon fiber is used as raw material, epoxy resin system ink is used as binder, and additive manufacturing of the preform is carried out by continuous fiber ink direct writing technology. By adjusting the process parameters, the volume fraction of continuous fibers in the continuous fiber preform is controlled within the range of 20% to 50% to ensure that the preform has sufficient structural strength, while ensuring that the fiber content in the final part meets the requirements for thermal shock resistance.

[0037] The formed continuous fiber composite preform was placed in an oven and cured at 150°C for 2 hours to allow the epoxy resin ink to fully crosslink and cure. Subsequently, the cured preform was embedded with Al₂O₃ powder with a particle size of 50–90 μm and placed in a furnace with a protective atmosphere for carbonization treatment. The preform was heated to 1000°C at a heating rate of 5°C / min and held at that temperature for 2 hours. During carbonization, the epoxy resin binder inside the preform was converted into pyrolytic carbon, yielding a carbonized preform ceramic.

[0038] The aforementioned carbonized preform ceramic underwent post-treatment. A BN interface layer was deposited on the surface of the continuous fibers using chemical vapor deposition (CVD). This interface layer induces toughening mechanisms such as interface debonding, fiber bridging, and fiber pull-out during subsequent thermal shock, effectively protecting the continuous fibers. Simultaneously, a precursor impregnation-pyrolysis technique was employed, and through multiple impregnation-pyrolysis cycles, the carbon density of the carbonized preform ceramic was adjusted to 0.9 g / cm³. 3 This provides suitable matrix conditions for subsequent high-temperature metal infiltration.

[0039] The carbonized preform ceramic, after ceramic post-treatment, undergoes high-temperature metal infiltration. Specifically, the carbonized preform ceramic is embedded in silicon-zirconium alloy powder and placed in an atmosphere furnace. The atmosphere furnace is first evacuated, then high-purity argon gas is introduced to atmospheric pressure. This evacuation-argon gas introduction process is repeated at least twice to completely remove residual oxygen from the furnace. Subsequently, the atmosphere furnace is heated to 1800℃~2200℃ under a protective atmosphere and held for 2~4 hours, allowing zirconium and silicon elements to infiltrate into the interior of the carbonized preform ceramic, ultimately yielding an ultra-high temperature ceramic matrix composite material.

[0040] Similarly, tests showed that the fracture toughness of the ultra-high temperature ceramic matrix composite material prepared in this embodiment is higher than 10 MPa·m.1 / 2 It is far higher than that of traditional ultra-high temperature ceramics by about 4 MPa·m 1 / 2 It exhibits superior fracture toughness; its service temperature in an oxygen-rich environment exceeds 2000℃, while that of traditional high-temperature ceramics is only 1200℃; at the same time, this material has excellent thermal shock resistance. When thermal shock-induced cracks propagate to the fiber / matrix interface, a large amount of crack propagation energy is dissipated through interface debonding, fiber bridging, and fiber pull-out, forcibly preventing cracks from penetrating the matrix, thus inhibiting thermal shock damage from a mechanistic perspective.

[0041] It should be understood that expressions such as "comprising" and "may include" as used in this application indicate the existence of the disclosed functions, operations, or constituent elements, and do not limit one or more additional functions, operations, and constituent elements. In this application, terms such as "comprising" and / or "having" may be interpreted as indicating a specific characteristic, number, operation, constituent element, component, or combination thereof, but should not be interpreted as excluding the existence or possibility of adding one or more other characteristics, numbers, operations, constituent elements, components, or combinations thereof.

[0042] It should be understood that the terms “center,” “upper,” “lower,” “front,” “rear,” “left,” “right,” “vertical,” “horizontal,” “inner,” “outer,” “clockwise,” “counterclockwise,” “axial,” “radial,” and “circumferential” indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this application.

[0043] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this application, "multiple" means two or more, unless otherwise explicitly specified.

[0044] In this application, unless otherwise expressly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection between two components. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0045] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. An additive manufacturing method for ultra-high temperature ceramic matrix composite materials, characterized in that, Includes the following steps: S1: Continuous fiber composite material preforms are prepared using continuous fiber additive manufacturing technology and then carbonized to obtain carbonized preform ceramics; S2: Perform ceramic post-treatment on the carbonized preform ceramic to regulate its carbon density and form an interface layer on the surface of the continuous fibers in the carbonized preform ceramic. S3: The carbonized preform ceramic that has undergone ceramic post-treatment is infiltrated with zirconium metal and / or hafnium metal at high temperature to obtain an ultra-high temperature ceramic matrix composite material.

2. The additive manufacturing method for an ultra-high temperature ceramic matrix composite material as described in claim 1, characterized in that, The continuous fiber additive manufacturing technology adopts any one of the following: continuous fiber ink direct writing technology, continuous fiber composite filament fused deposition modeling technology, or continuous fiber composite filament laser additive manufacturing technology.

3. The additive manufacturing method for an ultra-high temperature ceramic matrix composite material as described in claim 1, characterized in that, The volume fraction of continuous fibers in the continuous fiber composite preform is 20%-50%.

4. The additive manufacturing method for an ultra-high temperature ceramic matrix composite material as described in claim 3, characterized in that, The continuous fiber is high-purity carbon fiber with a purity of not less than 98.5%.

5. The additive manufacturing method for an ultra-high temperature ceramic matrix composite material as described in claim 3, characterized in that, The continuous fibers are coated with resin, which is a thermosetting resin or a thermoplastic resin.

6. The additive manufacturing method for an ultra-high temperature ceramic matrix composite material as described in claim 5, characterized in that, When the continuous fibers are coated with thermoplastic resin, the continuous fiber composite preform is subjected to a shaping treatment before carbonization.

7. The additive manufacturing method for an ultra-high temperature ceramic matrix composite material as described in claim 6, characterized in that, The method for shaping the continuous fiber composite material preform is as follows: a thermosetting resin layer is coated on the outside of the continuous fiber composite material preform, and the continuous fiber composite material preform is carbonized after the thermosetting resin layer is cured.

8. The additive manufacturing method for an ultra-high temperature ceramic matrix composite material as described in claim 1, characterized in that, In step S2, the ceramic post-treatment includes precursor impregnation pyrolysis and chemical vapor infiltration. Precursor impregnation pyrolysis is used to control the carbon density of the carbonized preform ceramic, and chemical vapor infiltration is used to form an interface layer on the surface of the continuous fibers in the carbonized preform ceramic.

9. The additive manufacturing method for an ultra-high temperature ceramic matrix composite material as described in claim 1, characterized in that, In step S3, the method for infiltrating zirconium metal and / or hafnium metal into the carbide preform ceramic is as follows: the carbide preform ceramic that has undergone ceramic post-treatment is embedded in one or more of pure zirconium powder, pure hafnium powder, zirconium-hafnium alloy powder, silicon-hafnium alloy powder, or silicon-zirconium alloy powder, and heated to 1800℃~2200℃ under a protective atmosphere to infiltrate zirconium metal and / or hafnium metal into the carbide preform ceramic.

10. The additive manufacturing method for an ultra-high temperature ceramic matrix composite material as described in claim 9, characterized in that, The infiltration of zirconium metal and / or hafnium metal into the carbide preform ceramic is carried out in an atmosphere furnace. First, the atmosphere furnace is evacuated, and then high-purity argon gas is introduced to atmospheric pressure. The evacuation and argon gas introduction steps are repeated at least twice.

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