A preparation method for improving photocuring forming performance and high-temperature performance of carbide composite ceramic material

Abstract

The application belongs to the technical field of carbide and composite ceramic additive manufacturing, and particularly relates to a preparation method for improving the photocuring forming performance and high-temperature performance of a carbide composite ceramic material. In the application, refractory metal is deposited on the surface layer of carbide powder to improve the solidification performance of the carbide ceramic material, and then the carbide composite ceramic with enhanced high-temperature performance is obtained through photocuring additive and densification heat treatment. Compared with the photocuring performance and high-temperature performance of the ceramic slurry prepared by directly using carbide material, the refractory metal modified layer prepared by the application is uniformly deposited on the surface layer of the carbide, which can effectively improve the solidification depth of the ceramic slurry, and cooperate with high-temperature pyrolysis and in-situ reaction sintering, so that the high-temperature reinforcing phase is uniformly distributed in the ceramic matrix, and the density and high-temperature performance of the carbide composite ceramic are improved.

Description

Technical Field

[0001] This invention belongs to the field of additive manufacturing technology of high-temperature carbides and their composite ceramics, specifically relating to a preparation method for improving the photocuring forming performance and high-temperature performance of carbide composite ceramic materials. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Carbide ceramics, due to their excellent high-temperature resistance, outstanding mechanical properties, and chemical stability, are widely used in harsh environments such as high temperature, high pressure, and corrosion in aerospace, nuclear engineering, and automotive manufacturing. To further improve the high-temperature resistance and oxidation resistance of carbide ceramics, they are often reinforced with reinforcing phase materials such as zirconium carbide, hafnium carbide, and titanium carbide. The doping of reinforcing phases greatly expands the development space and possibilities for the application of carbide ceramics in extreme environments.

[0004] Carbide ceramic components typically possess high strength, complex structures, and geometric shapes, making it difficult for traditional fabrication methods to meet the demands for high-precision, efficient, and environmentally friendly processing of complex structures. Photopolymerization additive manufacturing, through layer-by-layer stacking and curing, can achieve near-net-shape fabrication of complex structures, offering advantages such as fast curing speed, high forming accuracy, and minimal material waste, thus improving the efficiency and flexibility of carbide ceramic fabrication. However, the high refractive index of carbide ceramics and reinforcing phase materials significantly absorbs and scatters incident light during photopolymerization, affecting the curing performance and forming efficiency of the carbide ceramic preform.

[0005] In existing research on photopolymer additive manufacturing methods for carbide ceramics, patent CN202110176975.X proposes a method to improve the photopolymerization performance of silicon carbide ceramics by preparing a silicon oxide coating layer on the surface of silicon carbide through a high-temperature oxidation method. Subsequently, a carbon source resin is used to react and generate a secondary phase SiC. However, no high-temperature reinforcing phase material is introduced to improve the high-temperature resistance of the ceramic. Patent CN202110427400.0 proposes a method to improve the curing efficiency and overall performance of photopolymer 3D printed silicon carbide ceramics by coating modified silicon carbide particles with graphene. Its characteristic is that the graphene-coated modified silicon carbide particles are prepared by wet ball milling, neglecting the high-energy ball milling process. The uneven coating of graphene on the surface of the silicon carbide ceramic will affect the consistency and stability of photopolymerization performance and high-temperature resistance. Therefore, a practical method to improve the photosensitive properties, curing performance, and sintered ceramic performance of carbide ceramics urgently needs to be researched and proposed. Summary of the Invention

[0006] To address the problems of high refractive index, poor curing performance, and low density and properties of silicon carbide materials in photocuring additive manufacturing, this invention proposes a method for improving the photocuring forming performance and high-temperature performance of carbide composite ceramic materials. First, a refractory metal with a low refractive index and enhanced high-temperature resistance is deposited on the surface of carbide ceramic particles. This refractory metal modification layer improves the photosensitive properties of the carbide particles. The slurry prepared from the modified carbide ceramic particles achieves a greater curing depth during photocuring additive manufacturing. Then, through high-temperature pyrolysis and in-situ reaction sintering, a refractory metal carbide reinforcing phase is formed between the carbide grain boundaries, improving the material's density and high-temperature performance.

[0007] Specifically, the present invention is achieved through the following technical solution:

[0008] In a first aspect, the present invention provides surface-modified carbide ceramic particles for photocurable additive manufacturing, comprising: a carbide ceramic particle core and a surface modification layer;

[0009] The carbide ceramic particle material is selected from at least one of silicon carbide and boron carbide;

[0010] The surface modification layer material is selected from at least one of the refractory metal elements zirconium, hafnium, tantalum and titanium.

[0011] In a second aspect, the present invention provides a method for surface modification of high refractive index carbide ceramic powder, comprising: loading surface-pretreated ceramic powder into a fluidized bed chemical vapor deposition reactor, introducing a precursor compound of a refractory metal and reacting it together with a carrier gas to deposit a modified metal layer on the surface of the carbide ceramic particles.

[0012] In a third aspect, the present invention provides a method for photocuring additive manufacturing of carbide ceramics, comprising: mixing surface-modified carbide ceramic particles with photosensitive resin to prepare a ceramic slurry, performing photocuring additive manufacturing, and cleaning to obtain a carbide composite ceramic blank;

[0013] The photosensitive resin composition includes a prepolymer monomer premix, a photoinitiator, and a dispersant.

[0014] In a fourth aspect, the present invention provides a method for densification and heat treatment enhancement of photocurable additive-molded carbide composite ceramics, comprising: subjecting a carbide composite ceramic green body to high-temperature thermal degreasing; subjecting the degreased ceramic green body to high-temperature in-situ reaction sintering; and subjecting the surface modified metal material to in-situ reaction with organic pyrolysis carbon and the core of the carbide particles to obtain a refractory metal carbide reinforcing phase with enhanced high-temperature performance.

[0015] In a fifth aspect, the present invention provides a high-temperature resistant carbide composite ceramic prepared by photocuring additive manufacturing.

[0016] One or more embodiments of the present invention have the following beneficial effects:

[0017] 1) In this invention, carbide ceramic particles are loaded into a fluidized bed chemical vapor deposition reactor. The refractory metal precursor compound reacts with the gas carrier in the gas phase environment of the fluidized bed, and a refractory metal modified layer is deposited on the surface of the carbide ceramic particles. After cooling and sieving, the desired carbide ceramic particle material with a surface modified layer with a low refractive index is obtained. This can reduce the scattering and absorption of incident light by the carbide ceramic particles in the photocuring additive manufacturing stage, and improve the curing depth and molding accuracy of the carbide ceramic.

[0018] 2) The densification heat treatment enhancement method for carbide composite ceramics disclosed in this invention uses a two-stage heat treatment process of high-temperature thermal degreasing and high-temperature in-situ reaction sintering. The first step, high-temperature thermal degreasing, is used to decompose the organic components in the ceramic body and provide a carbon source. The second step, high-temperature in-situ reaction sintering, is used to promote the formation of the high-temperature resistant reinforcing phase of refractory metal carbides, thereby improving the density and high-temperature performance of the carbide composite ceramic material.

[0019] 3) This invention employs high-temperature reinforcing refractory metal elements to modify the surface of carbide ceramic particles, thereby improving the photocuring and high-temperature performance of carbide composite ceramic materials. Compared to existing surface modification methods, the deposition efficiency and uniformity of the metal-modified layer on the surface of carbide ceramic particles via fluidized bed chemical vapor deposition are higher. Furthermore, it enables highly efficient and customized preparation of single or composite metal-modified layers, offering strong scalability.

[0020] 4) The photocurable additive manufacturing method for carbide composite ceramics disclosed in this invention uniformly deposits refractory metals on the surface of carbide ceramic particles, which helps the high-temperature reinforcing phase in the sintered carbide composite ceramics to be uniformly distributed between ceramic grains, thereby improving the density and high-temperature performance of the carbide composite ceramics and further broadening the application prospects of photocurable additive manufacturing of carbide composite ceramics in high-temperature environments. Attached Figure Description

[0021] The accompanying drawings, which form part of this specification, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. Hereinafter, embodiments of the invention will be described in detail with reference to the accompanying drawings, wherein:

[0022] Figure 1 This is a flowchart of Embodiment 1 of the present invention, which describes the fabrication of a high-temperature performance-enhanced carbide composite ceramic material using photopolymer additive manufacturing.

[0023] Figure 2 This refers to the curing depth data under different exposure energies in the embodiments and comparative examples of this invention;

[0024] Figure 3 The data provided are the oxyacetylene ablation rate data for the embodiments and comparative examples of this invention. Detailed Implementation

[0025] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer.

[0026] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the exemplary embodiments according to this disclosure. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms “comprising” and / or “including” are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0027] To address the poor curing performance of high-refractive-index carbide ceramic materials during photocuring additive manufacturing and to enhance their density and high-temperature performance, this invention proposes a method for preparing carbide composite ceramic materials that improves their photocuring and high-temperature performance. First, a refractory metal with a low refractive index and enhanced high-temperature performance is deposited on the surface of carbide ceramic particles. This surface modification improves the photosensitivity of the carbide particles. The slurry prepared from the modified carbide ceramic particles achieves a greater curing depth during photocuring additive manufacturing. Then, through high-temperature thermal debinding and in-situ reaction sintering, a refractory metal carbide reinforcing phase is formed between the grain boundaries of the carbide matrix, thereby improving the material's density and high-temperature resistance.

[0028] Specifically, the present invention is achieved through the following technical solution:

[0029] In a first aspect, the present invention provides surface-modified carbide ceramic particles for photocurable additive manufacturing, comprising: a carbide ceramic particle core and a surface modification layer;

[0030] The surface modification layer material is selected from refractory metal elements that have high-temperature strengthening properties.

[0031] Depositing a refractory metal modification layer on the surface of high-refractive-index carbide ceramic particles using a surface modification method can reduce the scattering and absorption of incident light by the carbide particles, thereby improving the curing performance of the photocurable additive manufacturing process of carbide ceramics. Simultaneously, the refractory metal on the surface layer generates a refractory metal carbide reinforcing phase during high-temperature thermal debinding and high-temperature in-situ reaction sintering, which can enhance the high-temperature performance of the carbide ceramic material.

[0032] In one or more embodiments of the present invention, the carbide ceramic particle matrix is ​​selected from at least one of silicon carbide and boron carbide, preferably silicon carbide.

[0033] In one or more embodiments of the present invention, the metal coating is selected from at least one of the refractory metal elements zirconium, hafnium, tantalum and titanium, preferably zirconium.

[0034] The core of the carbide ceramic particles is preferably silicon carbide, and the surface modification layer is preferably refractory metal zirconium. Zirconium metal has the characteristics of low refractive index, good chemical compatibility with silicon carbide core, and high temperature reinforcing phase formed by reaction with carbon under high temperature conditions. It is suitable for improving the photocuring forming performance and high temperature performance of carbide composite ceramic materials.

[0035] In a second aspect, the present invention provides a method for surface modification of high refractive index carbide ceramic powder, comprising: loading surface-pretreated ceramic powder particles into a fluidized bed chemical vapor deposition reactor, introducing a precursor compound of a refractory metal and reacting it together with a carrier gas to deposit a modified metal layer on the surface of the carbide ceramic particles.

[0036] Fluidized bed chemical vapor deposition technology can be used to deposit a refractory metal modified layer with uniform composition and controllable thickness on the surface of carbide ceramic particles.

[0037] In this invention, the principle of refractory metal deposition on the surface of carbide ceramic particles is as follows: pretreated carbide ceramic particles are loaded into a fluidized bed reactor, and the precursor compound of the metal is introduced into the reactor along with the carrier gas. Under appropriate conditions, a chemical reaction occurs. The surface activity of the carbide ceramic particle surface makes it easy for the refractory metal precursor compound to be adsorbed and decomposed on its surface, generating metal atoms or metal compounds, which are then deposited to form a refractory metal modified coating.

[0038] In one or more embodiments of the present invention, the refractory metal precursor compound is selected from zirconium tetrachloride, hafnium tetrachloride, tantalum pentachloride, and titanium tetrachloride.

[0039] Preferably, the carrier gas is a mixture of hydrogen and argon;

[0040] This invention first pre-treats the surface of carbide ceramic particles, then transfers the dried and dispersed carbide ceramic particles into a reactor. Precursor compounds such as zirconium tetrachloride and hafnium tetrachloride are introduced into the fluidized bed reactor along with a carrier gas. Under certain deposition reaction temperature and reaction time conditions, a chemical reaction occurs, depositing a refractory metal modified layer with good photosensitive properties on the surface of the core of the carbide ceramic particles. After cooling and sieving, the surface-modified carbide ceramic particle material for photocurable additive manufacturing is obtained.

[0041] Preferably, the molar ratio of the refractory metal precursor compound to hydrogen is 1:1 to 1:6, more preferably 1:2;

[0042] Preferably, the hydrogen flow rate is 0.1-1 L / min, more preferably 0.2 L / min;

[0043] Preferably, the argon flow rate is 0.2-2 L / min, more preferably 0.4 L / min;

[0044] Preferably, the reaction temperature of the deposition process is 400-1200℃, and more preferably 800℃;

[0045] Preferably, the deposition process takes 10-60 min, more preferably 20 min;

[0046] For example, silicon carbide ceramic particles are used as the core material to be modified and loaded into a fluidized bed reactor. Zirconium tetrachloride is used as the precursor compound and a mixture of hydrogen and argon is used as the carrier gas. The hydrogen flow rate is 0.2 L / min and the argon flow rate is 0.4 L / min. The molar ratio of zirconium tetrachloride to hydrogen is 1:2. Zirconium tetrachloride and the carrier gas are deposited at a reaction temperature of 800℃ for 20 min, so that zirconium tetrachloride decomposes and deposits on the surface of silicon carbide particles to form a zirconium-modified layer. After cooling and sieving, zirconium-modified silicon carbide ceramic particle material is obtained.

[0047] In a third aspect, the present invention provides a method for photocuring additive manufacturing of carbide ceramics, comprising: mixing surface-modified carbide ceramic particles for photocuring additive manufacturing with photosensitive resin to prepare a composite ceramic slurry, performing photocuring additive manufacturing, and cleaning to obtain the final product.

[0048] In one or more embodiments of the present invention, the photosensitive resin component includes: prepolymer monomer premix, photoinitiator, and dispersant;

[0049] Preferably, the prepolymer monomer premix comprises a multifunctional prepolymer monomer and a bifunctional prepolymer monomer, wherein the volume ratio of the multifunctional prepolymer monomer to the bifunctional prepolymer monomer is 1:1 to 4:1.

[0050] Preferably, the multifunctional prepolymer monomer includes at least one of: bis(trimethylolpropane)acrylate, ethoxypentaerythritol tetraacrylate, and pentaerythritol tetraacrylate.

[0051] Preferably, the bifunctional prepolymer monomer is selected from at least one of 1,6-hexanediol diacrylate, diethylene glycol diacrylate, 1,4-butanediol acrylate, and tripropylene glycol diacrylate.

[0052] Preferably, the multifunctional prepolymer monomer is bis(trimethylolpropane) acrylate, the difunctional prepolymer monomer is 1,6-hexanediol diacrylate, and the volume ratio of the multifunctional prepolymer monomer to the difunctional monomer is 3:1.

[0053] Preferably, the photoinitiator is at least one selected from phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexylphenyl ketone, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and the amount of photoinitiator added is 1-4% of the mass of the premixed solution;

[0054] Preferably, the dispersant is selected from at least one of DisperBYK-111, DisperBYK-142, and DisperBYK-180, and the amount of dispersant added is 1-5% of the mass of the premix.

[0055] Preferably, the photoinitiator is phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and the amount of photoinitiator added is 2% of the mass of the premix; the dispersant is DisperBYK-111, and the amount of dispersant added is 2% of the mass of the premix.

[0056] In one or more embodiments of the present invention, the solid content of the carbide composite ceramic slurry is 30-60 vol%, preferably 45 vol%.

[0057] Preferably, the mixing method is planetary ball milling, with a ball milling speed of 300-1200 rad / min and a ball milling time of 2-10 h;

[0058] Preferably, the ball milling parameters are: ball milling speed 400 rad / min, ball milling time 3 h;

[0059] Preferably, the photopolymerization additive manufacturing parameters are: incident ultraviolet light wavelength 405 nm, incident light power 40-120 mW / cm². 2 Unconstrained exposure time: 5-40 s; Model slice thickness: 25 μm.

[0060] Preferably, the photopolymerization additive manufacturing parameters are: incident light power 80 mW / cm². 2 Unrestricted exposure time: 12 seconds;

[0061] Preferably, the ceramic body cleaning method is ultrasonic cleaning with anhydrous ethanol solution, and the cleaning time is 3-10 min, preferably 5 min.

[0062] The manufacturing method of carbide composite ceramics using photopolymerization additive manufacturing technology can obtain ceramic green bodies with high forming accuracy and good interfacial bonding. This method can fully leverage the performance advantages of photopolymerization technology in the additive manufacturing of complex-shaped carbide composite ceramic components for high-temperature applications. The combination of high-refractive-index multifunctional prepolymer monomers and low-viscosity bifunctional prepolymer monomers can reduce the refractive index difference between the photosensitive resin premix and the carbide ceramic powder, improving the curability and flowability of the ceramic slurry.

[0063] In a fourth aspect, the present invention provides a densification heat treatment method for photocurable additively formed carbide composite ceramics, comprising: subjecting the photocurable ceramic preform to high-temperature thermal degreasing and high-temperature in-situ reaction sintering.

[0064] In one or more embodiments of the present invention, the densification heat treatment adopts a two-stage heat treatment. The first stage is high-temperature thermal degreasing, with a degreasing temperature of 600-1200 ℃, a degreasing atmosphere of argon, and a time of 1-4 h. The second stage is high-temperature in-situ reaction sintering, with a sintering atmosphere of argon, a sintering temperature of 1600-2200 ℃, and a time of 2-10 h.

[0065] Preferably, the first stage of high-temperature thermal degreasing is performed at a temperature of 1000 ℃ for 2 hours.

[0066] Preferably, the second stage involves high-temperature in-situ reaction sintering at a temperature of 1800 °C for 6 h.

[0067] The purpose of the first stage, high-temperature thermal degreasing, is to cause the organic matter in the ceramic green body to undergo cracking and carbonization reactions under high-temperature inert gas atmosphere, providing a carbon source for the subsequent high-temperature sintering process, while also giving the ceramic green body a certain strength. The second stage, high-temperature in-situ reaction sintering, causes the refractory metal modified layer on the surface of the carbide ceramic particle core to undergo a phase transformation reaction with the carbon element and the silicon carbide core, forming a refractory metal carbide high-temperature reinforcing phase at the grain boundaries of the carbide ceramic particles, improving the density of the carbide composite ceramic and enhancing its high-temperature performance.

[0068] In a fifth aspect, the present invention provides a high-temperature resistant carbide composite ceramic prepared by a photocurable additive manufacturing method.

[0069] The present invention will be further described in detail below with reference to specific embodiments. It should be noted that the specific embodiments are explanations of the present invention and not limitations thereof.

[0070] Example 1

[0071] Using silicon carbide ceramic particles as the modified core material, they were loaded into a fluidized bed reactor. Zirconium tetrachloride was used as the precursor compound, and a mixture of hydrogen and argon was used as the carrier gas. The hydrogen flow rate was 0.2 L / min, the argon flow rate was 0.4 L / min, and the molar ratio of zirconium tetrachloride to hydrogen was 1:2. After the zirconium tetrachloride and the carrier gas were deposited at a reaction temperature of 800℃ for 20 min, the mixture was cooled and sieved through a 1000-mesh sieve to obtain zirconium-modified silicon carbide ceramic particle material for photopolymer additive manufacturing.

[0072] A ceramic slurry was prepared by mixing refractory metal-modified silicon carbide ceramic powder with photosensitive resin. The photosensitive resin consisted of a premix of bis(trimethylolpropane)acrylate and 1,6-hexanediol diacrylate prepolymer monomers in a volume ratio of 3:1, a photoinitiator of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide at 2% of the premix mass, and a dispersant of DisperBYK-111 at 2% of the premix mass. The ceramic slurry was prepared by planetary ball milling with a solid content of 45 vol%. The milling parameters were: milling speed 400 rad / min and milling time 3 h. After vacuum degassing, the modified silicon carbide ceramic slurry for photocurable additive manufacturing was obtained.

[0073] Photopolymerization additive manufacturing was performed using modified silicon carbide ceramic slurry. The photopolymerization additive manufacturing parameters were: ultraviolet light wavelength 405 nm, ceramic preform model slice thickness 25 μm, and incident light power 80 mW / cm². 2 The unconstrained exposure time was 12 s. The photocured ceramic blank was placed in anhydrous ethanol solution and ultrasonically cleaned for 5 min to obtain the silicon carbide composite ceramic blank.

[0074] The silicon carbide composite ceramic green body is first thermally degreased in an argon atmosphere at 1000℃ for 2 hours to allow the organic matter in the ceramic green body to decompose and carbonize. Then, it is sintered in an argon atmosphere at 1800℃ for 6 hours to allow the modified zirconium metal to undergo a phase transformation reaction to generate a zirconium carbide reinforcing phase, thereby enhancing the high-temperature performance of the ceramic and obtaining a dense carbide composite ceramic.

[0075] Figure 1 This is a flowchart illustrating the photocurable additive manufacturing process for improving the photocurable forming and high-temperature performance of carbide composite ceramic materials in this embodiment. Figure 2 and Figure 3 The data on the cured thickness of silicon carbide ceramics corresponding to Example 1 under different exposure energies and the data on the ablation rate of the oxyacetylene ablation test line for the high-temperature performance of the ceramics are shown respectively.

[0076] Example 2

[0077] Using silicon carbide ceramic particles as the modified core material, they were loaded into a fluidized bed reactor. Zirconium tetrachloride was used as the precursor compound, and a mixture of hydrogen and argon was used as the carrier gas. The hydrogen flow rate was 0.2 L / min, the argon flow rate was 0.4 L / min, and the molar ratio of zirconium tetrachloride to hydrogen was 1:2. After the zirconium tetrachloride and the carrier gas were deposited at a reaction temperature of 1000℃ for 40 min, the mixture was cooled and sieved through a 1000-mesh sieve to obtain zirconium-modified silicon carbide ceramic particle material for photopolymer additive manufacturing.

[0078] A ceramic slurry was prepared by mixing refractory metal-modified silicon carbide ceramic powder with photosensitive resin. The composition of the photosensitive resin was the same as in Example 1. The ceramic slurry was mixed by planetary ball milling. The solid content of the slurry was 45 vol%. The ball milling parameters were: ball milling speed 400 rad / min, ball milling time 3 h. After vacuum degassing treatment, the modified silicon carbide ceramic slurry for photocurable additive manufacturing was obtained.

[0079] Photopolymerization additive manufacturing was performed using modified silicon carbide ceramic slurry. The photopolymerization additive manufacturing parameters were: ultraviolet light wavelength 405 nm, ceramic preform model slice thickness 25 μm, and incident light power 80 mW / cm². 2 The unconstrained exposure time was 12 s. The photocured ceramic blank was placed in anhydrous ethanol solution and ultrasonically cleaned for 5 min to obtain the silicon carbide composite ceramic blank.

[0080] The silicon carbide composite ceramic preform was first thermally degreased in an argon atmosphere at 1000℃ for 2 hours, and then subjected to high-temperature in-situ reaction sintering in an argon atmosphere at 1800℃ for 6 hours to obtain dense carbide composite ceramic.

[0081] Example 3

[0082] Using silicon carbide ceramic particles as the modified core material, they were loaded into a fluidized bed reactor. Zirconium tetrachloride was used as the precursor compound, and a mixture of hydrogen and argon was used as the carrier gas. The hydrogen flow rate was 0.2 L / min, the argon flow rate was 0.4 L / min, and the molar ratio of zirconium tetrachloride to hydrogen was 1:2. After the zirconium tetrachloride and the carrier gas were deposited at a reaction temperature of 800℃ for 20 min, the mixture was cooled and sieved through a 1000-mesh sieve to obtain zirconium-modified silicon carbide ceramic particle material for photopolymer additive manufacturing.

[0083] A ceramic slurry was prepared by mixing refractory metal-modified silicon carbide ceramic powder with photosensitive resin. The composition of the photosensitive resin was the same as in Example 1. The ceramic slurry was mixed by planetary ball milling. The solid content of the slurry was 45 vol%. The ball milling parameters were: ball milling speed 400 rad / min, ball milling time 3 h. After vacuum degassing treatment, the modified silicon carbide ceramic slurry for photocurable additive manufacturing was obtained.

[0084] Photopolymerization additive manufacturing was performed using modified silicon carbide ceramic slurry. The photopolymerization additive manufacturing parameters were: ultraviolet light wavelength 405 nm, ceramic preform model slice thickness 25 μm, and incident light power 80 mW / cm². 2 The unconstrained exposure time was 12 s. The photocured ceramic blank was placed in anhydrous ethanol solution and ultrasonically cleaned for 5 min to obtain the silicon carbide composite ceramic blank.

[0085] The silicon carbide composite ceramic preform was first thermally degreased in an argon atmosphere at 1200℃ for 2 hours, and then subjected to high-temperature in-situ reaction sintering in an argon atmosphere at 2000℃ for 6 hours to obtain dense carbide composite ceramic.

[0086] Comparative Example 1

[0087] A ceramic slurry was prepared by mixing silicon carbide ceramic particles with photosensitive resin. The composition of the photosensitive resin was the same as in Example 1, and the other parameters were the same as in Example 1.

[0088] Compared with Example 1, the difference is that silicon carbide powder and photosensitive resin premix were directly used to prepare the slurry and then the ceramic was prepared.

[0089] Comparative Example 2

[0090] A ceramic slurry was prepared by mixing silicon carbide ceramic powder, zirconium carbide reinforcing phase material and photosensitive resin. The composition of the photosensitive resin was the same as in Example 1, the amount of zirconium carbide added was 3% of the mass of silicon carbide powder, and the other parameters were the same as in Example 1.

[0091] The difference compared to Example 1 is that: the ceramic slurry is prepared directly using silicon carbide powder and zirconium carbide reinforcing phase.

[0092] Comparative Example 3

[0093] The difference from Example 1 is that only a single heat treatment step is used: high-temperature argon atmosphere sintering at a temperature of 1800°C for 6 hours. All other parameters are the same as in Example 1.

[0094] Comparative Example 4

[0095] The difference from Example 1 is that the heat treatment process is performed without a protective atmosphere. All other parameters are the same as in Example 1.

[0096] Figure 2 and Figure 3The figures show the curing depth and linear ablation rate data for the examples and comparative examples. Compared to Comparative Example 1, the curing depth of the slurry in the examples is increased, and the efficiency of photopolymerization is improved. Comparative Example 2 has a similar linear ablation rate to the examples, but its curing depth is lower, resulting in poorer curing properties. Although Comparative Examples 3 and 4 have the same ceramic slurry composition as Example 1, the changes in heat treatment conditions in the comparative examples have a significant impact on the ceramic phase composition and high-temperature resistance.

[0097] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing carbide composite ceramic materials with improved photocurable forming properties and high-temperature properties, characterized in that, Includes the following steps: (1) Carbide ceramic powder is loaded into a fluidized bed chemical vapor deposition reactor, and a precursor compound of refractory metal modification layer material is introduced and reacted together with a carrier gas to deposit a refractory metal surface modification layer on the surface of the carbide ceramic particles, thereby obtaining surface-modified carbide ceramic particles with improved curing performance; the surface-modified carbide ceramic particles include a carbide ceramic particle core and a refractory metal surface modification layer deposited on the surface of the carbide ceramic particle core; the material of the carbide ceramic particle core is selected from at least one of silicon carbide and boron carbide; the material of the refractory metal surface modification layer is selected from at least one of the refractory metal elements zirconium, hafnium, tantalum and titanium; (2) The surface-modified carbide ceramic particles are mixed with photosensitive resin to prepare a ceramic slurry, which is then photocured and additively prepared. After cleaning, a carbide composite ceramic blank is obtained. (3) The carbide composite ceramic body is subjected to two-stage heat treatment consisting of high-temperature thermal degreasing and high-temperature in-situ reaction sintering. During the high-temperature thermal degreasing process, the organic matter in the ceramic body undergoes cracking and carbonization reaction to form organic pyrolytic carbon, which provides a carbon source for subsequent high-temperature in-situ reaction sintering. During the high-temperature in-situ reaction sintering process, the refractory metal surface modification layer reacts in-situ with the organic pyrolytic carbon and the core of the carbide ceramic particles to form a refractory metal carbide high-temperature reinforcing phase at the grain boundary of the carbide ceramic particles, thereby obtaining a carbide composite ceramic with enhanced high-temperature performance.

2. The preparation method for improving the photocurable forming performance and high-temperature performance of carbide composite ceramic materials according to claim 1, characterized in that, In step (1), the precursor compound of the refractory metal modified layer material is selected from at least one of zirconium tetrachloride, hafnium tetrachloride, tantalum pentachloride, and titanium tetrachloride, and the carrier gas is a mixture of hydrogen and argon.

3. The preparation method for improving the photocurable forming performance and high-temperature performance of carbide composite ceramic materials according to claim 1, characterized in that, The coating deposition conditions in step (1) include: The molar ratio of the precursor compound to hydrogen is 1:1 to 1:6; The hydrogen flow rate is 0.1-1 L / min, and the argon flow rate is 0.2-2 L / min; The deposition process takes place at a temperature of 400-1200℃ for 10-60 minutes.

4. The preparation method for improving the photocurable forming performance and high-temperature performance of carbide composite ceramic materials according to claim 1, characterized in that, The photosensitive resin components in step (2) include: prepolymer monomer premix, photoinitiator, and dispersant; The prepolymer monomer premix includes: multifunctional prepolymer monomers and bifunctional prepolymer monomers, wherein the volume ratio of the multifunctional prepolymer monomers to the bifunctional prepolymer monomers is 1:1 to 4:

1.

5. The preparation method for improving the photocurable forming performance and high-temperature performance of carbide composite ceramic materials according to claim 1, characterized in that, In step (2), the solid content of the composite ceramic slurry is 30-60 vol%; the mixing method is planetary ball milling, the ball milling speed is 300-1200 rad / min, and the ball milling time is 2-10 h.

6. The preparation method for improving the photocurable forming performance and high-temperature performance of carbide composite ceramic materials according to claim 1, characterized in that, The photopolymerization process parameters in step (2) are: incident light power of 40-120 mW / cm², and unconstrained exposure time of 5-40 s; The method for cleaning the ceramic blank is ultrasonic cleaning with anhydrous ethanol solution, and the cleaning time is 3-10 min.

7. The preparation method for improving the photocurable forming performance and high-temperature performance of carbide composite ceramic materials according to claim 1, characterized in that, The two heat treatment parameters in step (3) are: argon atmosphere protection, high-temperature thermal degreasing temperature of 600-1200℃ and time of 1-4h, and high-temperature in-situ reaction sintering temperature of 1600-2200℃ and time of 2-10h.

8. A high-temperature performance-enhanced carbide composite ceramic, characterized in that, It is prepared by the preparation method according to any one of claims 1-7.

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