Fiber-reinforced ceramic photocuring slurry, preparation method and reinforced ceramic material

Abstract

The invention belongs to the technical field of ceramics and slurry thereof, and particularly relates to fiber-reinforced ceramic photocuring slurry, a preparation method and a reinforced ceramic material. The slurry provided by the invention consists of ceramic powder, ceramic composite short fibers, light-cured resin, a photoinitiator, a dispersing agent, a plasticizer and the like, wherein the ceramic composite short fibers are zirconium oxide and silicon oxide composite fibers; the light-cured resin contains a photosensitive resin monomer and a prepolymer; and the photoinitiator is compounded by a short-wavelength initiator and a long-wavelength initiator. The preparation method comprises the following steps: modifying the ceramic composite short fibers with a silane coupling agent, mixing the modified ceramic composite short fibers with all the materials, and carrying out ball milling and defoaming. The obtained slurry is subjected to 3D printing photocuring molding and degreasing sintering, and a reinforced ceramic material can be prepared. The slurry can be used for manufacturing a high-performance ceramic material through composite short fiber synergistic enhancement, long and short wavelength initiator synergistic curing and fiber surface modification, and the curing depth, the three-point bending strength and the fracture toughness are remarkably improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of ceramics and their slurries, and particularly relates to a fiber-reinforced ceramic photocurable slurry, a preparation method, and a reinforced ceramic material. Background Art

[0002] As an advanced manufacturing technology, ceramic 3D printing can achieve the rapid preparation of complex structures and shows unique advantages in fields such as aerospace and medical implants. Among them, the stereolithography apparatus (SLA) technology has become an important direction for ceramic additive manufacturing due to its high precision, smooth surface, and strong adaptability to complex structures. However, the layer-by-layer curing mechanism relied on by SLA has inherent defects: the interlayer interface becomes a stress concentration area and a crack propagation path, resulting in the strength and toughness of the printed parts being lower than those of traditional forming processes. Especially for color ceramic printing, the absorption of ultraviolet light by coloring oxides weakens the light penetration depth, further reducing the curing efficiency and exacerbating the problem of insufficient interlayer bonding force, which limits its application in high-reliability scenarios.

[0003] Ceramic fiber reinforcement is an effective means to improve the mechanical properties of ceramic materials. Existing fiber reinforcement mainly uses the fused deposition modeling (FDM) technology, in which ceramic fibers are added to a thermoplastic material containing ceramic powder, and the enhanced effect is achieved by layer-by-layer extrusion and molten stacking. However, this process has problems such as rough surface and low dimensional accuracy, and it is difficult to meet the manufacturing requirements of complex and precision components. In contrast, if ceramic fibers can be introduced into the photosensitive resin slurry in SLA, it is expected to combine the dual advantages of "fiber reinforcement" and "high-precision photocuring forming". Summary of the Invention

[0004] Aiming at the deficiencies of the existing technology, the present invention provides a fiber-reinforced ceramic photocurable slurry, a preparation method, and a reinforced ceramic material.

[0005] In the implementation process of the present invention, it is found that the fiber-reinforced slurry for SLA faces multiple technical challenges. First, the interface between the fiber and the resin is weakly bonded. The surface polarity of the ceramic fiber is poorly compatible with the photosensitive resin, resulting in low load transfer efficiency, easy fiber pull-out, and difficulty in fully exerting the reinforcing effect. Second, the curing is uneven and the curing depth is insufficient. A single photoinitiator has a narrow ultraviolet light absorption wavelength range, and the shallow curing and deep curing are not synchronized. Especially in slurries containing colorants or high fillers, the light attenuation is significant, and the problem of insufficient deep curing is exacerbated. Third, the fibers are not easily fully dispersed. The large aspect ratio of the ceramic fiber leads to a large steric hindrance, and there is a large interfacial energy between its surface polarity and the non-polar resin matrix, jointly resulting in the tendency of the ceramic fibers to entangle and aggregate with each other rather than being uniformly distributed, affecting the structural consistency and mechanical properties after curing.

[0006] The object of the present invention is to provide a ceramic photocurable slurry capable of high-precision forming and having excellent mechanical properties, and a high-performance ceramic product.

[0007] The first aspect of the present invention is to provide a fiber-reinforced ceramic photocurable slurry, comprising ceramic powder, ceramic composite fiber, photocurable resin, photoinitiator, coloring oxide, dispersant, and plasticizer.

[0008] The ceramic powder is one or more of zirconia, alumina, zirconia-toughened alumina, and alumina-toughened zirconia.

[0009] The ceramic composite fiber is a composite fiber of zirconia fiber and silica fiber, accounting for 1.5% - 4.0% of the mass of the ceramic powder, wherein the mass ratio of zirconia to silica is 1 - 2; and the ceramic composite fiber is subjected to silane coupling surface treatment before being formulated into a slurry.

[0010] The photocurable resin includes a photosensitive resin monomer and a prepolymer; the photosensitive resin monomer is a mixture of several of hexanediol diacrylate (HDDA), isodecyl acrylate (IDA), trimethylolpropane triacrylate (TMPTA), and pentaerythritol tetraacrylate (PPTTA), accounting for 75% - 85% of the mass of the photocurable resin; the prepolymer is one or more of epoxy acrylate resin (EA), polyurethane acrylate resin (PUA), and bisphenol A epoxy acrylate (BPA-EP), accounting for 15% - 25% of the mass of the photocurable resin.

[0011] The photoinitiator includes a short-wavelength initiator and a long-wavelength initiator, wherein the short-wavelength initiator is an ultraviolet photoinitiator with an absorption wavelength in the range of 240 - 280 nm, the long-wavelength initiator is an ultraviolet photoinitiator with an absorption wavelength in the range of 320 - 400 nm, the mass ratio of the short-wavelength initiator to the long-wavelength initiator is 0.5 - 2, and the total amount of the photoinitiator accounts for 1.2% - 2.2% of the mass of the photocurable resin.

[0012] As a further optimized scheme of the fiber-reinforced ceramic photocurable slurry, the length of the composite fiber is 5 - 20 μm, and the diameter is 1 - 4 μm.

[0013] As a further optimized scheme of the fiber-reinforced ceramic photocurable slurry, the short-wavelength initiator is selected from 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-2-methyl-1-phenylpropanone (1173), and the long-wavelength initiator is selected from benzoin diethyl ether (651), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (819), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO).

[0014] As a further optimization scheme of the fiber-reinforced ceramic photocuring slurry, the coloring oxide is one or more of iron oxide, cobalt oxide, cerium oxide, niobium oxide, and erbium oxide, accounting for 0.8% - 1.5% of the mass of the ceramic powder.

[0015] As a further optimization scheme of the fiber-reinforced ceramic photocuring slurry, the dispersant is one or more of BYK110, BYK218, BYK111, and KOS110, accounting for 1% - 3% of the mass of the ceramic powder.

[0016] As a further optimization scheme of the fiber-reinforced ceramic photocuring slurry, the plasticizer is one or more of polyethylene glycol 200 (PEG200), polyethylene glycol 400 (PEG400), polypropylene glycol 400 (PPG400), dibutyl phthalate (DBP), and dioctyl phthalate (DOP), accounting for 20% - 25% of the mass of the photocuring resin.

[0017] As a further optimization scheme of the fiber-reinforced ceramic photocuring slurry, it further includes a leveling agent, and the leveling agent is one or more of TEGO450 and TEGOPREN5847, accounting for 8% - 15% of the mass of the photocuring resin.

[0018] As a further optimization scheme of the fiber-reinforced ceramic photocuring slurry, it further includes an antifoaming agent, and the antifoaming agent is Foamex N, accounting for 5% - 10% of the mass of the photocuring resin.

[0019] The second aspect of the present invention is to provide a preparation method of the above-mentioned fiber-reinforced ceramic photocuring slurry, including the following steps: Step (1): Modify the surface of the ceramic composite fiber with a silane coupling agent; Step (2): Mix the surface-modified ceramic composite fiber with other materials evenly according to the formulation amount and perform defoaming treatment to obtain the fiber-reinforced ceramic photocuring slurry.

[0020] As a further optimization scheme of the above preparation method, it includes the following steps: Step (1): Add the ceramic composite fiber into an ethanol solution containing 2 - 4wt% of the silane coupling agent γ-methacryloxypropyltrimethoxysilane, ultrasonically disperse for 20 - 40 minutes, filter, dry at 55 - 70°C for 3 - 6 hours, and then heat-treat at 170 - 190°C for 0.5 - 2 hours; Step (2): The surface-modified ceramic composite fibers, together with a photocurable resin, a photoinitiator, a dispersant, a plasticizer, and optionally a coloring oxide, a leveling agent, and an antifoaming agent, are added to a mixing container, and vacuum degassed and mixed at a rotation speed of 500 - 2000 rpm for 5 - 12 minutes. Then, ceramic powder is added, and the mixture is transferred to a planetary ball mill and ball-milled and mixed at a rotation speed of 100 - 300 rpm for 5 - 12 hours. Finally, vacuum degassing is performed again for 10 - 30 minutes to obtain a fiber-reinforced ceramic photocurable slurry.

[0021] The third aspect of the present invention is to provide a reinforced ceramic material, which is prepared by 3D printing photocuring molding, debinding, and sintering using the above-mentioned fiber-reinforced ceramic photocurable slurry.

[0022] Beneficial effects The fiber-reinforced ceramic photocurable slurry provided by the present invention uses a composite system with a photocurable resin as the matrix and ceramic powder as the aggregate, and adopts zirconia and silica composite fibers. Utilizing their synergistic effect, it plays a bridging effect during the propagation of matrix cracks, improves the refractive index of the material, and acts as a sintering aid, enhancing the interfacial bonding force with the resin matrix and the load transfer efficiency. At the same time, the photoinitiator uses a combination of short-wavelength and long-wavelength initiators to form "surface - deep layer synergistic curing", improving the problem of insufficient photocuring depth of colored ceramics, while enhancing the time uniformity and spatial uniformity of curing, and reducing internal stress concentration. In addition, surface modification treatment is performed on the ceramic composite fibers, further enhancing the interfacial bonding force between the fibers and the resin matrix. These measures work together to significantly improve the curing depth after slurry curing and the mechanical properties after ceramic sintering. The present invention provides a high-quality slurry for preparing high-performance reinforced ceramic materials. This slurry is suitable for 3D printing photocuring molding, and excellent reinforced ceramic materials can be obtained through debinding and sintering. Description of the drawings

[0023] Figure 1 It is a composition diagram of the photocurable ceramic slurry for Examples 1 - 3.

[0024] Figure 2 It is a composition diagram of the photocurable ceramic slurry for Comparative Examples 1 - 3.

[0025] Figure 3 It is a composition diagram of the photocurable ceramic slurry for Comparative Examples 4 - 6.

[0026] Figure 4 It is a performance test result diagram of the examples and comparative examples. Detailed implementation manners

[0027] The present invention will be further illustrated below through specific examples. These examples are exemplary, aiming to illustrate the problem and explain the present invention, and are not a limitation.

[0028] The fiber-reinforced ceramic photocurable slurry of the present invention comprises ceramic powder, ceramic composite fiber, photocurable resin, photoinitiator, coloring oxide, dispersant, plasticizer, leveling agent, and defoaming agent.

[0029] The ceramic powder is one or more of zirconia (ZrO2), alumina (Al2O3), zirconia toughened alumina (ZTA), and alumina toughened zirconia (ATZ).

[0030] The ceramic composite fiber is a composite fiber of zirconia fiber and silica fiber, accounting for 1.5% - 4.0% of the mass of the ceramic powder, with a fiber length of 5 - 20 μm and a diameter of 1 - 4 μm, and the mass ratio of zirconia to silica is 1 - 2.

[0031] The photocurable resin comprises photosensitive resin monomers and oligomers (prepolymers). Among them, the photosensitive resin monomers are a mixture of several of hexanediol diacrylate (HDDA), isodecyl acrylate (IDA), trimethylolpropane triacrylate (TMPTA), and pentaerythritol tetraacrylate (PPTTA), accounting for 75% - 85% of the mass of the photocurable resin; the oligomers are one or more of epoxy acrylate resin (EA), polyurethane acrylate resin (PUA), and bisphenol A epoxy acrylate resin (BPA-EP), accounting for 15% - 25% of the mass of the photocurable resin.

[0032] The photoinitiator is a mixture of short-wavelength initiator and long-wavelength initiator. The short-wavelength initiator is selected from 1-hydroxycyclohexyl phenyl ketone (184) and 2-hydroxy-2-methyl-1-phenylpropanone (1173); the long-wavelength initiator is selected from benzoin diethyl ether (651), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (819), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO); the mass ratio of the short-wavelength initiator to the long-wavelength initiator is between 0.5 - 2, and the total amount of the photoinitiator accounts for 1.2% - 2.2% of the mass of the photocurable resin.

[0033] The coloring oxide is one or more of iron oxide, cobalt oxide, cerium oxide, niobium oxide, and erbium oxide, accounting for 0.8% - 1.5% of the mass of the ceramic powder.

[0034] The dispersant is one or more of BYK110, BYK218, BYK111, and KOS110, accounting for 1% - 3% of the mass of the ceramic powder.

[0035] The plasticizer is one or more of polyethylene glycol 200 (PEG200), polyethylene glycol 400 (PEG400), polypropylene glycol 400 (PPG400), dibutyl phthalate (DBP), and dioctyl phthalate (DOP), accounting for 20% - 25% of the mass of the photocurable resin.

[0036] The leveling agent is one or more of TEGO450 and TEGOPREN5847, accounting for 8% - 15% of the mass of the photocurable resin.

[0037] The defoaming agent is Foamex N, accounting for 5% - 10% of the mass of the photocurable resin.

[0038] Source of raw materials: Zirconia powder: Saint - Gobain ZirPro (Handan) Co., Ltd.; Aluminum oxide powder: Hangzhou Wanjing New Materials Co., Ltd.; Zirconia toughened alumina (ZTA) powder: Obtained by mixing the zirconia powder and aluminum oxide powder from the above sources, and the mass ratio of zirconia powder to aluminum oxide powder is 1:4; Aluminum oxide toughened zirconia (ATZ) powder: Obtained by mixing the zirconia powder and aluminum oxide powder from the above sources, and the mass ratio of zirconia powder to aluminum oxide powder is 4:1; Epoxy acrylate resin (EA): L - 6111 of Guangdong Bluecol New Materials Co., Ltd.; Polyurethane acrylate resin (PUA): 6145 - 100 of Changxing Chemical Industry Co., Ltd.; Bisphenol A epoxy acrylate resin (BPA - EP): IBW - 71281 - 65 - 7 of Hubei Langbowan Biopharmaceutical Co., Ltd.; Zirconia ceramic fiber: Forsman Technology (Beijing) Co., Ltd., zirconia ultra - short fiber (4008006); Silica ceramic fiber: Forsman Technology (Beijing) Co., Ltd., nano - silica fiber (1407231).

[0039] The fiber - reinforced ceramic photocurable slurry of the present invention is prepared by the following steps: (1) Surface modification treatment of ceramic composite fiber First, perform surface modification on the ceramic composite fibers: Add the ceramic composite fibers (composite fibers of zirconia fibers and silica fibers) to an ethanol solution containing 2 - 4 wt% silane coupling agent, and ultrasonically disperse for 20 - 40 minutes to fully disperse the fibers in the solution. After dispersion, filter and separate the fibers, and place the filtered fibers in a drying environment at 55 - 70 °C for 3 - 6 hours to remove the ethanol solvent. Subsequently, transfer the dried fibers to an environment at 170 - 190 °C for heat treatment for 0.5 - 2 hours to complete the surface modification and enhance the interfacial bonding force between the fibers and the resin matrix. (2) Preparation of the slurry mixture According to the formulation amount, add the surface - modified ceramic composite fibers, coloring oxides, photosensitive resin monomers, oligomers, dispersants, plasticizers, leveling agents, defoamers, and initiators into a mixing container together. Place the mixing container in a vacuum degassing machine and mix at a rotation speed of 500 - 2000 rpm for 5 - 12 minutes to initially mix all components evenly. Then, add ceramic powder to the uniformly mixed system, and transfer the mixed material to a planetary ball mill. Mill and mix at a rotation speed of 100 - 300 rpm for 5 - 12 hours to ensure that the ceramic powder is fully dispersed and mixed with other components. After ball milling, place the slurry in a vacuum environment again for defoaming treatment for 10 - 30 minutes to remove the bubbles introduced during the mixing process, and finally obtain a uniform and stable fiber - reinforced ceramic photocurable slurry.

[0040] Examples 1 - 3 and Comparative Examples 1 - 6 The photocurable ceramic slurries in Examples 1 - 3 are formulated according to Figure 1 the formula shown, and the photocurable ceramic slurries in Comparative Examples 1 - 3 are formulated according to Figure 2 the formula shown, and the photocurable ceramic slurries in Comparative Examples 4 - 6 are formulated according to Figure 3 the formula shown.

[0041] The preparation of the photocurable ceramic slurry is processed according to the following steps.

[0042] (1) Surface modification treatment of ceramic composite fibers First, perform surface modification on the ceramic composite fibers: Add the ceramic composite fibers (composite fibers of zirconia fibers and silica fibers) to an ethanol solution containing 3 wt% silane coupling agent (γ - methacryloxypropyltrimethoxysilane), and ultrasonically disperse for 30 minutes to fully disperse the fibers in the solution. After dispersion, filter and separate the fibers, and place the filtered fibers in a drying environment at 60 °C for 4 hours to remove the ethanol solvent. Subsequently, transfer the dried fibers to an environment at 180 °C for heat treatment for 1 hour to complete the surface modification and enhance the interfacial bonding force between the fibers and the resin matrix. (2)Preparation of Slurry Mixture According to the formula amount, the surface-modified ceramic composite fibers, coloring oxides, photosensitive resin monomers, oligomers, dispersants, plasticizers, leveling agents, defoamers, and initiators are added into a mixing container together. The mixing container is placed in a vacuum degassing machine and mixed at a rotation speed of 1500 rpm for 8 minutes to preliminarily mix all components evenly. Then, ceramic powder is added to the uniformly mixed system, and then the mixed material is transferred to a planetary ball mill and ball-milled and mixed at a rotation speed of 200 rpm for 10 hours to ensure that the ceramic powder is fully dispersed and mixed with other components. After the ball milling is completed, the slurry is placed in a vacuum environment again for defoaming treatment for 20 minutes to remove the bubbles introduced during the mixing process, and finally a uniform and stable fiber-reinforced ceramic photocuring slurry is obtained.

[0043] Test Example The slurries prepared in the examples and comparative examples are injected into an SLA-100 ceramic photocuring printer, and the single-layer printing size is set as X: 10 mm × Y: 10 mm × Z: 0.1 mm. After completing the single-layer printing, the printed parts are taken out and the uncured slurry on the surface is cleaned, and then placed under a high-precision confocal measuring instrument to measure the depth of the cured layer.

[0044] The slurries prepared in the examples and comparative examples are 3D printed, and the printing size is set as X: 30 mm × Y: 5 mm × Z: 4 mm. After the printing is completed, the residual slurry on the surface of the green ceramic body is cleaned, and then the green body is put into a debinding and sintering furnace for debinding and sintering treatment. The debinding process parameters are: heating from room temperature to 380 °C at a rate of 0.5 °C / min, holding at 380 °C for 5 h, then heating to 600 °C at a rate of 0.3 °C, and holding at 600 °C for 2 h, and continuing to cool to room temperature at a rate of 1 °C / min. The sintering process parameters are: heating to 1580 °C at a rate of 2 °C / min, holding for 2 h, and cooling to room temperature at a rate of 2 °C / min.

[0045] After the sintered specimen is polished, the fracture toughness is measured by a microhardness tester. The specific method is: applying a load of 10 kg on the polished surface of the specimen to form an indentation through a conical diamond indenter, so that prefabricated cracks are generated at the four vertices of the indentation. The fracture toughness value (K IC ) is calculated. The calculation formula is: K IC = 0.016×(E / H V)^(1 / 2)×(P / (C^(3 / 2))). Where E is the elastic modulus of the material, in GPa; Hv is the Vickers hardness of the material, in GPa; the crack length C is half of the indentation diagonal length, in millimeters (mm); the load P is the force applied to the indenter, in Newtons (N). According to GB / T 6569-2006, the flexural strength of the specimen was tested by a three-point bending test, and the loading speed was 0.5 mm / min.

[0046] The test results are as Figure 4 shown.

[0047] From the comparison between Comparative Example 1 and Example 1, and Comparative Example 6 and Example 3, it can be seen that the difference in initiators has a significant impact on the performance. In Examples 1 and 3, initiators combining short and long wavelengths were used, while in Comparative Examples 1 and 6, single initiators were used. In terms of performance, the curing depth, three-point bending strength, and fracture toughness of Example 1 were all significantly better than those of Comparative Example 1; the curing depth, three-point bending strength, and fracture toughness of Example 3 were also all significantly better than those of Comparative Example 6. Short-wavelength initiators (such as 184, 1173) absorb short ultraviolet waves (240 - 280 nm), but the light penetration is shallow, and only the surface layer of the material can be effectively cured in a short time; long-wavelength initiators (such as TPO, 651) absorb long waves (320 - 400 nm), and the light penetration is deeper, which can initiate the deep curing of the material. When the two are compounded, the short-wavelength initiator mainly acts on the surface layer, and the long-wavelength initiator simultaneously promotes the deep curing, forming "surface - deep synergistic curing", avoiding problems such as "surface over-curing / deep under-curing" or "surface under-curing / deep over-shrinkage" caused by the limitation of the penetration depth, thus significantly improving the uniformity of the curing depth, reducing the internal stress concentration, being beneficial to the material to maintain stability and denseness during the sintering process, and finally obtaining high-strength ceramic parts.

[0048] The differences between Comparative Example 2 and Example 2, and between Comparative Example 3 and Example 3 lie in whether ceramic composite fibers are added. For Comparative Examples 2 and 3 without added ceramic composite fibers, their curing depth, three-point bending strength, and fracture toughness are all lower than those of the corresponding examples. Among the ceramic composite fibers, zirconia fibers can play a bridging role during the propagation of matrix cracks, hindering crack propagation, and silica fibers can improve the refractive index of the material and act as a sintering aid. During high-temperature sintering, a glassy phase will be formed, filling the gaps between ceramic particles and promoting atomic diffusion between particles, thereby significantly improving the densification degree of the sintered body. After the two are compounded, a good interfacial bond is formed with the matrix, improving the curing depth and mechanical properties. Comparative Example 4 only uses single zirconia fibers compared to Example 1, and Comparative Example 5 only uses silica fibers compared to Example 2, and their performance shows a downward trend compared to the compounding of the two fibers. Although single zirconia fibers can, to a certain extent, hinder crack propagation, they limit the light penetration depth, and the interfacial bond and load transfer effects are insufficient. Although single silica fibers can improve the refractive index, their own strength and interfacial bonding ability are lower than those of zirconia fibers, and neither of them can achieve the significant strengthening effect of the composite fibers. The synergy between zirconia and silica fibers not only improves the crack resistance ability through the bridging effect of zirconia fibers, but also promotes deep curing by means of the refractive index improvement of silica fibers, while forming a good interfacial bond to enhance the interlayer load transfer efficiency, thus significantly optimizing the curing depth of the slurry, and the bending strength and fracture toughness after sintering.

[0049] In summary, the synergistic compounding of long- and short-wavelength initiators and zirconia / silica composite fibers in the present invention significantly improves the material properties. It not only improves the curing depth and uniformity through the "surface-deep layer synergistic curing" mechanism to reduce internal stress, but also utilizes the crack bridging effect of zirconia fibers and the refractive index adjustment and sintering aid effects of silica fibers to enhance the interfacial bond and load transfer efficiency, significantly improving the curing depth after slurry curing, and the bending strength and fracture toughness after sintering, achieving a significant improvement in the comprehensive properties of fiber-reinforced ceramic photocurable slurries and ceramic materials.

[0050] The above embodiments are exemplary, aiming to illustrate the technical concept and characteristics of the present invention, so that those skilled in this field can understand the content of the present invention and implement it accordingly, and should not be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit and essence of the present invention should be covered within the protection scope of the present invention.

Claims

1. A fiber-reinforced ceramic photocuring slurry, characterized in that: Including ceramic powder, ceramic composite fiber, photocurable resin, photoinitiator, coloring oxide, dispersant, plasticizer; The ceramic powder is one or more of zirconium oxide, aluminum oxide, zirconium oxide toughened aluminum oxide, and aluminum oxide toughened zirconium oxide; The ceramic composite fiber is a composite fiber of zirconium oxide fiber and silicon oxide fiber, accounting for 1.5%-4.0% of the mass of the ceramic powder, wherein the mass ratio of zirconium oxide to silicon oxide is 1-2; and the ceramic composite fiber is subjected to silane coupling surface treatment before being prepared into slurry; The photocurable resin includes photosensitive resin monomers and prepolymers; the photosensitive resin monomers are a mixture of hexanediol diacrylate, isodecyl acrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate, accounting for 75%-85% of the mass of the photocurable resin; the prepolymers are one or more of epoxy acrylic resin, polyurethane acrylic resin, and bisphenol A epoxy acrylic resin, accounting for 15%-25% of the mass of the photocurable resin; The photoinitiator includes a short-wavelength initiator and a long-wavelength initiator, wherein the short-wavelength initiator is an ultraviolet light initiator with an absorption wavelength in the range of 240-280nm, and the long-wavelength initiator is an ultraviolet light initiator with an absorption wavelength in the range of 320-400nm. The mass ratio of the short-wavelength initiator to the long-wavelength initiator is 0.5-2, and the total amount of the photoinitiator accounts for 1.2%-2.2% of the mass of the photocurable resin.

2. The fiber-reinforced ceramic photocuring slurry according to claim 1, characterized in that: The composite fiber has a length of 5-20 μm and a diameter of 1-4 μm.

3. The fiber-reinforced ceramic photocuring slurry according to claim 1 or 2, characterized in that: The short wavelength initiator is selected from 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylacetone, and the long wavelength initiator is selected from benzoin diethyl ether, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

4. The fiber-reinforced ceramic photocuring slurry according to claim 3, characterized in that: The coloring oxide is one or more of iron oxide, cobalt oxide, cerium oxide, niobium oxide, and erbium oxide, accounting for 0.8%-1.5% of the mass of the ceramic powder.

5. The fiber-reinforced ceramic photocuring slurry according to claim 4, characterized in that: The dispersant is one or more of BYK110, BYK218, BYK111, and KOS110, accounting for 1%-3% of the mass of the ceramic powder.

6. The fiber-reinforced ceramic photocuring slurry according to claim 5, characterized in that: The plasticizer is one or more of polyethylene glycol 200, polyethylene glycol 400, polypropylene glycol 400, dibutyl phthalate, and dioctyl phthalate, accounting for 20%-25% of the mass of the photocurable resin.

7. The fiber-reinforced ceramic photocuring slurry according to claim 6, characterized in that: It also includes a leveling agent, which is one or more of TEGO450 and TEGOPREN5847, accounting for 8%-15% of the mass of the photocurable resin; and a defoamer, which is Foamex N, accounting for 5%-10% of the mass of the photocurable resin.

8. The method for preparing the fiber-reinforced ceramic photocuring slurry according to any one of claims 1 to 7, characterized in that: The following steps are involved: Step (1): using a silane coupling agent to modify the surface of the ceramic composite fiber; Step (2): uniformly mixing the surface-modified ceramic composite fiber with other materials according to the formula amount and performing a degassing treatment to obtain the fiber-reinforced ceramic photocuring slurry.

9. The method for preparing the fiber-reinforced ceramic photocuring slurry according to claim 8, characterized in that: The following steps are involved: Step (1): adding the ceramic composite fiber to an ethanol solution containing 2-4wt% of silane coupling agent γ-methacryloxypropyltrimethoxysilane, ultrasonically dispersing for 20-40 minutes, filtering, drying at 55-70°C for 3-6 hours, and then heat treating at 170-190°C for 0.5-2 hours; Step (2) Add the surface-modified ceramic composite fiber together with the photocurable resin, photoinitiator, dispersant, plasticizer and optional coloring oxide, leveling agent and defoaming agent into a mixing container, perform vacuum degassing and mixing at a speed of 500-2000 rpm for 5-12 minutes, then add the ceramic powder, transfer to a planetary ball mill, perform ball milling and mixing at a speed of 100-300 rpm for 5-12 hours, and finally perform vacuum degassing again for 10-30 minutes to obtain the fiber-reinforced ceramic photocurable slurry.

10. A reinforced ceramic material, characterized in that: The fiber-reinforced ceramic photocurable slurry according to any one of claims 1 to 7 is prepared by 3D printing photocuring molding, degreasing and sintering.

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