Alumina solidified slurry, alumina toughened zirconia ceramic and method for preparing the same

Abstract

The application relates to the field of ceramic manufacturing, and particularly discloses an alumina solidification slurry, alumina toughened zirconia ceramic and a preparation method thereof. The alumina solidification slurry is used for jetting and solidifying a zirconia powder layer, and comprises the following components in parts by weight: photocuring resin 20-70 parts, UV monomer 20-70 parts, photoinitiator 1-10 parts, dispersant 0.1-5 parts and alumina powder 60-200 parts; the average particle size of the alumina powder is less than or equal to 5 microns. By implementing the application, the mixing uniformity of zirconia and alumina can be improved, and the mechanical properties of the zirconia ceramic material are improved.

Description

Technical Field

[0001] This invention relates to the field of ceramic manufacturing, and in particular to an alumina curing slurry, an alumina-toughened zirconia ceramic, and a method for preparing the same. Background Technology

[0002] Alumina-toughened zirconia is an excellent high-temperature resistant ceramic material that combines the advantages of both alumina and zirconia, such as high temperature resistance, oxidation resistance, creep resistance, and corrosion resistance, and has broad application prospects in various fields.

[0003] On the other hand, traditional ceramic forming and processing faces numerous challenges due to the hard and brittle nature of ceramic materials. 3D printing technology, however, offers rapid forming and high-fidelity structural features, overcoming the limitations of traditional processing to manufacture complex geometric structures and expanding the freedom of design for ceramic parts. 3D printing technology is based on the discrete-addition molding principle. It selectively sprays binder onto layers of powder material (such as gypsum powder, ceramic powder, and metal powder) through a nozzle, causing the powder material to bond and solidify layer by layer, ultimately forming a three-dimensional solid model. During each layer printing process, the print head selectively sprays binder onto the powder surface according to the two-dimensional slicing data of the model. Powder not sprayed with binder remains loose, providing support without the need for additional support structures. After printing one layer, the printing table descends by one layer thickness, and a new powder layer is applied, continuing the printing of the next layer, in a cycle until the model is complete.

[0004] However, when using 3DP printing technology to prepare alumina-toughened zirconia ceramics, due to the zirconia powder (5.8~6.3 g / cm³), 3 ) and alumina powder (3.7~3.9 g / cm³) 3 The densities of the two powders differ significantly. If these two powders are premixed, the uniformity of powder mixing during printing becomes a major problem. Uneven distribution of the toughening agent in the ceramic powder will affect the performance of the printed parts. In addition, the balance between printing accuracy and efficiency, high cost, and limitations on the size and shape of the printed parts are also issues that need to be addressed. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide an alumina curing slurry and its preparation method, which can be used to spray-cur zirconia powder layers, improve the mixing uniformity of zirconia and alumina, and thus improve the mechanical properties of zirconia ceramic materials.

[0006] The technical problem to be solved by the present invention is to provide an alumina-toughened zirconia ceramic and its preparation method, which can effectively improve the mechanical properties of zirconia ceramic.

[0007] To address the aforementioned technical problems, this invention provides an alumina curing slurry for spray curing zirconia powder layers, comprising the following components in parts by weight: 20-70 parts of UV-curable resin, 20-70 parts of UV monomer, 1-10 parts of photoinitiator, 0.1-5 parts of dispersant, and 60-200 parts of alumina powder; The alumina powder has an average particle size of ≤5μm.

[0008] As an improvement to the above technical solution, the photocurable resin is selected from one or more of RJ313, 6233, DR-U384, DS-2547, and SU 571M100; and / or The UV monomer is selected from one or more of TPGDA, DPHA, HDDA, TMPTA, and PDDA; and / or The photoinitiator is selected from one or more of Irgacure TPO, Irgacure 1173, and Irgacure 819; The dispersant is selected from one or more of Duramax D-3019, BYK-9076, and BYK-P104S.

[0009] As an improvement to the above technical solution, the photocurable resin is selected from RJ313, DS-2547, or SU 571M100; and / or The photoinitiator is selected from Irgacure TPO or Irgacure 819.

[0010] As an improvement to the above technical solution, the UV monomer is selected as a mixture of TPGDA and HDDA, with a weight ratio of TPGDA to HDDA of 1:1 to 1.4:1; or The UV monomer is a mixture of TPGDA and DPHA, with a weight ratio of TPGDA to DPHA of 0.6:1 to 1:1; or The UV monomer is a mixture of PDDA and TMPTA, with a weight ratio of PDDA to TMPTA of 0.8:1 to 1.2:1.

[0011] As an improvement to the above technical solution, the solid content of the alumina curing slurry is 15~30 vol%, and its viscosity is 75~100 mPa•s.

[0012] Accordingly, the present invention also discloses a method for preparing an alumina curing slurry, which is used to prepare the above-mentioned alumina curing slurry, comprising: The photocurable resin, UV monomer, and photoinitiator are mixed evenly to obtain an intermediate. The intermediate, dispersant and alumina powder are mixed evenly to obtain alumina cured slurry.

[0013] Accordingly, the present invention also discloses a method for preparing alumina-toughened zirconia ceramic, which includes the following steps: S1: Zirconia powder layer is formed using zirconia powder; S2: Spray alumina curing slurry at a predetermined position on the zirconium oxide powder layer; S3: Use ultraviolet light irradiation to initially cure the alumina curing slurry; S4: Repeat steps S1 to S3 until a ceramic green body is obtained; S5: Sinter the ceramic green body to obtain the alumina-toughened zirconia ceramic finished product; The alumina curing slurry comprises the following components in parts by weight: 20-70 parts of UV-curable resin, 20-70 parts of UV monomer, 1-10 parts of photoinitiator, 0.1-5 parts of dispersant, and 60-200 parts of alumina powder; The zirconium oxide powder has an average particle size ≥ 10 μm, and the alumina powder has an average particle size ≤ 5 μm.

[0014] As an improvement to the above technical solution, in step S1, the thickness of the zirconium oxide powder layer is 0.1~0.5 mm; and / or In step S2, the spray saturation of the alumina curing slurry is 50-80%; and / or In step S3, the initial curing power is 50~100mW / cm. 2 The initial curing time is 2-5 seconds; and / or In step S5, the sintering temperature is 1400~1600℃.

[0015] As an improvement to the above technical solution, the particle size of the zirconium oxide powder and the particle size of the alumina powder conform to the following relationship:

[0016] in, The particle sizes are 10%, 50%, and 90% of the cumulative distribution of zirconium oxide powder, respectively. The particle sizes are 10%, 50%, and 90% of the cumulative alumina powder distribution, respectively.

[0017] Accordingly, the present invention also discloses an alumina-toughened zirconia ceramic, which is prepared by the above-described method for preparing alumina-toughened zirconia ceramic.

[0018] Implementing this invention has the following beneficial effects: In one embodiment of the present invention, the alumina curing slurry for spraying and curing zirconia powder layers comprises: 20-70 parts of photocurable resin, 20-70 parts of UV monomer, 1-10 parts of photoinitiator, 0.1-5 parts of dispersant, and 60-200 parts of alumina powder; wherein the average particle size of the alumina powder is ≤5μm. By controlling the proportion of each component and the particle size distribution of the alumina powder, the fluidity and wettability of the slurry are improved, ensuring that it uniformly covers the surface of the zirconia powder during spraying. After UV irradiation, the photocurable resin rapidly crosslinks to form a stable network structure, effectively promoting the dispersion and fixation of alumina particles in the zirconia powder matrix, thereby improving the interfacial bonding strength. This slurry solves the problem of component segregation caused by large density differences in the traditional zirconia and alumina powder premixing process, achieving controllable distribution of the toughening phase, and providing a good foundation for the preparation of high-performance alumina-toughened zirconia ceramics. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments.

[0020] In a first aspect, the present invention provides an alumina curing slurry for spray curing a zirconium oxide powder layer, comprising the following components in parts by weight: The product comprises 20-70 parts of UV-curable resin, 20-70 parts of UV monomer, 1-10 parts of photoinitiator, 0.1-5 parts of dispersant, and 60-200 parts of alumina powder; wherein the average particle size of the alumina powder is ≤5μm.

[0021] The alumina curing slurry of this invention improves the slurry's fluidity and wettability by controlling the component ratio and particle size distribution, ensuring uniform coverage of the zirconia powder surface during spraying. After UV irradiation, the photocurable resin rapidly crosslinks, forming a stable network structure, effectively promoting the dispersion and fixation of alumina particles in the zirconia powder matrix, thereby improving interfacial bonding strength. This slurry solves the component segregation problem caused by density differences in traditional zirconia and alumina powder premixing processes, achieving controllable distribution of the toughening phase and providing a good foundation for preparing high-performance alumina-toughened zirconia ceramics. In practical applications, the slurry is sprayed onto the surface of a laid zirconia powder layer, rapidly cured by UV light to form a uniform composite layer. Layers are stacked to obtain a dense green body, which is then degreased and sintered at high temperature to finally obtain an alumina-toughened zirconia ceramic material with excellent mechanical properties, including a flexural strength exceeding 800 MPa, a hardness exceeding 12 GPa, and a fracture toughness of 8 MPa•m. 1 / 2 above.

[0022] The UV-curable resin is selected from acrylate or epoxy acrylate materials, which have excellent photoresponsiveness and crosslinking density, and can synergistically work with UV monomers to improve curing speed and structural stability. Specifically, the UV-curable resin can be one or more of RJ313, 6233, DR-U384, DS-2547, and SU 571M100, but is not limited to these. Preferably, the UV-curable resin is selected from RJ313, DS-2547, or SU 571M100.

[0023] Specifically, the amount of photocurable resin used is 20-70 parts. When the amount is less than 20 parts, the cured network structure is incomplete, affecting the film-forming properties and bonding strength of the slurry, resulting in poor bonding between alumina and zirconium oxide. When the amount exceeds 70 parts, the viscosity of the slurry increases significantly, and the fluidity decreases, which is not conducive to uniform spraying. For example, the amount of photocurable resin used is 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, or 65 parts, but is not limited thereto. Preferably, the amount of photocurable resin used is 30-50 parts, more preferably 35-45 parts.

[0024] The UV monomer is the main copolymer component, participating in the crosslinking reaction to improve curing speed and network density. Simultaneously, the UV monomer can adjust the viscosity of the alumina-cured slurry, improve its rheological properties, and ensure good atomization and spreadability during spraying. Specifically, the UV monomer can be tripropylene glycol diacrylate (TPGDA), dipentaerythritol hexaacrylate (DPHA), 1,6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), triethylene glycol diacrylate (TEGDA), diethylene glycol diacrylate (PDDA), or combinations thereof, but is not limited thereto. Preferably, in some embodiments, the UV monomer is selected from one or more of TPGDA, DPHA, HDDA, TMPTA, and PDDA. More preferably, the UV monomer can be based on the following three combinations: (1) TPGDA and DPHA, wherein the weight ratio of TPGDA to DPHA is (0.6~1):1, exemplarily 0.65:1, 0.7:1, 0.75:1, 0.8:1, 0.85:1 or 0.9:1, but not limited thereto.

[0025] (2) TPGDA and HDDA, wherein the weight ratio of TPGDA to HDDA is (1.0~1.4):1, for example 1.05:1, 1.1:1, 1.15:1, 1.2:1, 1.25:1, 1.3:1 or 1.35:1, but not limited thereto.

[0026] (3) PDDA and TMPTA, wherein the weight ratio of PDDA to TMPTA is (0.8~1.2):1, for example 0.85:1, 0.9:1, 0.95:1, 1.0:1, 1.05:1, 1.1:1 or 1.15:1, but not limited thereto.

[0027] Specifically, the amount of UV monomer used is 20-70 parts. When the amount is less than 20 parts, the system's reactivity is insufficient, and the curing rate slows down; when the amount exceeds 70 parts, the slurry viscosity is too low, which easily leads to sagging and interlayer slippage during the spraying process. For example, the amount of UV monomer used is 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, or 65 parts, but is not limited to these. Preferably, the amount of UV monomer used is 30-55 parts, more preferably 33-45 parts.

[0028] The photoinitiator is used to generate free radicals or cations under ultraviolet light irradiation, initiating the polymerization reaction and promoting rapid crosslinking and curing of UV monomers. Specifically, the photoinitiator can be one or more of Irgacure TPO, Irgacure 1173, or Irgacure 819, but is not limited to these.

[0029] Specifically, the amount of photoinitiator used is 1 to 10 parts. For example, the amount of photoinitiator used is 1.5 parts, 2 parts, 2.5 parts, 3.5 parts, 4.5 parts, 5.5 parts, 6.5 parts, 7.5 parts, 8.5 parts, or 9.5 parts, but is not limited thereto. Preferably, the amount of photoinitiator used is 1 to 5 parts, more preferably 1 to 3.5 parts.

[0030] The dispersant is used to improve the wetting and dispersion stability of alumina powder in the slurry and prevent agglomeration and sedimentation. Specifically, one or more of Duramax D-3019, BYK-9076, and BYK-P104S are selected as the dispersant, but it is not limited to these.

[0031] Specifically, the amount of dispersant used is 0.1 to 5 parts. When the amount of dispersant is less than 0.1 parts, it is difficult to effectively wet the powder particles, resulting in poor dispersion. When the amount exceeds 5 parts, excessive dispersant may introduce air bubbles and affect the rheological properties of the slurry. For example, the amount of dispersant used is 0.5 parts, 1.0 parts, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, or 4.5 parts, but is not limited thereto. Preferably, the amount of dispersant used is 0.5 to 3.0 parts, more preferably 1 to 3 parts.

[0032] The amount of alumina powder used is 60-200 parts. When the amount is less than 60 parts, the density and mechanical strength of the printed parts decrease significantly; when it exceeds 200 parts, the viscosity of the paste increases sharply, the flowability deteriorates, and the spraying is affected. Exemplarily, the amount of alumina powder used is 65 parts, 70 parts, 80 parts, 90 parts, 100 parts, 120 parts, 140 parts, 160 parts, 180 parts, or 195 parts, but is not limited thereto. Preferably, the amount of alumina powder used is 60-100 parts, but is not limited thereto.

[0033] Specifically, the average particle size of the alumina powder is ≤5μm, specifically 0.2~3μm, to ensure good flowability of the slurry. Preferably, the average particle size of the alumina powder is 0.2~1μm. It should be noted that the average particle size (D50) refers to the particle size value corresponding to a cumulative volume fraction of 50% in the cumulative particle size distribution curve, which can be measured by Mastersizer 3000 or Mastersizer 2000, but is not limited to these.

[0034] Specifically, the solid content of the alumina curing slurry obtained based on the above material combination is 15~30 vol%, and its viscosity is 75~100 mPa•s (25℃), which can well meet the spraying requirements.

[0035] As a second aspect of the present invention, the present invention also discloses a method for preparing an alumina curing slurry, which includes: (1) Mix the photocurable resin, UV monomer and photoinitiator evenly to obtain an intermediate; The mixing temperature is ≤25℃, preferably 20~25℃.

[0036] (2) Mix the intermediate, dispersant and alumina powder evenly to obtain alumina curing slurry.

[0037] As a third aspect of the present invention, a method for preparing alumina-toughened zirconia ceramic is disclosed, comprising the following steps: S1: Zirconia powder layer is formed using zirconia powder; S2: Spray alumina curing slurry at a predetermined position on the zirconia powder layer; S3: Use ultraviolet light irradiation to initially cure the alumina curing slurry; S4: Repeat steps S1 to S3 until a ceramic green body is obtained; S5: Sinter the ceramic green body to obtain the finished alumina-toughened zirconia ceramic product; The alumina curing slurry comprises the following components in parts by weight: 20-70 parts of UV-curable resin, 20-70 parts of UV monomer, 1-10 parts of photoinitiator, 0.1-5 parts of dispersant, and 60-200 parts of alumina powder; The average particle size of zirconium oxide powder is ≥10μm, and the average particle size of alumina powder is ≤5μm.

[0038] Specifically, in step S1, the thickness of the zirconia powder layer is controlled between 0.1 and 0.5 mm. If the thickness is too large, it will affect both the mixing of alumina powder and zirconia powder and the penetration depth of ultraviolet light, resulting in insufficient pre-curing of the alumina curing slurry. If it is too thin, the number of printing layers needs to be increased, reducing the molding efficiency. For example, the thickness of the zirconia powder layer is 0.16 mm, 0.22 mm, 0.28 mm, 0.34 mm, 0.4 mm, or 0.46 mm, but is not limited to these.

[0039] Specifically, in step S1, the average particle size of the zirconia powder is ≥10μm. If the particle size is too small, it will lead to poor powder flowability and affect the uniformity of powder spreading; moreover, it will make it difficult for the alumina powder in the alumina curing slurry to effectively enter the gaps between the zirconia powder to achieve effective filling, thus making it difficult to effectively improve the mechanical properties. Preferably, the average particle size of the zirconia powder is 10~20μm, more preferably 10~15μm.

[0040] Preferably, in some embodiments, the particle size of the zirconium oxide powder and the particle size of the alumina powder conform to the following relationship:

[0041] in, The cumulative particle size distribution curves of zirconium oxide powder show the particle sizes corresponding to cumulative volume fractions of 10%, 50%, and 90%, respectively. These figures represent the particle sizes corresponding to cumulative volume fractions of 10%, 50%, and 90% in the cumulative particle size distribution curves of alumina powder, respectively. Based on this control, it is not only effectively ensured that alumina powder can fully fill the voids between zirconia powder particles, significantly improving mechanical properties, but also that ultraviolet light penetration is guaranteed, achieving precise layer-by-layer molding. It should be noted that the cumulative particle size distribution curves of alumina powder and zirconia powder can be measured using Mastersizer 3000 or Mastersizer 2000, but are not limited to these methods.

[0042] Specifically, in step S2, the spray saturation of the alumina curing slurry is 50-80%. If the saturation is too low, it will lead to insufficient alumina filling, affecting density and mechanical properties; if it is too high, it will easily cause excessive diffusion of the slurry, affecting pattern accuracy and interlayer morphology. For example, the spray saturation is 55%, 60%, 65%, 70%, or 75%, but is not limited to these.

[0043] Specifically, in step S3, the power for initial curing is 50~100mW / cm. 2 The initial curing time is 2~5 seconds. Based on this curing condition, it can be ensured that the alumina curing slurry undergoes partial cross-linking and forms a stable initial structure.

[0044] Specifically, in step S5, the sintering temperature is 1400~1600℃, and the sintering temperature is maintained for 2~4 hours.

[0045] The alumina-toughened zirconia ceramic prepared by the above method has a flexural strength of 800 MPa, a hardness ≥12 GPa, and a fracture toughness ≥8 MPa•m. 1 / 2 .

[0046] The present invention will be further described below with reference to specific embodiments: Example 1 This embodiment provides an alumina curing slurry, the formulation of which is as follows: 40 parts RJ313 resin, 14 parts TPGDA, 20 parts DPHA, 3 parts Irgacure TPO, 1 part Irgacure 1173, 2 parts BYK-9076, and 80 parts alumina powder.

[0047] The particle size of the alumina powder is as follows: It is 0.05μm. The average particle size is 0.5 μm. It is 1.8μm.

[0048] The preparation method of the alumina curing slurry in this embodiment is as follows: Add 40 parts of RJ313 resin to a water-cooled mixing tank of a disperser. Turn on the water cooling system and maintain the water temperature below 25°C throughout the production process. While the disperser is running at 500 rpm, add 14 parts of TPGDA, 20 parts of DPHA, 3 parts of Irgacure TPO, and 1 part of Irgacure 1173. Continue dispersing at 500 rpm for 120 minutes to ensure complete dissolution and mixing, obtaining an intermediate. Then, sequentially add the intermediate, 2 parts of BYK-9076, and 80 parts of alumina powder to a horizontal ball mill jar and ball mill with alumina balls for 12 hours. Finally, pass the mixture through a 120-mesh sieve to obtain the final product.

[0049] The viscosity of the alumina curing slurry obtained in this embodiment is 90 mPa•s (25℃).

[0050] Example 2 This embodiment provides an alumina curing slurry, the formulation of which is as follows: DS-2547 resin 35 parts, TPGDA 22 parts, HDDA 18 parts, Irgacure TPO 2.5 parts, Irgacure 819 1 part, Duramax D-3019 1.5 parts, alumina powder 80 parts.

[0051] The particle size of the alumina powder is as follows: It is 0.05μm. The average particle size is 0.5 μm. It is 1.8μm.

[0052] The preparation method of the alumina curing slurry in this embodiment is as follows: Add 35 parts of DS-2547 resin to a water-cooled mixing tank of a disperser. Turn on the water cooling system and maintain the water temperature below 25°C throughout the production process. While the disperser is running at 500 rpm, add 18 parts of HDDA, 22 parts of TPGDA, 2.5 parts of Irgacure TPO, and 1 part of Irgacure 819. Continue dispersing at 500 rpm for 120 minutes to ensure complete dissolution and mixing, obtaining an intermediate. Then, sequentially add the intermediate, 1.5 parts of Duramax D-3019, and 80 parts of alumina powder to a horizontal ball mill jar and ball mill with alumina balls for 12 hours. Finally, pass the mixture through a 120-mesh sieve to obtain the final product.

[0053] The viscosity of the alumina curing slurry obtained in this embodiment is 81 mPa•s (25℃).

[0054] Example 3 This embodiment provides an alumina curing slurry, the formulation of which is as follows: 38 parts of SU 571M100 resin, 18 parts of TMPTA, 19 parts of PDDA, 3 parts of Irgacure 819, 2 parts of BYK-P104S, and 80 parts of alumina powder.

[0055] The particle size of the alumina powder is as follows: It is 0.05μm. The average particle size is 0.5 μm. It is 1.8μm.

[0056] The preparation method of the alumina curing slurry in this embodiment is as follows: Add 38 parts of SU 571M100 resin to a water-cooled mixing tank of a disperser. Turn on the water cooling system and maintain the water temperature below 25°C throughout the production process. While the disperser is running at 500 rpm, add 19 parts of PDDA, 18 parts of TMPTA, and 3 parts of Irgacure 819. Continue dispersing at 500 rpm for 120 minutes to ensure complete dissolution and mixing, obtaining an intermediate. Then, sequentially add the intermediate, 2 parts of BYK-P104S, and 80 parts of alumina powder to a horizontal ball mill jar and ball mill with alumina balls for 12 hours. Finally, pass the mixture through a 120-mesh sieve to obtain the final product.

[0057] The viscosity of the alumina curing slurry obtained in this embodiment is 77 mPa•s (25℃).

[0058] Comparative Example 1 This comparative example provides an alumina curing slurry, the formulation of which is as follows: 15 parts RJ313 resin, 75 parts TPGDA, 3 parts Irgacure TPO, 1 part Irgacure 1173, 2 parts BYK-9076, and 80 parts alumina powder.

[0059] The particle size of the alumina powder is as follows: It is 0.05μm. The average particle size is 0.5 μm. It is 1.8μm.

[0060] The preparation method of the alumina curing slurry in this comparative example is as follows: Add 15 parts of RJ313 resin to a water-cooled mixing tank of a disperser. Turn on the water cooling system and maintain the water temperature below 25°C throughout the production process. While the disperser is running at 500 rpm, add 75 parts of TPGDA, 3 parts of Irgacure TPO, and 1 part of Irgacure 1173. Continue dispersing at 500 rpm for 120 minutes to ensure complete dissolution and mixing, obtaining an intermediate. Then, sequentially add the intermediate, 2 parts of BYK-9076, and 80 parts of alumina powder to a horizontal ball mill jar and ball mill with alumina balls for 12 hours. Finally, pass the mixture through a 120-mesh sieve to obtain the final product.

[0061] The viscosity of the alumina curing slurry obtained in this comparative example is 31 mPa•s (25℃).

[0062] Comparative Example 2 This comparative example provides an alumina curing slurry, the formulation of which is as follows: 75 parts RJ313 resin, 15 parts TPGDA, 3 parts Irgacure TPO, 1 part Irgacure 1173, 2 parts BYK-9076, and 80 parts alumina powder.

[0063] The particle size of the alumina powder is as follows: It is 0.05μm. The average particle size is 0.5 μm. It is 1.8μm.

[0064] The preparation method of the alumina curing slurry in this comparative example is as follows: Add 75 parts of RJ313 resin to a water-cooled mixing tank of a disperser. Turn on the water cooling system and maintain the water temperature below 25°C throughout the production process. While the disperser is running at 500 rpm, add 15 parts of TPGDA, 3 parts of Irgacure TPO, and 1 part of Irgacure 1173. Continue dispersing at 500 rpm for 120 minutes to ensure complete dissolution and mixing, obtaining an intermediate. Then, sequentially add the intermediate, 2 parts of BYK-9076, and 80 parts of alumina powder to a horizontal ball mill jar and ball mill with alumina balls for 12 hours. Finally, pass the mixture through a 120-mesh sieve to obtain the final product.

[0065] The viscosity of the alumina curing slurry obtained in this comparative example is 184 mPa•s (25℃).

[0066] Comparative Example 3 This comparative example provides an alumina curing slurry, the formulation of which is as follows: 40 parts RJ313 resin, 14 parts TPGDA, 20 parts DPHA, 3 parts Irgacure TPO, 1 part Irgacure 1173, 2 parts BYK-9076, and 220 parts alumina powder.

[0067] The particle size of the alumina powder is as follows: It is 0.05μm. The average particle size is 0.5 μm. It is 1.8μm.

[0068] The preparation method of the alumina curing slurry in this comparative example is as follows: Add 40 parts of RJ313 resin to a water-cooled mixing tank of a disperser. Turn on the water cooling system and maintain the water temperature below 25°C throughout the production process. While the disperser is running at 500 rpm, add 14 parts of TPGDA, 20 parts of DPHA, 3 parts of Irgacure TPO, and 1 part of Irgacure 1173. Continue dispersing at 500 rpm for 120 minutes to ensure complete dissolution and mixing, obtaining an intermediate. Then, sequentially add the intermediate, 2 parts of BYK-9076, and 220 parts of alumina powder to a horizontal ball mill jar and ball mill with alumina balls for 12 hours. Finally, pass the mixture through a 120-mesh sieve to obtain the final product.

[0069] The viscosity of the alumina curing slurry obtained in this comparative example is 215 mPa•s (25℃).

[0070] Comparative Example 4 This comparative example provides an alumina curing slurry, the formulation of which is as follows: 40 parts RJ313 resin, 14 parts TPGDA, 20 parts DPHA, 3 parts Irgacure TPO, 1 part Irgacure 1173, 2 parts BYK-9076, and 80 parts alumina powder.

[0071] The particle size of the alumina powder is as follows: It is 4.3μm. The average particle size is 10.4 μm. It is 29.5μm.

[0072] The preparation method of the alumina curing slurry in this comparative example is as follows: Add 40 parts of RJ313 resin to a water-cooled mixing tank of a disperser. Turn on the water cooling system and maintain the water temperature below 25°C throughout the production process. While the disperser is running at 500 rpm, add 14 parts of TPGDA, 20 parts of DPHA, 3 parts of Irgacure TPO, and 1 part of Irgacure 1173. Continue dispersing at 500 rpm for 120 minutes to ensure complete dissolution and mixing, obtaining an intermediate. Then, sequentially add the intermediate, 2 parts of BYK-9076, and 80 parts of alumina powder to a horizontal ball mill jar and ball mill with alumina balls for 12 hours. Finally, pass the mixture through a 120-mesh sieve to obtain the final product.

[0073] The viscosity of the alumina curing slurry obtained in this comparative example is 55 mPa•s (25℃).

[0074] The alumina curing slurries obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were tested as follows: (1) After standing for 48 hours, observe whether there is sedimentation or stratification; (2) The printing was performed using the method described in Example 4. During the printing process, a portion of the cross-section of 2-3 layers of pre-cured zirconia powder was randomly selected, and the coverage of the alumina-cured ceramic slurry was observed using an electron microscope. The specific results are shown in the table below:

[0075] Example 4 This embodiment provides a method for preparing alumina-toughened zirconia ceramic, which includes the following steps: S1: Zirconia powder layer is formed using zirconia powder; The particle size of the zirconium oxide powder is as follows: It is 5.3 μm. The average particle size is 12.8 μm. The thickness is 19.6 μm. The thickness of the single-layer zirconia powder layer is 0.33 mm.

[0076] S2: Spray the alumina curing slurry of Example 1 at a predetermined position on the zirconium oxide powder layer; wherein the spray saturation is 55%.

[0077] S3: Ultraviolet light irradiation is used to initially cure the alumina curing slurry; the curing power is 80mW / cm. 2 The curing time is 3 seconds; S4: Repeat steps S1 to S3 until a ceramic green body is obtained; S5: Sinter the ceramic green body to obtain the alumina-toughened zirconia ceramic product; wherein the sintering temperature is 1450℃ and the holding time is 3h. Example 5 This embodiment provides a method for preparing alumina-toughened zirconia ceramics, which includes the following steps: S1: Zirconia powder layer is formed using zirconia powder; The particle size of the zirconium oxide powder is as follows: It is 5.3 μm. The average particle size is 12.8 μm. The thickness is 19.6 μm. The thickness of the single-layer zirconia powder layer is 0.33 mm.

[0078] S2: Spray the alumina curing slurry of Example 2 at a predetermined position on the zirconium oxide powder layer; wherein the spray saturation is 65%.

[0079] S3: Ultraviolet light irradiation is used to initially cure the alumina curing slurry; the curing power is 80mW / cm. 2 The curing time is 3.5 seconds. S4: Repeat steps S1 to S3 until a ceramic green body is obtained; S5: Sinter the ceramic green body to obtain the alumina-toughened zirconia ceramic product; wherein the sintering temperature is 1450℃ and the holding time is 3h.

[0080] Example 6 This embodiment provides a method for preparing alumina-toughened zirconia ceramics, which includes the following steps: S1: Zirconia powder layer is formed using zirconia powder; The particle size of the zirconium oxide powder is as follows: It is 5.3 μm. The average particle size is 12.8 μm. The thickness is 19.6 μm. The thickness of the single-layer zirconia powder layer is 0.33 mm.

[0081] S2: Spray the alumina curing slurry of Example 3 at a predetermined position on the zirconium oxide powder layer; wherein the spray saturation is 60%.

[0082] S3: Ultraviolet light irradiation is used to initially cure the alumina curing slurry; the curing power is 80mW / cm. 2 The curing time is 3 seconds; S4: Repeat steps S1 to S3 until a ceramic green body is obtained; S5: Sinter the ceramic green body to obtain the alumina-toughened zirconia ceramic product; wherein the sintering temperature is 1450℃ and the holding time is 3h.

[0083] Example 7 This embodiment provides a method for preparing alumina-toughened zirconia ceramic, which differs from Example 5 in that: The particle size of zirconium oxide powder is as follows: It is 4.2μm. The average particle size is 11.4 μm. The thickness is 22.3 μm. The thickness of the single-layer zirconia powder layer is 0.25 mm.

[0084] Everything else is the same as in Example 5.

[0085] The alumina-toughened zirconia ceramics obtained in Examples 4-7 were tested, and the specific results are shown in the table below:

[0086] The above description is a preferred embodiment of the invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the invention, and these improvements and modifications are also considered to be within the scope of protection of the invention.

Claims

1. A method for preparing alumina-toughened zirconia ceramic, characterized in that, Includes the following steps: S1: A zirconia powder layer is formed using zirconia powder; wherein the thickness of the zirconia powder layer is 0.1~0.5 mm; S2: Spraying alumina curing slurry at a predetermined position on the zirconium oxide powder layer; wherein the spray saturation of the alumina curing slurry is 50~80%; S3: Ultraviolet light irradiation is used to initially cure the alumina curing slurry; wherein the power of the initial curing is 50~100mW / cm. 2 The initial curing time is 2-5 seconds; S4: Repeat steps S1 to S3 until a ceramic green body is obtained; S5: Sinter the ceramic green body to obtain the alumina-toughened zirconia ceramic finished product; The alumina curing slurry is composed of the following components in parts by weight: 20-70 parts of UV-curable resin, 20-70 parts of UV monomer, 1-10 parts of photoinitiator, 0.1-5 parts of dispersant, and 60-200 parts of alumina powder; The solid content of the alumina curing slurry is 15~30 vol%, and its viscosity at 25℃ is 75~100 mPa•s; Wherein, the average particle size of the zirconium oxide powder is ≥10μm, and the average particle size of the alumina powder is 0.2~3μm; and the particle size of the zirconium oxide powder and the particle size of the alumina powder conform to the following relationship: in, The particle sizes are 10%, 50%, and 90% of the cumulative distribution of zirconium oxide powder, respectively. The particle sizes are 10%, 50%, and 90% of the cumulative alumina powder distribution, respectively.

2. The method for preparing alumina-toughened zirconia ceramic as described in claim 1, characterized in that, In step S5, the sintering temperature is 1400~1600℃.

3. The method for preparing alumina-toughened zirconia ceramic as described in claim 1, characterized in that, The average particle size of the zirconium oxide powder is 10~20μm.

4. The method for preparing alumina-toughened zirconia ceramic as described in claim 1, characterized in that, The photocurable resin is selected from one or more of RJ313, 6233, DR-U384, DS-2547, and SU 571M100; and / or The UV monomer is selected from one or more of TPGDA, DPHA, HDDA, TMPTA, and PDDA; and / or The photoinitiator is selected from one or more of Irgacure TPO, Irgacure 1173, and Irgacure 819; The dispersant is selected from one or more of Duramax D-3019, BYK-9076, and BYK-P104S.

5. The method for preparing alumina-toughened zirconia ceramic as described in claim 1, characterized in that, The photocurable resin is selected from RJ313, DS-2547, or SU 571M100; and / or The photoinitiator is selected from Irgacure TPO or Irgacure 819.

6. The method for preparing alumina-toughened zirconia ceramic as described in claim 1, characterized in that, The UV monomer is selected from a mixture of TPGDA and HDDA, with a weight ratio of TPGDA to HDDA of 1:1 to 1.4:1; or The UV monomer is a mixture of TPGDA and DPHA, with a weight ratio of TPGDA to DPHA of 0.6:1 to 1:1; or The UV monomer is a mixture of PDDA and TMPTA, with a weight ratio of PDDA to TMPTA of 0.8:1 to 1.2:

1.

7. The method for preparing alumina-toughened zirconia ceramic as described in claim 1, characterized in that, The preparation method of the alumina curing slurry includes: The photocurable resin, UV monomer, and photoinitiator are mixed evenly to obtain an intermediate. The intermediate, dispersant and alumina powder are mixed evenly to obtain alumina cured slurry.

8. An alumina-toughened zirconia ceramic, characterized in that, It is prepared by the method for preparing alumina-toughened zirconia ceramic as described in any one of claims 1 to 7.

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