WO2021248813A1 - Alumina ceramic and preparation method therefor - Google Patents

Alumina ceramic and preparation method therefor Download PDF

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WO2021248813A1
WO2021248813A1 PCT/CN2020/128669 CN2020128669W WO2021248813A1 WO 2021248813 A1 WO2021248813 A1 WO 2021248813A1 CN 2020128669 W CN2020128669 W CN 2020128669W WO 2021248813 A1 WO2021248813 A1 WO 2021248813A1
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alumina
slurry
powder
sintering
dispersant
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PCT/CN2020/128669
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French (fr)
Chinese (zh)
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甘志俭
程银兵
杨斌
庄志杰
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基迈克材料科技（苏州）有限公司
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Definitions

  • the invention relates to the technical field of ceramics, in particular to an alumina ceramic and a preparation method thereof.
  • the content of alumina in high-purity alumina powder is greater than 99wt%, and it has the characteristics of uniform particle size, easy dispersion, stable chemical properties, etc. It has incomparable optical, electrical, magnetic, and thermal properties that ordinary alumina powder (alumina content greater than 80wt%) cannot match. And mechanical properties, high-purity alumina ceramics have been widely used as anti-plasma erosion materials in semiconductor and liquid crystal display etching manufacturing equipment. Among semiconductor equipment, the value of precision ceramics accounts for about 20% of the equipment value, and the global market has an output value of approximately US$6 billion. The production of semiconductor alumina precision ceramic components is in its infancy in China. The current accelerated development of the domestic semiconductor industry will inevitably lead to an increase in the demand for semiconductor alumina precision ceramics.
  • alumina ceramics are different. Among them, a large number of methods used in industrial production are isostatic pressing, high temperature sintering, grinding processing, polishing and other processes. This method is mainly suitable for alumina ceramics with a purity of 95%. , But it is not suitable for other alumina ceramics such as alumina ceramics with a purity of 99%.
  • the alumina ceramics prepared by the above methods have problems such as low density and low mechanical strength of the ceramics, and cannot meet the requirements of semiconductor devices for alumina ceramics.
  • alumina ceramic and a preparation method thereof that can improve the density and mechanical properties.
  • a method for preparing alumina ceramics which includes the following steps:
  • the alumina powder is made into a slurry to obtain an alumina slurry with a particle size D90 less than or equal to 0.8 ⁇ m; the alumina slurry is dried to obtain alumina fine powder; the content of alumina in the alumina powder is ⁇ 99wt%;
  • the first dispersant and the lubricant are heated and melted, the alumina fine powder and the ultraviolet light absorber are added, mixed uniformly, and then vacuumed to obtain an alumina light-cured slurry;
  • the conditions of the normal pressure debinding and sintering are: heating up to 550°C to 650°C at a rate of (0.2 ⁇ 1)°C/min, holding for 6h to 10h, and then heating up to 1200°C at a rate of (1 ⁇ 5)°C/min ⁇ 1400°C, keep for 5h ⁇ 8h.
  • the above preparation method uses high-purity alumina powder as a raw material to obtain alumina slurry with D90 ⁇ 0.8 ⁇ m through ball milling, and then dry to prepare nano-scale, high-activity spherical alumina fine powder, which is then made into a light-curing slurry.
  • 3D printing is used to form a blank to meet the requirements of semiconductor equipment for ceramic shape and dimensional accuracy. It is often pressed and sintered at low temperature to make alumina ceramics. Due to the small particle size and high sintering activity of alumina fine powder, sintering can be completed within 1400 °C, and the sintered alumina grains at low temperature will not undergo abnormal mutations.
  • the grain size is uniform, and high-density, high-density, high-density, Alumina ceramics with high mechanical properties meet the demand for alumina ceramics in semiconductor equipment.
  • the alumina ceramic body of this method can be sintered under normal pressure and within 1400°C. Therefore, the sintering requirements can be met by using an ordinary normal pressure sintering furnace, which can reduce equipment cost input, and the sintering temperature is low, which can greatly reduce Energy costs.
  • the content of alumina in the alumina powder is ⁇ 99.99%
  • the D50 is 0.3 ⁇ m to 0.6 ⁇ m
  • the BET is 10 m 2 /g to 20 m 2 /g.
  • the conditions for the normal pressure debinding and sintering are: heating up to 600°C at a rate of (0.2 ⁇ 1)°C/min, holding for 6h ⁇ 10h, and then at a rate of (2 ⁇ 5)°C/min Raise the temperature to 1200°C ⁇ 1400°C and keep it for 6h ⁇ 8h.
  • the aluminum oxide particles are 80 to 85 parts
  • the photosensitive resin is 5 to 10 parts
  • the first dispersant is 1-10 parts
  • the lubricant is 2-10 parts
  • the ultraviolet light absorber is 1-5 parts.
  • the photosensitive resin is selected from at least one of epoxy acrylic resin, urethane acrylic resin, and polyester acrylic resin.
  • the first dispersant is selected from at least one of stearic acid, oleic acid, and polyethylene glycol.
  • the lubricant is selected from at least one of paraffin wax and glycerin.
  • the ultraviolet light absorber is selected from at least one of phenyl salicylate, 2,4-dihydroxybenzophenone, and resorcinol monobenzoate.
  • the step of preparing alumina powder into a slurry is: after mixing water, a second dispersant and the high-purity alumina powder, ball milling for 2h-6h, the high-purity alumina
  • the weight ratio of the powder to the water is (4-7):(3-6)
  • the weight of the second dispersant is 1% to 3% of the high-purity alumina powder
  • the second dispersant For organic solvents.
  • the second dispersant is selected from at least one of polyvinyl alcohol, polyethylene glycol, and polystyrene.
  • the drying adopts a spray drying method, and the inlet air temperature of the drying is 250° C. to 350° C., the outlet air temperature is 100° C. to 150° C., and the rotation speed is 9000 rpm to 12000 rpm.
  • the step of grinding and polishing the alumina ceramic is further included to control the surface roughness Ra of the alumina ceramic after grinding and polishing Ra ⁇ 0.1 ⁇ m.
  • an alumina ceramic is provided, which is prepared by the above-mentioned preparation method of alumina ceramic.
  • FIG. 1 is a schematic diagram of a method for preparing alumina ceramics according to an embodiment.
  • the molding methods of alumina ceramic products mainly adopt dry pressing, grouting, extrusion, cold isostatic pressing, injection, casting, hot pressing and hot isostatic pressing. These molding methods are not easy to prepare with complex shapes and sizes. The problem of high-precision green bodies.
  • the present invention uses high-purity alumina as a raw material, combined with a 3D printing molding method, and then performs low-temperature and atmospheric sintering at 1400°C and below to prepare alumina ceramics with high density, fine grains, and high mechanical properties. Meet the requirements of semiconductor equipment for alumina ceramics.
  • An embodiment of the present invention provides a method for preparing an alumina ceramic sintered body, as shown in FIG. 1, including the following steps S10 to S18.
  • the alumina powder is made into a slurry and dried to obtain alumina fine powder.
  • alumina powder with alumina content ⁇ 99wt% is made into slurry to obtain alumina slurry with particle size D90 ⁇ 0.8 ⁇ m, and then dried to obtain alumina fine powder.
  • the content of alumina in the alumina powder is ⁇ 99.99 wt%
  • the D50 is 0.3 ⁇ m to 0.6 ⁇ m
  • the BET (specific surface area) is 10 m 2 /g to 20 m 2 /g.
  • D90 represents the particle size whose cumulative distribution of particles is 90%, that is, the volume content of particles smaller than this size accounts for 90% of all particles.
  • D50 represents the particle size at which the cumulative distribution of particles is 50%, also called median particle.
  • a D50 of 0.3 ⁇ m to 0.6 ⁇ m means that the volume of particles with a particle size of 0.3 ⁇ m to 0.6 ⁇ m in the alumina powder accounts for 50%, and the volume of particles smaller than 0.3 ⁇ m and larger than 0.6 ⁇ m accounts for 50%.
  • the step of preparing the alumina powder into a slurry is: after mixing the ball milling medium, the second dispersant and the alumina powder, ball milling for 2h-6h, the weight ratio of the alumina powder to the ball milling medium is (4 ⁇ 7): (3 ⁇ 6), the weight of the second dispersant is 1% ⁇ 3% of the high purity alumina powder.
  • the ball milling medium is selected from water and volatile organic solvents; preferably, the ball milling medium is water.
  • the second dispersant is selected from at least one of polyvinyl alcohol, polyethylene glycol and polystyrene; preferably, the second dispersant is polyvinyl alcohol.
  • high-purity alumina powder is added, and after stirring to form a slurry, ball milling is performed in a high-speed nano-sand mill.
  • the high-purity alumina powder accounts for 40% to 70% of the total weight of the high-purity alumina powder and the ball milling medium, and the weight of the second dispersant is 1% to 3% of the weight of the high-purity alumina powder.
  • Use water as the ball milling medium and alumina ball as the milling ball is 2h-6h, and the particle size of the slurry obtained after ball milling is D90 ⁇ 0.8 ⁇ m.
  • a centrifugal spray dryer is used for spray drying, and the centrifugal drying of spray drying has an inlet air temperature of 250°C to 350°C, an outlet temperature of 100°C to 150°C, and an atomization speed of 9000rpm to 12000rpm to prepare Nano-level, high bulk density spherical alumina fine powder.
  • the first dispersant and the lubricant are heated and melted, the alumina fine powder and the ultraviolet light absorber are added, mixed uniformly, and then vacuumed to obtain the alumina light-cured slurry.
  • the amount of alumina fine powder is 80 to 85 parts by weight, the photosensitive resin is 5 to 10 parts, and the first dispersant is 1 to 10 parts.
  • the amount of the agent is 2-10 parts, and the amount of the ultraviolet light absorber is 1-5 parts.
  • the photosensitive resin is selected from at least one of polyacrylic resin, epoxy acrylic resin, urethane acrylic resin, and polyester acrylic resin;
  • the first dispersant is selected from stearic acid, oleic acid, and polyethylene glycol
  • the lubricant is selected from paraffin wax and/or glycerin;
  • the ultraviolet light absorber is selected from at least one of phenyl salicylate, 2,4-dihydroxybenzophenone and resorcinol monobenzoate A sort of.
  • the photosensitive resin is a polyacrylic resin
  • the first dispersant is stearic acid
  • the lubricant is paraffin wax
  • the ultraviolet light absorber is phenyl salicylate.
  • the polyacrylic resin is melted at 190°C ⁇ 200°C, after cooling to 100°C ⁇ 120°C, stearic acid is added, after melting, the temperature is reduced to 80°C ⁇ 100°C, paraffin wax is added to melt, and after the organic fat is completely melted, Continue to add alumina fine powder under stirring. After the addition is complete, add ultraviolet light absorber and continue to stir for 2h ⁇ 4h until the slurry is uniformly mixed. Then vacuum treatment is carried out to eliminate bubbles in the slurry to obtain aluminum oxide light curing Slurry. In this way, defects such as holes in the aluminum oxide light-curing slurry can be avoided during molding.
  • the alumina light-cured slurry prepared in step S12 is printed and molded by a 3D printer according to the design drawings to obtain an alumina ceramic body.
  • 3D printing molding can meet the requirements of semiconductor equipment for shape complex and high dimensional accuracy, and high production efficiency.
  • the alumina ceramic body undergoes atmospheric pressure debinding and sintering to obtain alumina ceramics.
  • the conditions for normal pressure debinding and sintering are: heating up to 550°C to 650°C at a rate of (0.2 ⁇ 1)°C/min, holding for 6h to 10h, and then heating up to 1200°C at a rate of (1 ⁇ 5)°C/min °C ⁇ 1400°C, keep for 5h ⁇ 8h.
  • the present invention uses nano-grade high-purity alumina powder as the raw material, can complete debinding and sintering at 1400°C or less, and can avoid the excessively large sintering temperature (such as 1600°C ⁇ 1700°C) causing part of the crystal grain size in the ceramic to be too large.
  • the mechanical strength of the body is reduced and it is easy to crack.
  • the ceramic grain size obtained by sintering is uniform, high density, and high mechanical properties, which can meet the needs of alumina ceramics for semiconductor equipment.
  • the conditions for normal pressure debinding and sintering are: heating up to 600°C at a rate of (0.2 ⁇ 1)°C/min, holding for 6h-10h, and then heating up to 1200°C at a rate of (2 ⁇ 5)°C/min °C ⁇ 1400°C, keep for 6h ⁇ 8h.
  • an atmospheric pressure sintering furnace is used to perform debinding and sintering of the alumina ceramic body.
  • the debinding and sintering work can be completed at one time, avoiding the need to cool down and then increase the temperature to perform the sintering operation after the debinding furnace is used alone to complete the debinding.
  • it can save the installation of debinding equipment, shorten the sintering time and improve production efficiency.
  • a CNC grinder is used to perform fine processing operations such as surface grinding, drilling, and grooving on the sintered alumina ceramic.
  • the alumina ceramic is polished with a neutral polishing liquid, and the surface roughness Ra of the alumina ceramic is controlled by grinding and polishing to be less than or equal to 0.1 ⁇ m.
  • Another embodiment of the present invention provides an alumina ceramic prepared by the above preparation method.
  • the alumina ceramic has high density and good mechanical properties, and can meet the requirements of semiconductor equipment for ceramic materials.
  • the surface roughness Ra of the alumina ceramic is less than or equal to 0.1 ⁇ m.
  • the alumina ceramic prepared by the above method of the present invention has a density of 3.9g/cm 3 and above, a compressive strength>2600Mpa, a volume resistivity>10 14 ⁇ cm, a hardness (HRA) of 88, and a flexural strength of 350MPa ⁇ 360MPa, the thermal expansion coefficient is 7.5 ⁇ 10 -6 /°C ⁇ 8.5 ⁇ 10 -6 /°C, which meets the requirements for the use of alumina precision ceramics in semiconductor equipment.
  • Raw material high-purity alumina powder: alumina purity 99.99% or more, particle size D50: 0.4 ⁇ m, BET: 13m 2 /g.
  • alumina ceramic body Place the formed alumina ceramic body in the atmospheric pressure debinding and sintering furnace.
  • the furnace temperature is increased to 600°C at a heating rate of 0.5°C/min, and kept at this temperature for 6 hours to complete the debinding operation of the alumina ceramics, and completely remove Organic grease; alumina ceramics continue to heat up to 1400°C at a heating rate of 2.5°C/min, and keep it at 1400°C for 6 hours.
  • the alumina can be discharged from the sintering furnace when the temperature is naturally lowered to below 200°C, and the firing is completed to obtain an alumina ceramic sintered body.
  • the alumina ceramic sintered body is polished by a neutral polishing liquid after CNC grinding and finishing, and its surface roughness Ra ⁇ 0.1 ⁇ m.
  • Raw material high-purity alumina powder: alumina purity 99.99% or more, particle size D50: 0.3 ⁇ m, BET: 15m 2 /g.
  • alumina ceramic body Place the formed alumina ceramic body in the atmospheric pressure debinding and sintering furnace.
  • the furnace temperature is increased to 600°C at a heating rate of 0.5°C/min, and kept at this temperature for 6 hours to complete the debinding operation of the alumina ceramics, and completely remove Organic grease; alumina ceramics continue to heat up to 1350°C at a heating rate of 2.0°C/min, and keep it at 1350°C for 8 hours.
  • the alumina can be discharged from the sintering furnace when the temperature is naturally lowered to below 200°C, and the firing is completed to obtain an alumina ceramic sintered body.
  • the alumina ceramic sintered body is polished by a neutral polishing liquid after CNC grinding and finishing, and its surface roughness Ra ⁇ 0.1 ⁇ m.
  • Raw material high-purity alumina powder: alumina purity 99.99% or more, particle size D50: 0.3 ⁇ m, BET: 18m 2 /g.
  • alumina ceramic body Place the formed alumina ceramic body in an atmospheric degreasing and sintering furnace.
  • the temperature of the furnace is increased to 600°C at a heating rate of 0.5°C/min, and the alumina ceramics degreasing operation is completed by keeping it at this temperature for 6 hours. Removal of organic grease; the alumina ceramic continues to be heated to 1300°C at a heating rate of 2.0°C/min, and kept at 1300°C for 7 hours.
  • the alumina can be discharged from the sintering furnace when the temperature is naturally lowered to below 200°C, and the firing is completed to obtain an alumina ceramic sintered body.
  • Raw material high-purity alumina powder: alumina purity 99.99% or more, particle size D50: 2.5 ⁇ m, BET: 8m 2 /g.
  • alumina ceramic body Place the formed alumina ceramic body in an atmospheric degreasing and sintering furnace.
  • the temperature of the furnace is increased to 600°C at a heating rate of 0.5°C/min, and the alumina ceramics degreasing operation is completed by keeping it at this temperature for 6 hours.
  • Remove organic grease; alumina ceramics continue to heat up to 1400°C at a heating rate of 2.5°C/min, and keep it at 1400°C for 6 hours.
  • the alumina can be discharged after the sintering furnace is naturally cooled to below 200°C, and the firing is completed.
  • Raw material high-purity alumina powder: alumina purity 99.99% or more, particle size D50: 2.5 ⁇ m, BET: 8m 2 /g.
  • the alumina slurry is dried in a spray dryer at a drying temperature of 280°C and an atomizing plate rotating speed of 10,000 rpm to prepare spherical alumina powder.
  • Raw material alumina purity 95%, particle size D50: 0.3 ⁇ m, BET: 15 m 2 /g.
  • the slurry is dried in a spray dryer at a drying temperature of 280° C. and an atomizing plate rotating speed of 10000 rpm to prepare spherical alumina ultrafine powder.
  • the alumina ceramic body is placed in the atmospheric pressure debinding and sintering furnace.
  • the furnace temperature is increased to 600°C at a heating rate of 0.5°C/min, and the alumina ceramic body is debinding at this temperature for 6 hours to completely remove organic Grease;
  • Alumina ceramics continue to heat up to 1350°C at a heating rate of 2.0°C/min, and keep it at 1350°C for 8 hours.
  • the alumina can be discharged after the sintering furnace is naturally cooled to below 200°C, and the firing is completed.
  • test standards for each performance test item are as follows:
  • Examples 1 to 3 of the present invention use high-purity alumina powder as the raw material, after ball milling, spray drying, 3D printing, and low-temperature and atmospheric sintering, which can produce high density, fine grains, and high strength.
  • Precision alumina ceramics with high toughness, high hardness, high temperature resistance, low thermal expansion coefficient, and insulation.
  • the density of comparative example 1 alumina ceramics is too small, not completely sintered and compact, and does not meet the requirements of the use of alumina precision ceramics for semiconductor equipment, indicating that the performance indicators of alumina raw material powder have a significant effect on reducing the sintering temperature.
  • the particle size of the alumina raw material powder When the size of the slurry is too large or the size of the slurry after grinding is too large, the powder sintering activity will be reduced, and compact sintering cannot be completed at a lower temperature, resulting in low density of the sintered ceramics, and other performance indicators of the corresponding ceramics also decreasing.
  • Comparative Example 2 and Comparative Example 1 using the same alumina powder and treatment process, the density of alumina ceramics is increased when the sintering temperature is changed to 1700°C. However, the process requires high sintering temperature, energy consumption and equipment costs.
  • the performance parameters of the fired alumina ceramics still have a gap with the performance of the embodiment of the present invention, especially the compressive strength and flexural strength are obviously inferior to the embodiment of the present invention.
  • Comparative Example 3 and Example 2 used alumina raw material powder with the same particle size, but the purity of the alumina was 95%, and the other treatment processes were the same.
  • the alumina raw material powder Purity has a great influence on the preparation of alumina ceramics for semiconductor equipment.
  • the impurities contained in alumina are immiscible with alumina during the high temperature liquid phase reaction process, which prevents the fusion of alumina crystals, increases the energy required for the reaction, and causes The density of sintered products is not high, and the corresponding mechanical properties such as hardness, compressive strength and flexural strength are poor.

Abstract

Disclosed are an alumina ceramic and a preparation method therefor. The method comprises the following steps: preparing alumina powder into a slurry to obtain an alumina slurry having a particle size D90 of less than or equal to 0.8 μm; drying the alumina slurry to obtain alumina fine powder; the content of alumina in the alumina powder being ≥ 99 wt%; heating and melting a photosensitive resin, a first dispersing agent and a lubricant, then adding the alumina fine powder and an ultraviolet absorber, and performing a vacuumizing treatment after mixing same uniformly to obtain an alumina light curing slurry; performing 3D printing and forming on the alumina light curing slurry to obtain an alumina ceramic green body; performing atmospheric degreasing and sintering on the alumina ceramic green body to obtain an alumina ceramic; and conditions for the atmospheric degreasing and sintering being as follows: increasing the temperature to 550°C to 650°C at a rate of (0.2 to 1)°C/min, maintaining the temperature for 6 h to 10 h, and then increasing the temperature to 1200 °C to 1400 °C at a rate of (1 to 5)°C/min, and maintaining the temperature for 5 h to 8 h. The alumina ceramic prepared by using the method has a high density and good mechanical properties, and can meet requirements of a semiconductor device for a ceramic material.

Description

氧化铝陶瓷及其制备方法Alumina ceramics and preparation method thereof
本申请要求2020年6月9日向中国国家知识产权局的申请号为202010517344.5的专利申请的优先权。This application claims the priority of the patent application with the application number 202010517344.5 to the State Intellectual Property Office of China on June 9, 2020.
技术领域Technical field
本发明涉及陶瓷技术领域，特别是涉及一种氧化铝陶瓷及其制备方法。The invention relates to the technical field of ceramics, in particular to an alumina ceramic and a preparation method thereof.
背景技术Background technique
高纯氧化铝粉中氧化铝的含量大于99wt％，具有粒度均匀、易分散、化学性能稳定等特点，具有普通氧化铝粉(氧化铝含量大于80wt％)无法比拟的光、电、磁、热和机械性能，在半导体及液晶显示屏的刻蚀制造装备中，高纯氧化铝陶瓷作为抗等离子冲蚀材料已经得到了广泛应用。半导体设备中，精密陶瓷的价值约占设备价值的20％左右，全球市场约有60亿美元的产值。半导体氧化铝精密陶瓷元器件的生产在国内属于起步阶段，目前国内半导体行业的加速发展，必然导致半导体用氧化铝精密陶瓷的需求量加大。The content of alumina in high-purity alumina powder is greater than 99wt%, and it has the characteristics of uniform particle size, easy dispersion, stable chemical properties, etc. It has incomparable optical, electrical, magnetic, and thermal properties that ordinary alumina powder (alumina content greater than 80wt%) cannot match. And mechanical properties, high-purity alumina ceramics have been widely used as anti-plasma erosion materials in semiconductor and liquid crystal display etching manufacturing equipment. Among semiconductor equipment, the value of precision ceramics accounts for about 20% of the equipment value, and the global market has an output value of approximately US$6 billion. The production of semiconductor alumina precision ceramic components is in its infancy in China. The current accelerated development of the domestic semiconductor industry will inevitably lead to an increase in the demand for semiconductor alumina precision ceramics.
目前氧化铝陶瓷的制作方法各不相同，其中，大量被工业化生产使用的方法是采用等静压成型、高温烧结、打磨加工、抛光等工艺，该方法主要适用于纯度为95％的氧化铝陶瓷，但对其它氧化铝陶瓷如纯度为99％的氧化铝陶瓷并不适合。上述方法制得的氧化铝陶瓷存在致密度较低、陶瓷的机械强度不高等问题，不能满足半导体设备对氧化铝陶瓷的要求。At present, the production methods of alumina ceramics are different. Among them, a large number of methods used in industrial production are isostatic pressing, high temperature sintering, grinding processing, polishing and other processes. This method is mainly suitable for alumina ceramics with a purity of 95%. , But it is not suitable for other alumina ceramics such as alumina ceramics with a purity of 99%. The alumina ceramics prepared by the above methods have problems such as low density and low mechanical strength of the ceramics, and cannot meet the requirements of semiconductor devices for alumina ceramics.
发明内容Summary of the invention
基于此，有必要提供一种能够提高致密度及机械性能的氧化铝陶瓷及其制备方法。本发明的一个方面，提供一种氧化铝陶瓷的制备方法，包括如下步骤：Based on this, it is necessary to provide an alumina ceramic and a preparation method thereof that can improve the density and mechanical properties. In one aspect of the present invention, there is provided a method for preparing alumina ceramics, which includes the following steps:
将氧化铝粉制成浆料，得到粒径D90小于或等于0.8μm的氧化铝浆料；将所述氧化铝浆料干燥，得到氧化铝细粉；所述氧化铝粉中氧化铝的含量≥99wt％；The alumina powder is made into a slurry to obtain an alumina slurry with a particle size D90 less than or equal to 0.8 μm; the alumina slurry is dried to obtain alumina fine powder; the content of alumina in the alumina powder is ≥ 99wt%;
将光敏树脂、第一分散剂和润滑剂加热融化后，加入所述氧化铝细粉和紫外光吸收剂，混合均匀后进行抽真空处理，得到氧化铝光固化浆料；After the photosensitive resin, the first dispersant and the lubricant are heated and melted, the alumina fine powder and the ultraviolet light absorber are added, mixed uniformly, and then vacuumed to obtain an alumina light-cured slurry;
将所述氧化铝光固化浆料经3D打印成型，得到氧化铝陶瓷坯体；3D printing the aluminum oxide light-cured slurry to obtain an aluminum oxide ceramic body;
将所述氧化铝陶瓷坯体经过常压脱脂烧结，得到氧化铝陶瓷；Subjecting the alumina ceramic body to atmospheric pressure debinding and sintering to obtain alumina ceramics;
所述常压脱脂烧结的条件为：以(0.2～1)℃/min的速率升温至550℃～650℃，保温6h～10h，然后以(1～5)℃/min的速率升温至1200℃～1400℃，保温5h～8h。The conditions of the normal pressure debinding and sintering are: heating up to 550°C to 650°C at a rate of (0.2～1)°C/min, holding for 6h to 10h, and then heating up to 1200°C at a rate of (1～5)°C/min ～1400℃, keep for 5h～8h.
上述制备方法以高纯氧化铝粉为原料，经过球磨得到D90≤0.8μm的氧化铝浆料，然后干燥，制得纳米级、高活性的球形氧化铝细粉，而后制成光固化浆料，采用3D打印成型制坯，满足半导体设备对陶瓷形状和尺寸精度的要求，经常压脱脂低温烧结，制成氧化铝陶瓷。由于氧化铝细粉的粒径小、烧结活性高，从而可以在1400℃以内完成烧结，且在低温下烧结氧化铝晶粒不会发生异常突变，晶粒尺寸均匀，能够制备出高致密度、高机械性能的氧化铝陶瓷，满足半导体设备对氧化铝陶瓷的需求。The above preparation method uses high-purity alumina powder as a raw material to obtain alumina slurry with D90≤0.8μm through ball milling, and then dry to prepare nano-scale, high-activity spherical alumina fine powder, which is then made into a light-curing slurry. 3D printing is used to form a blank to meet the requirements of semiconductor equipment for ceramic shape and dimensional accuracy. It is often pressed and sintered at low temperature to make alumina ceramics. Due to the small particle size and high sintering activity of alumina fine powder, sintering can be completed within 1400 ℃, and the sintered alumina grains at low temperature will not undergo abnormal mutations. The grain size is uniform, and high-density, high-density, high-density, Alumina ceramics with high mechanical properties meet the demand for alumina ceramics in semiconductor equipment.
同时，该方法的氧化铝陶瓷坯体可在常压下、1400℃以内完成烧结，因此使用普通的常压烧结炉即可满足烧结要求，可减少设备成本投入，而且烧结温度低，可大幅降低能耗成本。At the same time, the alumina ceramic body of this method can be sintered under normal pressure and within 1400°C. Therefore, the sintering requirements can be met by using an ordinary normal pressure sintering furnace, which can reduce equipment cost input, and the sintering temperature is low, which can greatly reduce Energy costs.
在其中一些实施例中，所述氧化铝粉中氧化铝的含量≥99.99％、D50为0.3μm～0.6μm、BET为10m 2/g～20m 2/g。 In some of the embodiments, the content of alumina in the alumina powder is ≥99.99%, the D50 is 0.3 μm to 0.6 μm, and the BET is 10 m 2 /g to 20 m 2 /g.
在其中一些实施例中，所述常压脱脂烧结的条件为：以(0.2～1)℃/min的速率升温至600℃，保温6h～10h，然后以(2～5)℃/min的速率升温至1200℃～1400℃，保温6h～8h。In some of the embodiments, the conditions for the normal pressure debinding and sintering are: heating up to 600°C at a rate of (0.2～1)°C/min, holding for 6h～10h, and then at a rate of (2～5)°C/min Raise the temperature to 1200℃～1400℃ and keep it for 6h～8h.
在其中一些实施例中，在所述氧化铝光固化浆料中按重量份计，所述氧化铝颗粒为80～85份、所述光敏树脂为5～10份、所述第一分散剂为1～10份，所述润滑剂为2～10份、所述紫外光吸收剂为1～5份。In some of the embodiments, in the aluminum oxide light-curable slurry, in parts by weight, the aluminum oxide particles are 80 to 85 parts, the photosensitive resin is 5 to 10 parts, and the first dispersant is 1-10 parts, the lubricant is 2-10 parts, and the ultraviolet light absorber is 1-5 parts.
在其中一些实施例中，所述光敏树脂选自环氧丙烯酸树脂、聚氨酯丙烯酸树脂和聚酯丙烯酸树脂中的至少一种。In some embodiments, the photosensitive resin is selected from at least one of epoxy acrylic resin, urethane acrylic resin, and polyester acrylic resin.
在其中一些实施例中，所述第一分散剂选自硬脂酸、油酸和聚乙二醇中的至少一种。In some embodiments, the first dispersant is selected from at least one of stearic acid, oleic acid, and polyethylene glycol.
在其中一些实施例中，所述润滑剂选自石蜡和甘油中的至少一种。In some embodiments, the lubricant is selected from at least one of paraffin wax and glycerin.
在其中一些实施例中，所述紫外光吸收剂选自水杨酸苯酯、2，4-二羟基二苯甲酮和单苯甲酸间苯二酚酯中的至少一种。In some embodiments, the ultraviolet light absorber is selected from at least one of phenyl salicylate, 2,4-dihydroxybenzophenone, and resorcinol monobenzoate.
在其中一些实施例中，所述将氧化铝粉制成浆料的步骤为：将水、第二分散剂和所述高纯氧化铝粉混合后，球磨2h～6h，所述高纯氧化铝粉与所述水的重量比为(4～7):(3～6)，所述第二分散剂的重量为所述高纯氧化铝粉的1％～3％，所述第二分散剂为有机溶剂。In some of the embodiments, the step of preparing alumina powder into a slurry is: after mixing water, a second dispersant and the high-purity alumina powder, ball milling for 2h-6h, the high-purity alumina The weight ratio of the powder to the water is (4-7):(3-6), the weight of the second dispersant is 1% to 3% of the high-purity alumina powder, and the second dispersant For organic solvents.
在其中一些实施例中，所述第二分散剂选自聚乙烯醇、聚乙二醇和聚苯乙烯中的至少一种。In some embodiments, the second dispersant is selected from at least one of polyvinyl alcohol, polyethylene glycol, and polystyrene.
在其中一些实施例中，所述干燥采用喷雾干燥的方式，所述干燥的进风温度为250℃～350℃、出风温度为100℃～150℃、转速为9000rpm～12000rpm。In some of the embodiments, the drying adopts a spray drying method, and the inlet air temperature of the drying is 250° C. to 350° C., the outlet air temperature is 100° C. to 150° C., and the rotation speed is 9000 rpm to 12000 rpm.
在其中一些实施例中，在所述常压脱脂烧结之后还包括对所述氧化铝陶瓷进行打磨和抛光的步骤，以控制打磨和抛光后所述氧化铝陶瓷的表面粗糙度Ra≤0.1μm。In some of the embodiments, after the atmospheric pressure debinding and sintering, the step of grinding and polishing the alumina ceramic is further included to control the surface roughness Ra of the alumina ceramic after grinding and polishing Ra≤0.1 μm.
本发明的又一个方面，提供了一种氧化铝陶瓷，该氧化铝陶瓷为采用上述的氧化铝陶瓷的制备方法制得。In yet another aspect of the present invention, an alumina ceramic is provided, which is prepared by the above-mentioned preparation method of alumina ceramic.
附图说明Description of the drawings
图1为一实施方式的氧化铝陶瓷的制备方法的示意图。FIG. 1 is a schematic diagram of a method for preparing alumina ceramics according to an embodiment.
具体实施方式detailed description
为了便于理解本发明，下面将参照相关附图对本发明进行更全面的描述。附图中给出了本发明的较佳实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。In order to facilitate the understanding of the present invention, the present invention will be described more fully below with reference to the relevant drawings. The preferred embodiments of the present invention are shown in the accompanying drawings. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments, and are not intended to limit the present invention. The term "and/or" as used herein includes any and all combinations of one or more related listed items.
目前氧化铝陶瓷制品成型的方法主要采用干压、注浆、挤压、冷等静压、注射、流延、热压与热等静压成型等方法，这些成型方法存在不易制备形状复 杂、尺寸精度高的坯体的问题。而且，采用普通氧化铝粉体制备陶瓷需要在1700℃以上的高温炉内完成烧结，不但对烧结炉的性能要求较高、能耗高，且由于普通氧化铝粉体的粒径大，烧结活性低，在高温烧结时较难获得致密度高的氧化铝陶瓷，以及存在部分晶粒尺寸过大，导致陶瓷的机械强度不高，容易开裂，从而不能适用于半导体设备。At present, the molding methods of alumina ceramic products mainly adopt dry pressing, grouting, extrusion, cold isostatic pressing, injection, casting, hot pressing and hot isostatic pressing. These molding methods are not easy to prepare with complex shapes and sizes. The problem of high-precision green bodies. Moreover, the use of ordinary alumina powder to prepare ceramics needs to be sintered in a high-temperature furnace above 1700°C, which not only requires higher performance and energy consumption, but also because of the large particle size of ordinary alumina powder and the sintering activity Low, it is difficult to obtain high-density alumina ceramics during high-temperature sintering, and some of the crystal grains are too large, resulting in low mechanical strength and easy cracking of the ceramics, which makes it unsuitable for semiconductor devices.
因此，本发明以高纯氧化铝为原料，结合3D打印成型方法制坯后，在1400℃及以内进行低温常压烧结，制备高致密度、细晶粒、高机械性能的氧化铝陶瓷，能够满足半导体设备对氧化铝陶瓷的要求。Therefore, the present invention uses high-purity alumina as a raw material, combined with a 3D printing molding method, and then performs low-temperature and atmospheric sintering at 1400°C and below to prepare alumina ceramics with high density, fine grains, and high mechanical properties. Meet the requirements of semiconductor equipment for alumina ceramics.
本发明一实施方式提供一种氧化铝陶瓷烧结体的制备方法，如图1所示，包括如下步骤S10～S18。An embodiment of the present invention provides a method for preparing an alumina ceramic sintered body, as shown in FIG. 1, including the following steps S10 to S18.
S10、将氧化铝粉制成浆料、干燥，得到氧化铝细粉。S10. The alumina powder is made into a slurry and dried to obtain alumina fine powder.
具体地，将氧化铝含量≥99wt％的氧化铝粉制成浆料，得到粒径D90≤0.8μm的氧化铝浆料，然后干燥，得到氧化铝细粉。Specifically, alumina powder with alumina content ≥99wt% is made into slurry to obtain alumina slurry with particle size D90≤0.8 μm, and then dried to obtain alumina fine powder.
在一些实施例中，氧化铝粉中氧化铝的含量≥99.99wt％、D50为0.3μm～0.6μm、BET(比表面积)为10m 2/g～20m 2/g。 In some embodiments, the content of alumina in the alumina powder is ≥99.99 wt%, the D50 is 0.3 μm to 0.6 μm, and the BET (specific surface area) is 10 m 2 /g to 20 m 2 /g.
D90表示颗粒累积分布为90％的粒径，即小于此粒径的颗粒体积含量占全部颗粒的90％。D50表示颗粒累积分布为50％的粒径，也叫中位粒。D50为0.3μm～0.6μm表示氧化铝粉中颗粒粒径在0.3μm～0.6μm的颗粒体积占50％，小于0.3μm和大于0.6μm的颗粒体积共占50％。D90 represents the particle size whose cumulative distribution of particles is 90%, that is, the volume content of particles smaller than this size accounts for 90% of all particles. D50 represents the particle size at which the cumulative distribution of particles is 50%, also called median particle. A D50 of 0.3 μm to 0.6 μm means that the volume of particles with a particle size of 0.3 μm to 0.6 μm in the alumina powder accounts for 50%, and the volume of particles smaller than 0.3 μm and larger than 0.6 μm accounts for 50%.
在一些实施例中，将氧化铝粉制成浆料的步骤为：将球磨介质、第二分散剂和氧化铝粉混合后，球磨2h～6h，氧化铝粉与球磨介质的重量比为(4～7):(3～6)，第二分散剂的重量为高纯氧化铝粉的1％～3％。In some embodiments, the step of preparing the alumina powder into a slurry is: after mixing the ball milling medium, the second dispersant and the alumina powder, ball milling for 2h-6h, the weight ratio of the alumina powder to the ball milling medium is (4 ～7): (3～6), the weight of the second dispersant is 1%～3% of the high purity alumina powder.
进一步地，球磨介质选自水和易挥发的有机溶剂；较优地，球磨介质为水。第二分散剂选自聚乙烯醇、聚乙二醇和聚苯乙烯中的至少一种；较优地，第二分散剂为聚乙烯醇。Further, the ball milling medium is selected from water and volatile organic solvents; preferably, the ball milling medium is water. The second dispersant is selected from at least one of polyvinyl alcohol, polyethylene glycol and polystyrene; preferably, the second dispersant is polyvinyl alcohol.
在一些实施例中，将球磨介质与第二分散剂搅拌混匀后，加入高纯氧化铝粉，搅拌成浆后，在高速纳米砂磨机内进行球磨。其中高纯氧化铝粉占高纯氧化铝粉和球磨介质总重量的40％～70％，第二分散剂的重量为高纯氧化铝粉重量 的1％～3％。以水为球磨介质、氧化铝球为研磨球，球磨时间为2h～6h，球磨后所得浆料的粒径D90≤0.8μm。In some embodiments, after the ball milling medium and the second dispersant are stirred and evenly mixed, high-purity alumina powder is added, and after stirring to form a slurry, ball milling is performed in a high-speed nano-sand mill. The high-purity alumina powder accounts for 40% to 70% of the total weight of the high-purity alumina powder and the ball milling medium, and the weight of the second dispersant is 1% to 3% of the weight of the high-purity alumina powder. Use water as the ball milling medium and alumina ball as the milling ball, the milling time is 2h-6h, and the particle size of the slurry obtained after ball milling is D90≤0.8μm.
在一些实施例中，采用离心喷雾干燥机进行喷雾干燥，喷雾干燥的离心干燥进风温度为250℃～350℃、出风温度为100℃～150℃、雾化转速为9000rpm～12000rpm，制备出纳米级、高松装密度的球形氧化铝细粉。In some embodiments, a centrifugal spray dryer is used for spray drying, and the centrifugal drying of spray drying has an inlet air temperature of 250°C to 350°C, an outlet temperature of 100°C to 150°C, and an atomization speed of 9000rpm to 12000rpm to prepare Nano-level, high bulk density spherical alumina fine powder.
S12、融化有机脂、加入氧化铝细粉和紫外光吸收剂，混匀后真空处理，得到氧化铝光固化浆料。S12. Melt organic grease, add alumina fine powder and ultraviolet light absorber, mix well and vacuum process to obtain alumina light-cured slurry.
具体地，将光敏树脂、第一分散剂和润滑剂加热融化后，加入所述氧化铝细粉和紫外光吸收剂，混合均匀后进行抽真空处理，得到氧化铝光固化浆料。Specifically, after the photosensitive resin, the first dispersant and the lubricant are heated and melted, the alumina fine powder and the ultraviolet light absorber are added, mixed uniformly, and then vacuumed to obtain the alumina light-cured slurry.
在一些实施例中，在所述氧化铝光固化浆料中按重量份计，氧化铝细粉为80～85份、光敏树脂为5～10份、第一分散剂为1～10份，润滑剂为2～10份、紫外光吸收剂为1～5份。In some embodiments, in the alumina light-curable slurry, the amount of alumina fine powder is 80 to 85 parts by weight, the photosensitive resin is 5 to 10 parts, and the first dispersant is 1 to 10 parts. The amount of the agent is 2-10 parts, and the amount of the ultraviolet light absorber is 1-5 parts.
在一些实施例中，光敏树脂选自聚丙烯酸树脂、环氧丙烯酸树脂、聚氨酯丙烯酸树脂和聚酯丙烯酸树脂中的至少一种；第一分散剂选自硬脂酸、油酸和聚乙二醇中的至少一种；润滑剂选自石蜡和/或甘油；紫外光吸收剂选自水杨酸苯酯、2，4-二羟基二苯甲酮和单苯甲酸间苯二酚酯中的至少一种。In some embodiments, the photosensitive resin is selected from at least one of polyacrylic resin, epoxy acrylic resin, urethane acrylic resin, and polyester acrylic resin; the first dispersant is selected from stearic acid, oleic acid, and polyethylene glycol The lubricant is selected from paraffin wax and/or glycerin; the ultraviolet light absorber is selected from at least one of phenyl salicylate, 2,4-dihydroxybenzophenone and resorcinol monobenzoate A sort of.
较优地，光敏树脂为聚丙烯酸树脂，第一分散剂为硬脂酸，润滑剂为石蜡，紫外光吸收剂为水杨酸苯酯。Preferably, the photosensitive resin is a polyacrylic resin, the first dispersant is stearic acid, the lubricant is paraffin wax, and the ultraviolet light absorber is phenyl salicylate.
进一步地，将聚丙烯酸树脂在190℃～200℃融化，降温至100℃～120℃后，加入硬脂酸，融化后降温至80℃～100℃，加入石蜡融化，待有机脂完全融化后，在搅拌状态下持续加入氧化铝细粉，添加完成后加入紫外光吸收剂，继续搅拌2h～4h，直到浆料混合均匀，然后进行抽真空处理，消除浆料内的气泡，得到氧化铝光固化浆料。如此，可以避免氧化铝光固化浆料在成型时产生孔洞等缺陷。Furthermore, the polyacrylic resin is melted at 190℃～200℃, after cooling to 100℃～120℃, stearic acid is added, after melting, the temperature is reduced to 80℃～100℃, paraffin wax is added to melt, and after the organic fat is completely melted, Continue to add alumina fine powder under stirring. After the addition is complete, add ultraviolet light absorber and continue to stir for 2h～4h until the slurry is uniformly mixed. Then vacuum treatment is carried out to eliminate bubbles in the slurry to obtain aluminum oxide light curing Slurry. In this way, defects such as holes in the aluminum oxide light-curing slurry can be avoided during molding.
S14、3D打印成型，得到氧化铝陶瓷坯体。S14, 3D printing and forming, to obtain alumina ceramic body.
具体地，将步骤S12制得的氧化铝光固化浆料，按照设计图纸，采用3D打印机打印成型，得到氧化铝陶瓷坯体。Specifically, the alumina light-cured slurry prepared in step S12 is printed and molded by a 3D printer according to the design drawings to obtain an alumina ceramic body.
采用3D打印成型，可满足半导体设备对形状复合、尺寸精度高的要求，并 且生产效率高。The use of 3D printing molding can meet the requirements of semiconductor equipment for shape complex and high dimensional accuracy, and high production efficiency.
S16、氧化铝陶瓷坯体经过常压脱脂烧结，得到氧化铝陶瓷。S16. The alumina ceramic body undergoes atmospheric pressure debinding and sintering to obtain alumina ceramics.
具体地，常压脱脂烧结的条件为：以(0.2～1)℃/min的速率升温至550℃～650℃，保温6h～10h，然后以(1～5)℃/min的速率升温至1200℃～1400℃，保温5h～8h。Specifically, the conditions for normal pressure debinding and sintering are: heating up to 550°C to 650°C at a rate of (0.2～1)°C/min, holding for 6h to 10h, and then heating up to 1200°C at a rate of (1～5)°C/min ℃～1400℃, keep for 5h～8h.
本发明以纳米级高纯氧化铝粉为原料，可以在1400℃及以内完成脱脂烧结，可以避免因烧结温度过高(如1600℃～1700℃)导致陶瓷内部分晶粒尺寸过大，使得陶瓷体的机械强度降低，容易开裂的问题，烧结所得的陶瓷晶粒尺寸均匀，致密度高，机械性能高，满足半导体设备氧化铝陶瓷的需求。The present invention uses nano-grade high-purity alumina powder as the raw material, can complete debinding and sintering at 1400°C or less, and can avoid the excessively large sintering temperature (such as 1600°C ~ 1700°C) causing part of the crystal grain size in the ceramic to be too large. The mechanical strength of the body is reduced and it is easy to crack. The ceramic grain size obtained by sintering is uniform, high density, and high mechanical properties, which can meet the needs of alumina ceramics for semiconductor equipment.
在一些实施例中，常压脱脂烧结的条件为：以(0.2～1)℃/min的速率升温至600℃，保温6h～10h，然后以(2～5)℃/min的速率升温至1200℃～1400℃，保温6h～8h。In some embodiments, the conditions for normal pressure debinding and sintering are: heating up to 600°C at a rate of (0.2～1)°C/min, holding for 6h-10h, and then heating up to 1200°C at a rate of (2～5)°C/min ℃～1400℃, keep for 6h～8h.
在一些实施例中，采用常压烧结炉进行氧化铝陶瓷坯体的脱脂烧结。如此可一次性完成脱脂烧结工作，避免单独使用脱脂炉完成脱脂后，需降温再升温进行烧结作业。同时，相对真空烧结可节约脱脂设备设入，缩短烧结时间，提高生产效率。In some embodiments, an atmospheric pressure sintering furnace is used to perform debinding and sintering of the alumina ceramic body. In this way, the debinding and sintering work can be completed at one time, avoiding the need to cool down and then increase the temperature to perform the sintering operation after the debinding furnace is used alone to complete the debinding. At the same time, compared with vacuum sintering, it can save the installation of debinding equipment, shorten the sintering time and improve production efficiency.
S18、打磨、抛光。S18. Grinding and polishing.
在一些实施例中，采用CNC磨床对烧结后的氧化铝陶瓷进行表面打磨、钻孔、开槽等精细加工作业。In some embodiments, a CNC grinder is used to perform fine processing operations such as surface grinding, drilling, and grooving on the sintered alumina ceramic.
在一些实施例中，采用中性抛光液对氧化铝陶瓷进行抛光，通过打磨和抛光，以控制氧化铝陶瓷的表面粗造度Ra≤0.1μm。In some embodiments, the alumina ceramic is polished with a neutral polishing liquid, and the surface roughness Ra of the alumina ceramic is controlled by grinding and polishing to be less than or equal to 0.1 μm.
本发明另一实施方式提供一种采用上述制备方法制得的氧化铝陶瓷。该氧化铝陶瓷的致密度高、机械性能好，能够满足半导体设备对陶瓷材料的需求。Another embodiment of the present invention provides an alumina ceramic prepared by the above preparation method. The alumina ceramic has high density and good mechanical properties, and can meet the requirements of semiconductor equipment for ceramic materials.
在一些实施例中，氧化铝陶瓷的表面粗造度Ra≤0.1μm。In some embodiments, the surface roughness Ra of the alumina ceramic is less than or equal to 0.1 μm.
本发明上述方法制备得到的氧化铝陶瓷的密度达到3.9g/cm 3及以上、抗压强度＞2600Mpa、体积电阻率＞10 14Ω·cm、硬度(HRA)为88、抗折强度为350MPa～360MPa、热膨胀系数为7.5×10 -6/℃～8.5×10 -6/℃，符合半导体设备对氧化铝精密陶瓷的使用要求。 The alumina ceramic prepared by the above method of the present invention has a density of 3.9g/cm 3 and above, a compressive strength>2600Mpa, a volume resistivity>10 14 Ω·cm, a hardness (HRA) of 88, and a flexural strength of 350MPa～ 360MPa, the thermal expansion coefficient is 7.5×10 -6 /℃～8.5×10 -6 /℃, which meets the requirements for the use of alumina precision ceramics in semiconductor equipment.
以下为具体实施例。The following are specific examples.
实施例1Example 1
原材料：高纯氧化铝粉：氧化铝纯度99.99％以上，粒径D50：0.4μm，BET：13m 2/g。 Raw material: high-purity alumina powder: alumina purity 99.99% or more, particle size D50: 0.4μm, BET: 13m 2 /g.
1)、称取研磨介质纯水2000g，称取20g聚乙烯醇分散剂，将分散剂添加到纯水中搅拌分散均匀后，制成预混液。1) Weigh 2000 g of pure water for grinding media, weigh 20 g of polyvinyl alcohol dispersant, add the dispersant to the pure water, stir and disperse uniformly, to make a premix.
2)、向预混液内添加2000g高纯氧化铝粉，搅拌分散成浆料后，经高速砂磨机球磨5h，制备出粒径分布窄，粒径小的氧化铝浆料，经测其D90＜0.8μm。2) Add 2000g of high-purity alumina powder to the premixed liquid, stir and disperse it into a slurry, then ball mill it with a high-speed sand mill for 5 hours to prepare an alumina slurry with a narrow particle size distribution and a small particle size. The D90 is measured <0.8μm.
3)、将氧化铝浆料在干燥的进风温度为280℃、出风温度为120℃，雾化盘转速为10000rpm下，在喷雾干燥机内进行干燥作业，制备出球形氧化铝超细粉。3). Dry the alumina slurry in a spray dryer at an inlet air temperature of 280°C, an outlet air temperature of 120°C, and an atomizing disk rotation speed of 10000rpm to prepare spherical alumina ultrafine powder. .
4)、称取250g聚丙烯酸树脂在190℃油浴锅内进行融化，当聚丙烯酸树脂颗粒完全融化成液态后，体系降温至120℃，加入125g硬脂酸，使其熔化；体系温度再降温至80℃，加入50g石蜡，使其融化。整体有机物融化后，在搅拌机开启下，向体系内缓慢加入2000g步骤3制备的球形氧化铝超细粉，氧化铝超细粉在体系内分散成浆料态后再向体系内加入75g紫外光吸收剂水杨酸苯脂，持续搅拌3h。使整个光固化氧化铝浆料体系分布均匀，最后对该体系浆料真空处理15min后转移至3D打印机料罐。4) Weigh 250g of polyacrylic resin and melt it in an oil bath at 190°C. When the polyacrylic resin particles are completely melted into a liquid state, the system is cooled to 120°C, and 125g of stearic acid is added to make it melt; the temperature of the system is lowered again To 80°C, add 50g of paraffin wax to melt. After the whole organic matter is melted, with the mixer turned on, slowly add 2000g of the spherical alumina ultrafine powder prepared in step 3 into the system. After the alumina ultrafine powder is dispersed in the system into a slurry state, 75g of ultraviolet light absorption is added to the system. Add phenyl salicylate and continue to stir for 3h. Make the entire light-curing alumina slurry system evenly distributed, and finally the system slurry is vacuum treated for 15 minutes and then transferred to the 3D printer tank.
5)、使用光固化陶瓷3D打印机，按照图纸需求在紫外照射条件下，完成氧化铝陶瓷成型工作。5) Use a light-curing ceramic 3D printer to complete the aluminum oxide ceramic forming work under the conditions of ultraviolet irradiation according to the requirements of the drawings.
6)、将成型后氧化铝陶瓷坯体放置在常压脱脂烧结炉内，炉温按照0.5℃/min升温速率升温至600℃，并在该温度保温6h完成对氧化铝陶瓷脱脂作业，完全去除有机脂；氧化铝陶瓷继续按照2.5℃/min升温速率升温至1400℃，并在1400℃保温6h。高温烧结后氧化铝随烧结炉自然降温至200℃以下即可出炉，完成烧制，制得氧化铝陶瓷烧结体。6) Place the formed alumina ceramic body in the atmospheric pressure debinding and sintering furnace. The furnace temperature is increased to 600°C at a heating rate of 0.5°C/min, and kept at this temperature for 6 hours to complete the debinding operation of the alumina ceramics, and completely remove Organic grease; alumina ceramics continue to heat up to 1400°C at a heating rate of 2.5°C/min, and keep it at 1400°C for 6 hours. After high-temperature sintering, the alumina can be discharged from the sintering furnace when the temperature is naturally lowered to below 200°C, and the firing is completed to obtain an alumina ceramic sintered body.
7)、氧化铝陶瓷烧结体经CNC研磨精加工后再使用中性抛光液抛光，其表面粗糙度Ra＜0.1μm。7) The alumina ceramic sintered body is polished by a neutral polishing liquid after CNC grinding and finishing, and its surface roughness Ra<0.1μm.
实施例2Example 2
原材料：高纯氧化铝粉：氧化铝纯度99.99％以上，粒径D50：0.3μm，BET：15m 2/g。 Raw material: high-purity alumina powder: alumina purity 99.99% or more, particle size D50: 0.3μm, BET: 15m 2 /g.
1)、称取研磨介质纯水2000g，称取20g聚乙烯醇分散剂，将分散剂添加到纯水中搅拌分散均匀后，制成预混液。1) Weigh 2000 g of pure water for grinding media, weigh 20 g of polyvinyl alcohol dispersant, add the dispersant to the pure water, stir and disperse uniformly, to make a premix.
2)、向预混液内添加2000g高纯氧化铝粉，搅拌分散成浆料后，经高速砂磨机球磨4h，制备出粒径分布窄，粒径小的氧化铝浆料，其D90＜0.8μm。2) Add 2000g of high-purity alumina powder to the premixed solution, stir and disperse it into a slurry, and then ball mill it with a high-speed sand mill for 4 hours to prepare an alumina slurry with a narrow particle size distribution and a small particle size, with D90<0.8 μm.
3)、将氧化铝浆料在干燥进风温度为280℃、出风温度为120℃，雾化盘转速为10000rpm下，在喷雾干燥机内进行干燥作业，制备出球形氧化铝超细粉。3) Dry the alumina slurry in a spray dryer at a drying inlet air temperature of 280°C, an outlet air temperature of 120°C, and an atomizing disk rotating speed of 10,000 rpm to prepare spherical alumina ultrafine powder.
4)、称取200g聚丙烯酸树脂在190℃油浴锅内进行融化，当聚丙烯酸树脂颗粒完全融化成液态后，体系降温至120℃，加入150g硬脂酸，使其熔化；体系温度再降温至80℃，加入75g石蜡，使其融化。整体有机物融化后，在搅拌机开启下，向体系内缓慢加入2000g步骤3制备的球形氧化铝粉，氧化铝粉在体系内分散成浆料态后再向体系内加入75g紫外光吸收剂水杨酸苯酯，持续搅拌4h。使整个光固化氧化铝浆料体系分布均匀，最后对该体系浆料真空处理15min后转移至3D打印机料罐。4) Weigh 200g of polyacrylic resin and melt it in an oil bath at 190°C. When the polyacrylic resin particles are completely melted into a liquid state, the system is cooled to 120°C, and 150g of stearic acid is added to melt it; the temperature of the system is lowered again To 80°C, add 75 g of paraffin wax to melt. After the whole organic matter is melted, with the mixer turned on, slowly add 2000g of the spherical alumina powder prepared in step 3 into the system. After the alumina powder is dispersed in the system into a slurry state, 75g of the ultraviolet light absorber salicylic acid is added to the system. Phenyl ester, continue to stir for 4h. Make the entire light-curing alumina slurry system evenly distributed, and finally the system slurry is vacuum treated for 15 minutes and then transferred to the 3D printer tank.
5)、使用光固化陶瓷3D打印机，按照图纸需求在紫外照射条件下，完成氧化铝陶瓷成型工作。5) Use a light-curing ceramic 3D printer to complete the aluminum oxide ceramic forming work under the conditions of ultraviolet irradiation according to the requirements of the drawings.
6)、将成型后氧化铝陶瓷坯体放置在常压脱脂烧结炉内，炉温按照0.5℃/min升温速率升温至600℃，并在该温度保温6h完成对氧化铝陶瓷脱脂作业，完全去除有机脂；氧化铝陶瓷继续按照2.0℃/min升温速率升温至1350℃，并在1350℃保温8h。高温烧结后氧化铝随烧结炉自然降温至200℃以下即可出炉，完成烧制，制得氧化铝陶瓷烧结体。6) Place the formed alumina ceramic body in the atmospheric pressure debinding and sintering furnace. The furnace temperature is increased to 600°C at a heating rate of 0.5°C/min, and kept at this temperature for 6 hours to complete the debinding operation of the alumina ceramics, and completely remove Organic grease; alumina ceramics continue to heat up to 1350°C at a heating rate of 2.0°C/min, and keep it at 1350°C for 8 hours. After high-temperature sintering, the alumina can be discharged from the sintering furnace when the temperature is naturally lowered to below 200°C, and the firing is completed to obtain an alumina ceramic sintered body.
7)、氧化铝陶瓷烧结体经CNC研磨精加工后再使用中性抛光液抛光，其表面粗糙度Ra＜0.1μm。7) The alumina ceramic sintered body is polished by a neutral polishing liquid after CNC grinding and finishing, and its surface roughness Ra<0.1μm.
实施例3Example 3
原材料：高纯氧化铝粉：氧化铝纯度99.99％以上，粒径D50：0.3μm，BET： 18m 2/g。 Raw material: high-purity alumina powder: alumina purity 99.99% or more, particle size D50: 0.3μm, BET: 18m 2 /g.
1)、称取研磨介质纯水2000g，称取20g聚乙烯醇分散剂，将分散剂添加到纯水中搅拌分散均匀后，制成预混液。1) Weigh 2000 g of pure water for grinding media, weigh 20 g of polyvinyl alcohol dispersant, add the dispersant to the pure water, stir and disperse uniformly, to make a premix.
2)、向预混液内添加2000g高纯氧化铝粉，搅拌分散成浆料后，经高速砂磨机球磨4h，制备出粒径分布窄，粒径小的氧化铝浆料，其D90＜0.8μm。2) Add 2000g of high-purity alumina powder to the premixed solution, stir and disperse it into a slurry, and then ball mill it with a high-speed sand mill for 4 hours to prepare an alumina slurry with a narrow particle size distribution and a small particle size, with D90<0.8 μm.
3)、将氧化铝浆料在干燥进风温度为280℃、出风温度为120℃，雾化盘转速为10000rpm下，在喷雾干燥机内进行干燥作业，制备出球形氧化铝超细粉。3) Dry the alumina slurry in a spray dryer at a drying inlet air temperature of 280°C, an outlet air temperature of 120°C, and an atomizing disk rotating speed of 10,000 rpm to prepare spherical alumina ultrafine powder.
4)、称取225g聚丙烯酸树脂在190℃油浴锅内进行融化，当聚丙烯酸树脂颗粒完全融化成液态后，体系降温至120℃，加入100g硬脂酸，使其熔化；体系温度再降温至80℃，加入100g石蜡，使其融化。整体有机物融化后，在搅拌机开启下，向体系内缓慢加入2000g步骤3制备的球形氧化铝粉，氧化铝粉在体系内分散成浆料态后再向体系内加入75g紫外光吸收剂水杨酸苯酯，持续搅拌3h。使整个光固化氧化铝浆料体系分布均匀，最后对该体系浆料真空处理15min后转移至3D打印机料罐。4) Weigh 225g polyacrylic resin and melt it in an oil bath at 190℃. When the polyacrylic resin particles are completely melted into a liquid state, the system is cooled to 120℃, and 100g stearic acid is added to melt it; the temperature of the system is lowered again To 80°C, add 100g of paraffin wax to melt. After the whole organic matter is melted, with the mixer turned on, slowly add 2000g of the spherical alumina powder prepared in step 3 into the system. After the alumina powder is dispersed in the system into a slurry state, 75g of the ultraviolet light absorber salicylic acid is added to the system. Phenyl ester, continue to stir for 3h. Make the entire light-curing alumina slurry system evenly distributed, and finally the system slurry is vacuum treated for 15 minutes and then transferred to the 3D printer tank.
5)、使用光固化陶瓷3D打印机，按照图纸需求在紫外照射条件下，完成氧化铝陶瓷成型工作。5) Use a light-curing ceramic 3D printer to complete the aluminum oxide ceramic forming work under the conditions of ultraviolet irradiation according to the requirements of the drawings.
6)、将成型后的氧化铝陶瓷坯体放置在常压脱脂烧结炉内，炉温按照0.5℃/min升温速率升温至600℃，并在该温度保温6h完成对氧化铝陶瓷脱脂作业，完全去除有机脂；氧化铝陶瓷继续按照2.0℃/min升温速率升温至1300℃，并在1300℃保温7h。高温烧结后氧化铝随烧结炉自然降温至200℃以下即可出炉，完成烧制，制得氧化铝陶瓷烧结体。6) Place the formed alumina ceramic body in an atmospheric degreasing and sintering furnace. The temperature of the furnace is increased to 600°C at a heating rate of 0.5°C/min, and the alumina ceramics degreasing operation is completed by keeping it at this temperature for 6 hours. Removal of organic grease; the alumina ceramic continues to be heated to 1300°C at a heating rate of 2.0°C/min, and kept at 1300°C for 7 hours. After high-temperature sintering, the alumina can be discharged from the sintering furnace when the temperature is naturally lowered to below 200°C, and the firing is completed to obtain an alumina ceramic sintered body.
7)、将氧化铝陶瓷烧结体经CNC研磨精加工后再使用中性抛光液抛光，其表面粗糙度Ra＜0.1μm。7) After CNC grinding and finishing the alumina ceramic sintered body, it is polished with a neutral polishing liquid, and its surface roughness Ra<0.1μm.
对比例1Comparative example 1
原材料：高纯氧化铝粉：氧化铝纯度99.99％以上，粒径D50：2.5μm，BET：8m 2/g。 Raw material: high-purity alumina powder: alumina purity 99.99% or more, particle size D50: 2.5μm, BET: 8m 2 /g.
1)、称取研磨介质纯水2000g，称取20g聚乙烯醇分散剂，将分散剂添加到 纯水中搅拌分散均匀后，制成预混液。1). Weigh 2000 g of pure water for grinding media, weigh 20 g of polyvinyl alcohol dispersant, add the dispersant to the pure water, stir and disperse uniformly, to prepare a premix.
2)、向预混液内添加2000g高纯氧化铝粉，搅拌分散成浆料后，经高速砂磨机球磨5h，得到氧化铝浆料，其D90为5μm。2) Add 2000g of high-purity alumina powder to the premixed liquid, stir and disperse into a slurry, and then ball mill it with a high-speed sand mill for 5 hours to obtain an alumina slurry with a D90 of 5 μm.
3)、将氧化铝浆料在干燥进风温度为280℃、出风温度为120℃，雾化盘转速为10000rpm下，在喷雾干燥机内进行干燥作业，制备出球形氧化铝粉。3) Dry the alumina slurry in a spray dryer at a drying inlet air temperature of 280°C, an outlet air temperature of 120°C, and an atomizing disk rotating speed of 10000 rpm to prepare spherical alumina powder.
4)、称取250g聚丙烯酸树脂在190℃油浴锅内进行融化，当聚丙烯酸树脂颗粒完全融化成液态后，体系降温至120℃，加入125g硬脂酸，使其熔化；体系温度再降温至80℃，加入50g石蜡，使其融化。整体有机物融化后，在搅拌机开启下，向体系内缓慢加入2000g步骤3制备的球形氧化铝粉，氧化铝粉在体系内分散成浆料态后再向体系内加入75g紫外光吸收剂水杨酸苯酯，持续搅拌3h。使整个光固化氧化铝浆料体系分布均匀，最后对该体系浆料真空处理15min后转移至3D打印机料罐。4) Weigh 250g of polyacrylic resin and melt it in an oil bath at 190°C. When the polyacrylic resin particles are completely melted into a liquid state, the system is cooled to 120°C, and 125g of stearic acid is added to make it melt; the temperature of the system is lowered again To 80°C, add 50g of paraffin wax to melt. After the whole organic matter is melted, with the mixer turned on, slowly add 2000g of the spherical alumina powder prepared in step 3 into the system. After the alumina powder is dispersed in the system into a slurry state, 75g of the ultraviolet light absorber salicylic acid is added to the system. Phenyl ester, continue to stir for 3h. Make the entire light-curing alumina slurry system evenly distributed, and finally the system slurry is vacuum treated for 15 minutes and then transferred to the 3D printer tank.
5)、使用光固化陶瓷3D打印机，按照图纸需求在紫外照射条件下，完成氧化铝陶瓷成型工作。5) Use a light-curing ceramic 3D printer to complete the aluminum oxide ceramic forming work under the conditions of ultraviolet irradiation according to the requirements of the drawings.
6)、将成型后的氧化铝陶瓷坯体放置在常压脱脂烧结炉内，炉温按照0.5℃/min升温速率升温至600℃，并在该温度保温6h完成对氧化铝陶瓷脱脂作业，完全去除有机脂；氧化铝陶瓷继续按照2.5℃/min升温速率升温至1400℃，并在1400℃保温6h。高温烧结后氧化铝随烧结炉自然降温至200℃以下即可出炉，完成烧制。6) Place the formed alumina ceramic body in an atmospheric degreasing and sintering furnace. The temperature of the furnace is increased to 600°C at a heating rate of 0.5°C/min, and the alumina ceramics degreasing operation is completed by keeping it at this temperature for 6 hours. Remove organic grease; alumina ceramics continue to heat up to 1400°C at a heating rate of 2.5°C/min, and keep it at 1400°C for 6 hours. After high-temperature sintering, the alumina can be discharged after the sintering furnace is naturally cooled to below 200°C, and the firing is completed.
对比例2Comparative example 2
原材料：高纯氧化铝粉：氧化铝纯度99.99％以上，粒径D50：2.5μm，BET：8m 2/g。 Raw material: high-purity alumina powder: alumina purity 99.99% or more, particle size D50: 2.5μm, BET: 8m 2 /g.
1)、称取研磨介质纯水2000g，称取20g聚乙烯醇分散剂，将分散剂添加到纯水中搅拌分散均匀后，制成预混液。1) Weigh 2000 g of pure water for grinding media, weigh 20 g of polyvinyl alcohol dispersant, add the dispersant to the pure water, stir and disperse uniformly, to make a premix.
2)、向预混液内添加2000g高纯氧化铝粉，搅拌分散成浆料后，经高速砂磨机球磨5h，得到氧化铝浆料，其D90为5μm。2) Add 2000g of high-purity alumina powder to the premixed liquid, stir and disperse into a slurry, and then ball mill it with a high-speed sand mill for 5 hours to obtain an alumina slurry with a D90 of 5 μm.
3)、将氧化铝浆料在干燥温度为280℃，雾化盘转速为10000rpm下，在喷 雾干燥机内进行干燥作业，制备出球形氧化铝粉。3) The alumina slurry is dried in a spray dryer at a drying temperature of 280°C and an atomizing plate rotating speed of 10,000 rpm to prepare spherical alumina powder.
4)、称取250g聚丙烯酸树脂在190℃油浴锅内进行融化，当聚丙烯酸树脂颗粒完全融化成液态后，体系降温至120℃，加入125g硬脂酸，使其熔化；体系温度再降温至80℃，加入50g石蜡，使其融化。整体有机物融化后，在搅拌机开启下，向体系内缓慢加入2000g步骤3制备的球形氧化铝粉，氧化铝粉在体系内分散成浆料态后再向体系内加入75g紫外光吸收剂水杨酸苯酯，持续搅拌3h。使整个光固化氧化铝浆料体系分布均匀，最后对该体系浆料真空处理15min后转移至3D打印机料罐。4) Weigh 250g of polyacrylic resin and melt it in an oil bath at 190°C. When the polyacrylic resin particles are completely melted into a liquid state, the system is cooled to 120°C, and 125g of stearic acid is added to make it melt; the temperature of the system is lowered again To 80°C, add 50g of paraffin wax to melt. After the whole organic matter is melted, with the mixer turned on, slowly add 2000g of the spherical alumina powder prepared in step 3 into the system. After the alumina powder is dispersed in the system into a slurry state, 75g of the ultraviolet light absorber salicylic acid is added to the system. Phenyl ester, continue to stir for 3h. Make the entire light-curing alumina slurry system evenly distributed, and finally the system slurry is vacuum treated for 15 minutes and then transferred to the 3D printer tank.
5)、使用光固化陶瓷3D打印机，按照图纸需求在紫外照射条件下，完成氧化铝陶瓷成型工作。5) Use a light-curing ceramic 3D printer to complete the aluminum oxide ceramic forming work under the conditions of ultraviolet irradiation according to the requirements of the drawings.
6)、将成型后的氧化铝陶瓷坯体放置在常压脱脂烧结炉内，炉温按照0.5℃/min升温速率升温至600℃，并在该温度保温6h完成对氧化铝陶瓷脱脂作业，完全去除有机脂；氧化铝陶瓷继续按照2.5℃/min升温速率升温至1700℃，并在1700℃保温6h。高温烧结后氧化铝随烧结炉自然降温至200℃以下即可出炉，完成烧制。6) Place the formed alumina ceramic body in an atmospheric degreasing and sintering furnace. The temperature of the furnace is increased to 600°C at a heating rate of 0.5°C/min, and the alumina ceramics degreasing operation is completed by keeping it at this temperature for 6 hours. Removal of organic grease; the alumina ceramic continues to be heated to 1700°C at a heating rate of 2.5°C/min, and kept at 1700°C for 6 hours. After high-temperature sintering, the alumina can be discharged after the sintering furnace is naturally cooled to below 200°C, and the firing is completed.
对比例3Comparative example 3
原材料：氧化铝纯度95％，粒径D50：0.3μm，BET：15m 2/g。 Raw material: alumina purity 95%, particle size D50: 0.3 μm, BET: 15 m 2 /g.
1)、称取研磨介质纯水2000g，称取20g聚乙烯醇分散剂，分散剂溶液添加到纯水中搅拌分散均匀后，制成预混液。1) Weigh 2000 g of pure water for grinding media, weigh 20 g of polyvinyl alcohol dispersant, add the dispersant solution to the pure water, stir and disperse uniformly, to prepare a premix.
2)、向预混液内添加2000g氧化铝粉，搅拌分散成浆料后，该氧化铝浆料经高速砂磨机球磨4h，制备出粒径分布窄，粒径小的氧化铝浆料，其D90＜0.8μm。2) Add 2000g of alumina powder to the premixed liquid, stir and disperse it into a slurry, then the alumina slurry is ball milled with a high-speed sand mill for 4 hours to prepare an alumina slurry with a narrow particle size distribution and a small particle size. D90<0.8μm.
3)、该浆料在干燥温度为280℃，雾化盘转速为10000rpm下，在喷雾干燥机内进行干燥作业，制备出球形氧化铝超细粉。3) The slurry is dried in a spray dryer at a drying temperature of 280° C. and an atomizing plate rotating speed of 10000 rpm to prepare spherical alumina ultrafine powder.
4)、称取200g聚丙烯酸树脂在190℃油浴锅内进行融化，当聚丙烯酸树脂颗粒完全融化成液态后，体系降温至120℃，加入150g硬脂酸，使其熔化；体系温度再降温至80℃，加入75g石蜡，使其融化。整体有机物融化，在搅拌机 开启下，向体系内缓慢加入2000g步骤3制备的球形氧化铝超细粉，氧化铝超细粉在体系内分散成浆料态后再向体系75g紫外光吸收剂水杨酸苯脂，持续搅拌4h。使整个光固化氧化铝浆料体系分布均匀，最后对该体系浆料真空处理15min后转移至3D打印机料罐。4) Weigh 200g of polyacrylic resin and melt it in an oil bath at 190°C. When the polyacrylic resin particles are completely melted into a liquid state, the system is cooled to 120°C, and 150g of stearic acid is added to melt it; the temperature of the system is lowered again To 80°C, add 75g of paraffin wax to melt. The whole organic matter is melted. When the mixer is turned on, slowly add 2000g of the spherical alumina ultrafine powder prepared in step 3 into the system. After the alumina ultrafine powder is dispersed in the system into a slurry state, 75g of ultraviolet light absorber salicylic acid is added to the system. Acid phenyl resin, continue to stir for 4h. Make the entire light-cured alumina slurry system evenly distributed, and finally the system slurry is vacuum treated for 15 minutes and then transferred to the 3D printer tank.
5)、使用光固化陶瓷3D打印机，按照图纸需求在紫外照射条件下，完成氧化铝陶瓷成型工作。5) Use a light-curing ceramic 3D printer to complete the aluminum oxide ceramic forming work under the conditions of ultraviolet irradiation according to the requirements of the drawings.
6)、成型后氧化铝陶瓷坯体放置在常压脱脂烧结炉内，炉温按照0.5℃/min升温速率升温至600℃，并在该温度保温6h完成对氧化铝陶瓷脱脂作业，完全去除有机脂；氧化铝陶瓷继续按照2.0℃/min升温速率升温至1350℃，并在1350℃保温8h。高温烧结后氧化铝随烧结炉自然降温至200℃以下即可出炉，完成烧制。6) After forming, the alumina ceramic body is placed in the atmospheric pressure debinding and sintering furnace. The furnace temperature is increased to 600°C at a heating rate of 0.5°C/min, and the alumina ceramic body is debinding at this temperature for 6 hours to completely remove organic Grease; Alumina ceramics continue to heat up to 1350°C at a heating rate of 2.0°C/min, and keep it at 1350°C for 8 hours. After high-temperature sintering, the alumina can be discharged after the sintering furnace is naturally cooled to below 200°C, and the firing is completed.
将实施例1～3及对比例1～3制得的氧化铝陶瓷进行性能测试，测试结果如下表1所示。The alumina ceramics prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were tested for performance, and the test results are shown in Table 1 below.
其中，各项性能测试项目的测试标准分别如下：Among them, the test standards for each performance test item are as follows:
密度：GB/T 25995-2010；Density: GB/T 25995-2010;
抗压强度：GB/T 4740-1999；Compressive strength: GB/T 4740-1999;
体积电阻率：GB/T 31838.2-2019；Volume resistivity: GB/T 31838.2-2019;
硬度(HRA)：GB/T 16534-2009；Hardness (HRA): GB/T 16534-2009;
抗折强度：GB/T 3002-2004；Flexural strength: GB/T 3002-2004;
热膨胀系数：GB T 16535-2008。Coefficient of thermal expansion: GB T 16535-2008.
表1Table 1
Figure PCTCN2020128669-appb-000001
Figure PCTCN2020128669-appb-000001
Figure PCTCN2020128669-appb-000002
Figure PCTCN2020128669-appb-000002
从上表2可知，本发明实施例1～3以高纯氧化铝粉为原料，经球磨、喷雾干燥、3D打印成型后采用低温常压烧结，能够制备高致密，细晶粒，高强度，高韧性，高硬度，耐高温，低热胀系数，绝缘的精密氧化铝陶瓷。而对比例1氧化铝陶瓷的密度偏小，未完全烧结致密，不符合半导体设备氧化铝精密陶瓷使用需求，说明氧化铝原料粉的性能指标对降低烧结温度有明显作用，氧化铝原料粉末粒径过大或研磨后浆料粒径过大时，粉体烧结活性降低，在较低温度下无法完成致密烧结，导致烧结的陶瓷密度偏低，相应陶瓷的其他性能指标也下降。对比例2与对比例1采用相同的氧化铝粉体与处理工艺下，改变烧结温度达1700℃时，氧化铝陶瓷密度得到提高，但是该工艺对烧结温度需求高，能耗与设备成本增加，同时烧制的氧化铝陶瓷性能参数与本发明实施例的性能仍有所差距，尤其是抗压强度和抗折强度明显较本发明实施例差。对比例3与实施例2采用相同粒径的氧化铝原料粉，但氧化铝的纯度为95％，其它处理工艺相同，然而从烧结后的氧化铝陶瓷性能参数分析，可得知氧化铝原料粉末纯度对制备半导体设备用氧化铝陶瓷有较大影响，氧化铝所含杂质在高温液相反应过程中与氧化铝不相溶，阻碍了氧化铝晶体相融合，增加了反应所需能量，同时导致烧结产品密度不高，相应其他性能如硬度、抗压强度和抗折强度等机械性能较差。It can be seen from Table 2 above that Examples 1 to 3 of the present invention use high-purity alumina powder as the raw material, after ball milling, spray drying, 3D printing, and low-temperature and atmospheric sintering, which can produce high density, fine grains, and high strength. Precision alumina ceramics with high toughness, high hardness, high temperature resistance, low thermal expansion coefficient, and insulation. However, the density of comparative example 1 alumina ceramics is too small, not completely sintered and compact, and does not meet the requirements of the use of alumina precision ceramics for semiconductor equipment, indicating that the performance indicators of alumina raw material powder have a significant effect on reducing the sintering temperature. The particle size of the alumina raw material powder When the size of the slurry is too large or the size of the slurry after grinding is too large, the powder sintering activity will be reduced, and compact sintering cannot be completed at a lower temperature, resulting in low density of the sintered ceramics, and other performance indicators of the corresponding ceramics also decreasing. In Comparative Example 2 and Comparative Example 1, using the same alumina powder and treatment process, the density of alumina ceramics is increased when the sintering temperature is changed to 1700°C. However, the process requires high sintering temperature, energy consumption and equipment costs. At the same time, the performance parameters of the fired alumina ceramics still have a gap with the performance of the embodiment of the present invention, especially the compressive strength and flexural strength are obviously inferior to the embodiment of the present invention. Comparative Example 3 and Example 2 used alumina raw material powder with the same particle size, but the purity of the alumina was 95%, and the other treatment processes were the same. However, from the analysis of the performance parameters of the sintered alumina ceramics, it can be known that the alumina raw material powder Purity has a great influence on the preparation of alumina ceramics for semiconductor equipment. The impurities contained in alumina are immiscible with alumina during the high temperature liquid phase reaction process, which prevents the fusion of alumina crystals, increases the energy required for the reaction, and causes The density of sintered products is not high, and the corresponding mechanical properties such as hardness, compressive strength and flexural strength are poor.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, all possible combinations of the various technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, All should be considered as the scope of this specification.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several implementation modes of the present invention, and their description is relatively specific and detailed, but they should not be understood as a limitation on the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims (10)

  1. 一种氧化铝陶瓷的制备方法，其特征在于，包括如下步骤：A method for preparing alumina ceramics is characterized in that it comprises the following steps:
    将氧化铝粉制成浆料，得到粒径D90小于或等于0.8μm的氧化铝浆料；将所述氧化铝浆料干燥，得到氧化铝细粉；所述氧化铝粉中氧化铝的含量≥99wt％；The alumina powder is made into a slurry to obtain an alumina slurry with a particle size D90 less than or equal to 0.8 μm; the alumina slurry is dried to obtain alumina fine powder; the content of alumina in the alumina powder is ≥ 99wt%;
    将光敏树脂、第一分散剂和润滑剂加热融化后，加入所述氧化铝细粉和紫外光吸收剂，混合均匀后进行抽真空处理，得到氧化铝光固化浆料；After the photosensitive resin, the first dispersant and the lubricant are heated and melted, the alumina fine powder and the ultraviolet light absorber are added, mixed uniformly, and then vacuumed to obtain an alumina light-cured slurry;
    将所述氧化铝光固化浆料经3D打印成型，得到氧化铝陶瓷坯体；3D printing the aluminum oxide light-cured slurry to obtain an aluminum oxide ceramic body;
    将所述氧化铝陶瓷坯体经过常压脱脂烧结，得到氧化铝陶瓷；Subjecting the alumina ceramic body to atmospheric pressure debinding and sintering to obtain alumina ceramics;
    所述常压脱脂烧结的条件为：以(0.2～1)℃/min的速率升温至550℃～650℃，保温6h～10h，然后以(1～5)℃/min的速率升温至1200℃～1400℃，保温5h～8h。The conditions of the normal pressure debinding and sintering are: heating up to 550°C to 650°C at a rate of (0.2～1)°C/min, holding for 6h to 10h, and then heating up to 1200°C at a rate of (1～5)°C/min ～1400℃, keep for 5h～8h.
  2. 根据权利要求1所述的氧化铝陶瓷的制备方法，其特征在于，所述氧化铝粉中氧化铝的含量≥99.99wt％、D50为0.3μm～0.6μm、BET为10m 2/g～20m 2/g。 The method for preparing alumina ceramics according to claim 1, characterized in that the content of alumina in the alumina powder is ≥99.99wt%, D50 is 0.3μm～0.6μm, and BET is 10m 2 /g～20m 2 /g.
  3. 根据权利要求1所述的氧化铝陶瓷的制备方法，其特征在于，所述常压脱脂烧结的条件为：以(0.2～1)℃/min的速率升温至600℃，保温6h～10h，然后以(2～5)℃/min的速率升温至1200℃～1400℃，保温6h～8h。The method for preparing alumina ceramics according to claim 1, characterized in that the conditions for the atmospheric debinding and sintering are: heating up to 600°C at a rate of (0.2-1)°C/min, holding for 6h-10h, and then Raise the temperature to 1200℃～1400℃ at a rate of (2～5)℃/min and keep it for 6h～8h.
  4. 根据权利要求1所述的氧化铝陶瓷的制备方法，其特征在于，在所述氧化铝光固化浆料中按重量份计，所述氧化铝细粉为80～85份、所述光敏树脂为5～10份、所述第一分散剂为1～10份，所述润滑剂为2～10份、所述紫外光吸收剂为1～5份。The method for preparing alumina ceramics according to claim 1, wherein in the alumina light-curing slurry, the alumina fine powder is 80 to 85 parts by weight, and the photosensitive resin is 5-10 parts, the first dispersant is 1-10 parts, the lubricant is 2-10 parts, and the ultraviolet light absorber is 1-5 parts.
  5. 根据权利要求4所述的氧化铝陶瓷的制备方法，其特征在于，所述光敏树脂选自聚丙烯酸树脂、环氧丙烯酸树脂、聚氨酯丙烯酸树脂和聚酯丙烯酸树脂中的至少一种；和/或The method for preparing alumina ceramics according to claim 4, wherein the photosensitive resin is selected from at least one of polyacrylic resin, epoxy acrylic resin, polyurethane acrylic resin and polyester acrylic resin; and/or
    所述第一分散剂选自硬脂酸、油酸和聚乙二醇中的至少一种；和/或The first dispersant is selected from at least one of stearic acid, oleic acid and polyethylene glycol; and/or
    所述润滑剂选自石蜡和甘油中的至少一种；和/或The lubricant is selected from at least one of paraffin wax and glycerin; and/or
    所述紫外光吸收剂选自水杨酸苯酯、2，4-二羟基二苯甲酮和单苯甲酸间苯二酚酯中的至少一种。The ultraviolet light absorber is selected from at least one of phenyl salicylate, 2,4-dihydroxybenzophenone, and resorcinol monobenzoate.
  6. 根据权利要求1所述的氧化铝陶瓷的制备方法，其特征在于， 所述将氧化铝粉制成浆料的步骤为：将水、第二分散剂和所述氧化铝粉混合后，球磨2h～6h，所述氧化铝粉与所述水的重量比为(4～7):(3～6)，所述第二分散剂的重量为所述氧化铝粉的1％～3％，所述第二分散剂为有机溶剂。The method for preparing alumina ceramics according to claim 1, wherein the step of preparing alumina powder into a slurry comprises: after mixing water, a second dispersant and the alumina powder, ball milling for 2 hours ~6h, the weight ratio of the alumina powder to the water is (4-7):(3-6), the weight of the second dispersant is 1%-3% of the alumina powder, so The second dispersant is an organic solvent.
  7. 根据权利要求6所述的氧化铝陶瓷的制备方法，其特征在于，所述第二分散剂选自聚乙烯醇、聚乙二醇和聚苯乙烯中的至少一种。The method for preparing alumina ceramics according to claim 6, wherein the second dispersant is selected from at least one of polyvinyl alcohol, polyethylene glycol and polystyrene.
  8. 根据权利要求1所述的氧化铝陶瓷的制备方法，其特征在于，所述干燥采用喷雾干燥的方式，所述干燥的进风温度为250℃～350℃、出风温度为100℃～150℃、转速为9000rpm～12000rpm。The method for preparing alumina ceramics according to claim 1, wherein the drying adopts a spray drying method, and the inlet air temperature of the drying is 250°C to 350°C, and the outlet air temperature is 100°C to 150°C. , Rotation speed is 9000rpm～12000rpm.
  9. 根据权利要求1～8任一所述的氧化铝陶瓷的制备方法，其特征在于，在所述常压脱脂烧结之后还包括对所述氧化铝陶瓷进行打磨和抛光的步骤，以控制打磨和抛光后所述氧化铝陶瓷的表面粗糙度Ra≤0.1μm。The method for preparing alumina ceramics according to any one of claims 1 to 8, characterized in that, after the atmospheric pressure degreasing and sintering, it further comprises the step of grinding and polishing the alumina ceramics to control the grinding and polishing The surface roughness Ra of the alumina ceramic described later is less than or equal to 0.1 μm.
  10. 一种氧化铝陶瓷，其特征在于，采用如权利要求1～9任一所述的氧化铝陶瓷的制备方法制得。An alumina ceramic, characterized in that it is prepared by the preparation method of alumina ceramic according to any one of claims 1-9.
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