Preparation method of microcrystal high-aluminum ballstone grinding functional ceramic material

Abstract

The invention discloses a preparation method of a microcrystal high-aluminum ballstone grinding functional ceramic material. The preparation method comprises the following steps: (1) preparing matrix particles; (2) preparing composite oxide layer coated particles; (3) preparing additive particles; (4) mixing bauxite, the composite oxide layer coated particles, the additive particles, titanium dioxide powder, talcum powder, potassium feldspar powder and water to prepare slurry, so as to obtain mixed slurry; removing iron, performing spray drying, adding deionized water, continuously rolling in a balling machine, gradually growing and forming to obtain a ball blank; and (5) drying and sintering to obtain the microcrystal high-aluminum ballstone grinding functional ceramic material. The microcrystal high-aluminum ballstone grinding functional ceramic material prepared by the method has good wear resistance, and has a wide application prospect in the field of modern industry as an efficient wear-resistant material.

Description

Technical Field

[0001] This invention relates to the field of functional ceramic materials technology, and in particular to a method for preparing microcrystalline high-alumina ball-grinding functional ceramic materials. Background Technology

[0002] Microcrystalline high-alumina balls belong to the field of fine functional ceramic materials, specifically referring to a grinding media with alumina (Al2O3) as the main crystalline phase and a microcrystalline structure. This material is primarily produced through a high-temperature sintering process that allows alumina crystals to develop into tiny, uniform grains, thereby endowing the material with excellent properties such as high hardness, high wear resistance, high-temperature impact resistance, and chemical stability. In industrial applications, microcrystalline high-alumina balls are mainly used as grinding media in grinding equipment such as ball mills, stirred mills, and vibratory mills, and are widely used in the grinding of building ceramic raw materials, ultrafine processing of mineral powders, preparation of special ceramic blanks, and dispersion and grinding of pigments, coatings, and chemical raw materials. Furthermore, with advancements in material preparation technology, highly wear-resistant microcrystalline high-alumina balls have also been extended to high-end manufacturing fields such as lithium battery positive and negative electrode materials, polishing and grinding materials, and electronic ceramic components.

[0003] The formation of high-alumina spherical microcrystalline structure depends on the formulation of raw materials and the firing process. Alumina in ceramics is prone to abnormal grain growth during the high-temperature sintering stage, which leads to the coarsening of some grains and the formation of a non-uniform structure in which coarse and fine grains coexist. This non-uniform structure will reduce the overall wear resistance and strength of the material. Summary of the Invention

[0004] Therefore, this invention provides a method for preparing a microcrystalline high-alumina ball grinding functional ceramic material, the steps of which include: (1) Add zirconium oxychloride octahydrate and glucose to deionized water, stir evenly, then add boric acid. After the addition is complete, heat in a water bath, stir, add sodium citrate solution, stir evenly after the addition is complete, let stand and age, then concentrate under reduced pressure, dry, heat to 1100-1200℃ after drying, calcine, and air cool to room temperature to obtain matrix particles. (2) Prepare a composite aqueous solution of lithium acetate and cerium acetate, and prepare an ethanol solution of tetraethyl silicate; immerse the matrix particles in the composite aqueous solution of lithium acetate and cerium acetate, maintain pressure under negative pressure, then separate the solid and liquid phases, dry the solid phase, calcine, and air-cool to room temperature after calcination, then immerse them again in the ethanol solution of tetraethyl silicate, maintain pressure under negative pressure, then separate the solid and liquid phases again, dry the solid phase, calcine, air-cool to room temperature, and then immerse them again in the composite aqueous solution of lithium acetate and cerium acetate; the above process of immersing in the composite aqueous solution of lithium acetate and cerium acetate, maintaining pressure under negative pressure, separating the solid and liquid phases, drying, calcining, air-cooling, immersing in the ethanol solution of tetraethyl silicate, maintaining pressure under negative pressure, separating the solid and liquid phases, drying, calcining, and air-cooling constitutes one loading process; repeat the above loading process for more than 10 sets, and calcine for more than 1 hour in the last time to fully decompose the particles and obtain the composite oxide layer coated particles. (3) Prepare a composite aqueous solution of magnesium nitrate and barium nitrate in a reactor; prepare an aqueous solution of ammonium fluoride; then add the aqueous solution of ammonium fluoride to the reactor under stirring. After the addition is completed, seal the reactor and heat it to above 180°C under ultrasonic conditions for hydrothermal reaction. Stir magnetically during the heat preservation process. After the heat preservation is completed, cool it to room temperature, open the reactor, separate the solid and liquid, wash the solid phase, dry it, and obtain the additive particles. (4) Add bauxite, the composite oxide layer coated particles, the additive particles, titanium dioxide powder, talc powder, potassium feldspar powder and water to a planetary ball mill for ball milling and mixing to obtain a mixed slurry; remove iron from the mixed slurry and then spray dry it to make powder particles; add deionized water to the powder particles and continuously roll them in a ball mill to gradually grow and form them to obtain ball blanks; (5) The blank is dried and then sintered in a kiln to obtain the microcrystalline high-alumina ball grinding functional ceramic material.

[0005] Further, in step (1), the ratio of zirconium oxychloride octahydrate and glucose added to deionized water is zirconium oxychloride octahydrate: glucose: deionized water = 5-7g: 12-15g: 200mL; the ratio of the amount of boric acid and sodium citrate solution added to the amount of zirconium oxychloride octahydrate added is boric acid: sodium citrate solution: zirconium oxychloride octahydrate = 3-4g: 10-15mL: 5-7g, wherein the concentration of sodium citrate in the sodium citrate solution is 20-30g / L, and the solvent is water.

[0006] Furthermore, in step (1), the static aging time is more than 24 hours; the calcination time is 8 to 12 hours.

[0007] Further, in step (2), in the composite aqueous solution of lithium acetate and cerium acetate, the concentration of lithium acetate is 22-26 g / L, the concentration of cerium acetate is 2-2.5 g / L, and the solvent is water; in the ethanol solution of tetraethyl silicate, the mass percentage of tetraethyl silicate is 5%-8%, and the solvent is ethanol.

[0008] Furthermore, in step (2), the calcination temperature is 500–550°C.

[0009] Further, in step (3), in the composite aqueous solution of magnesium nitrate and barium nitrate, the concentration of magnesium nitrate is 70-80 g / L, the concentration of barium nitrate is 55-60 g / L, and the solvent is water; in the aqueous solution of ammonium fluoride, the concentration of ammonium fluoride is 50-60 g / L, and the solvent is water; the volume ratio of the aqueous solution of ammonium fluoride added to the composite aqueous solution of magnesium nitrate and barium nitrate is 1:1.

[0010] Further, in step (4), the components are as follows by weight: 100 parts of bauxite, 20-30 parts of the composite oxide layer coated particles, 5-10 parts of the additive particles, 5-10 parts of titanium dioxide powder, 2-5 parts of talc powder, and 2-5 parts of potassium feldspar powder.

[0011] Further, in step (4), the ball-to-material mass ratio of the ball milling mixture is ball:material:water = 1.6~2:1:0.8~1; the ball milling time is 12~20h, and the rotation speed is 80~100 rpm; the material-to-water mass ratio of the powder particles to deionized water is powder particles:deionized water = 9:1.

[0012] Further, in step (5), the spherical blank is dried at 110-120℃ for 20-24 hours; then it is placed in a kiln and undergoes three stages: preheating, high-temperature sintering and cooling. First, the temperature is increased to 600-650℃ at a rate of 10℃ / min and held for 30-40 minutes. Then, the temperature is increased to 850-900℃ at a rate of 5℃ / min for preheating and held for 60-80 minutes. Then, the temperature is increased to 1250-1300℃ at a rate of 3℃ / min for high-temperature sintering for 60-90 minutes. Then, the temperature is decreased to 750-800℃ at a rate of 5℃ / min and held for 10-20 minutes. After holding, the temperature is decreased to 200-250℃ at a rate of 10℃ / min and held for 10-20 minutes. Finally, it is air-cooled to room temperature.

[0013] The beneficial effects of this invention are as follows: the microcrystalline high-alumina ball grinding functional ceramic material prepared by the method described in this invention has excellent wear resistance and, as a high-efficiency wear-resistant material, has broad application prospects in modern industrial fields. Introducing the composite oxide layer coating particles and additive particles described in this invention into traditional bauxite-based ceramic materials can further reduce the equivalent wear of the microcrystalline high-alumina balls and improve wear resistance. This may be because: this invention first prepares high-strength boron and zirconium hard matrix particles. By adding hard matrix particles into the ceramic matrix, grain boundaries can be effectively pinned, playing a second-phase strengthening role. Furthermore, the added zirconium undergoes phase transformation toughening during sintering, absorbing crack propagation energy and reducing the generation of microcracks during sintering. Subsequently, a Li-Ce-Si composite oxide layer is coated on the hard matrix particles. During sintering, this layer easily forms a eutectic liquid phase with aluminum in the bauxite, filling the pores and cracks in the green body and significantly increasing the bulk density of the material. Meanwhile, the eutectic liquid phase can lower the sintering temperature, promote grain rearrangement and mass transfer, resulting in a more uniform microstructure and thus reducing wear. Furthermore, the introduced silicon can form trace amounts of silica-oxygen glass phase during high-temperature sintering, thereby promoting ceramic sintering, refining grains, and further improving the ceramic's wear resistance and reducing the coefficient of friction. The added additive particles are magnesium-barium composite fluorides with high-temperature softening and ductility; their addition to bauxite-based ceramic materials after sintering also helps improve the coefficient of friction of microcrystalline high-alumina spherical particles. Detailed Implementation

[0014] The present invention will be further described below with reference to the embodiments.

[0015] A method for preparing a microcrystalline high-alumina ball grinding functional ceramic material, comprising the following steps: (1) Zirconium oxychloride octahydrate and glucose were added to deionized water. The ratio of zirconium oxychloride octahydrate to glucose to deionized water was 5g:12g:200mL. The mixture was stirred for 30 minutes until homogeneous. Then boric acid was added. After the addition was completed, the mixture was heated to 45°C in a water bath and kept warm. The mixture was stirred for 20 minutes. Then sodium citrate solution was added. The ratio of the amount of boric acid and sodium citrate solution added to the amount of zirconium oxychloride octahydrate added was 3g:10mL:5g. The concentration of sodium citrate in the sodium citrate solution was 20g / L, and the solvent was water. After the addition was completed, the mixture was kept warm at 45°C and stirred for 30 minutes. The mixture was then aged at room temperature for 24 hours. The mixture was then concentrated under reduced pressure and dried at 100°C for 24 hours to remove water. After drying, the mixture was calcined at 1100°C for 12 hours and then cooled to room temperature to obtain matrix particles. (2) Prepare a composite aqueous solution of lithium acetate and cerium acetate, wherein the concentration of lithium acetate is 22 g / L, the concentration of cerium acetate is 2 g / L, and the solvent is water; prepare an ethanol solution of tetraethyl silicate, wherein the mass percentage of tetraethyl silicate in the ethanol solution of tetraethyl silicate is 5%, and the solvent is ethanol; immerse the matrix particles in the composite aqueous solution of lithium acetate and cerium acetate, maintain the pressure at a negative pressure of 0.01 standard atmospheres for 10 min, then separate the solid and liquid phases, dry the solid phase at 100℃ for 15 min, calcine at 500℃ for 10 min, air cool to room temperature after calcination, and immerse the particles again in the ethanol solution of tetraethyl silicate. In an ethanol solution of ethyl acetate, the mixture is placed under a negative pressure of 0.01 atmospheres for 10 minutes, followed by solid-liquid separation. The solid phase is then dried at 100°C for 15 minutes, calcined at 500°C for 10 minutes, and air-cooled to room temperature. It is then immersed again in the composite aqueous solution of lithium acetate and cerium acetate. This process of immersion in the composite aqueous solution of lithium acetate and cerium acetate, under negative pressure, solid-liquid separation, drying, calcination, and air cooling, and immersion in an ethanol solution of tetraethyl silicate under negative pressure, solid-liquid separation, drying, calcination, and air cooling constitutes one loading process. This loading process is repeated 10 times. The final calcination at 500°C for 1 hour ensures complete decomposition, yielding composite oxide-coated particles. (3) Prepare a composite aqueous solution of magnesium nitrate and barium nitrate in a reactor; the concentration of magnesium nitrate in the composite aqueous solution of magnesium nitrate and barium nitrate is 70 g / L, the concentration of barium nitrate is 55 g / L, and the solvent is water; prepare an aqueous solution of ammonium fluoride; the concentration of ammonium fluoride in the aqueous solution of ammonium fluoride is 50 g / L, and the solvent is water; then add the aqueous solution of ammonium fluoride to the reactor under stirring, the volume ratio of the aqueous solution of ammonium fluoride to the composite aqueous solution of magnesium nitrate and barium nitrate is 1:1; after the addition is completed, seal the reactor, heat it to 180℃ under ultrasonic environment and keep it at that temperature for 80 h, and stir it magnetically during the heat preservation process; after the heat preservation is completed, cool it to room temperature, open the reactor, separate the solid and liquid phases, wash the solid phase with deionized water 3 times, and dry it at 100℃ for 2 h to obtain the additive particles; (4) Weigh each raw material component, and each component is as follows by weight: 100 parts of bauxite, 20 parts of the composite oxide layer coated particles, 5 parts of the additive particles, 5 parts of titanium dioxide powder, 2 parts of talc powder, and 2 parts of potassium feldspar powder; add bauxite, the composite oxide layer coated particles, the additive particles, titanium dioxide powder, talc powder, potassium feldspar powder and water into a planetary ball mill for ball milling and mixing to obtain a mixed slurry; the ball-to-material mass ratio of the ball-milled mixture is ball:material:water = 1.6:1:0.8; the ball milling time is 12 hours and the rotation speed is 100 rpm; remove iron from the mixed slurry and then spray dry to produce powder particles; add deionized water to the powder particles, and the material-to-water mass ratio of the powder particles to deionized water is powder particles:deionized water = 9:1; continuously roll in a ball mill, gradually grow and form, to obtain a ball blank; (5) The spherical blank is dried at 110℃ for 20h; then it is placed in a kiln for sintering, which goes through three stages: preheating, high-temperature sintering and cooling: first, the temperature is raised to 600℃ at a heating rate of 10℃ / min and held for 30min, then the temperature is raised to 850℃ at a heating rate of 5℃ / min for preheating and held for 60min, then the temperature is raised to 1250℃ at a high-temperature sintering rate of 3℃ / min for 90min, then the temperature is lowered to 750℃ at a heating rate of 5℃ / min and held for 20min, then the temperature is lowered to 200℃ at a heating rate of 10℃ / min and held for 20min, and finally air-cooled to room temperature; the microcrystalline high-alumina spherical grinding functional ceramic material is obtained.

[0016] Example 2 A method for preparing a microcrystalline high-alumina ball grinding functional ceramic material, comprising the following steps: (1) Zirconium oxychloride octahydrate and glucose were added to deionized water. The ratio of zirconium oxychloride octahydrate to glucose to deionized water was 6g:13g:200mL. The mixture was stirred for 30 minutes until homogeneous. Boric acid was then added. After the addition was completed, the mixture was heated to 45°C in a water bath and kept warm. The mixture was stirred for 20 minutes. Then, sodium citrate solution was added. The ratio of the amount of boric acid and sodium citrate solution added to the amount of zirconium oxychloride octahydrate added was 3g:10mL:6g. The concentration of sodium citrate in the sodium citrate solution was 25g / L, and the solvent was water. After the addition was completed, the mixture was kept warm at 45°C and stirred for 30 minutes. The mixture was then allowed to stand at room temperature for 24 hours. The mixture was then concentrated under reduced pressure and dried at 100°C for 24 hours to remove water. After drying, the mixture was heated to 1100°C and calcined for 10 hours. The mixture was then cooled to room temperature to obtain matrix particles. (2) Prepare a composite aqueous solution of lithium acetate and cerium acetate, wherein the concentration of lithium acetate is 24 g / L, the concentration of cerium acetate is 2 g / L, and the solvent is water; prepare an ethanol solution of tetraethyl silicate, wherein the mass percentage of tetraethyl silicate in the ethanol solution of tetraethyl silicate is 6%, and the solvent is ethanol; immerse the matrix particles in the composite aqueous solution of lithium acetate and cerium acetate, maintain the pressure at a negative pressure of 0.01 standard atmospheres for 10 min, then separate the solid and liquid phases, dry the solid phase at 100℃ for 15 min, calcine at 500℃ for 10 min, air cool to room temperature after calcination, and immerse the particles again in the ethanol solution of tetraethyl silicate. In an ethanol solution of ethyl acetate, the mixture is placed under a negative pressure of 0.01 atmospheres for 10 minutes, followed by solid-liquid separation. The solid phase is then dried at 100°C for 15 minutes, calcined at 500°C for 10 minutes, and air-cooled to room temperature. It is then immersed again in the composite aqueous solution of lithium acetate and cerium acetate. This process of immersion in the composite aqueous solution of lithium acetate and cerium acetate, under negative pressure, solid-liquid separation, drying, calcination, and air cooling, and immersion in an ethanol solution of tetraethyl silicate under negative pressure, solid-liquid separation, drying, calcination, and air cooling constitutes one loading process. This loading process is repeated 10 times. The final calcination at 500°C for 1 hour ensures complete decomposition, yielding composite oxide-coated particles. (3) Prepare a composite aqueous solution of magnesium nitrate and barium nitrate in a reactor; the concentration of magnesium nitrate in the composite aqueous solution of magnesium nitrate and barium nitrate is 75 g / L, the concentration of barium nitrate is 55 g / L, and the solvent is water; prepare an aqueous solution of ammonium fluoride; the concentration of ammonium fluoride in the aqueous solution of ammonium fluoride is 55 g / L, and the solvent is water; then add the aqueous solution of ammonium fluoride to the reactor under stirring, the volume ratio of the aqueous solution of ammonium fluoride to the composite aqueous solution of magnesium nitrate and barium nitrate is 1:1; after the addition is completed, seal the reactor, heat it to 180℃ under ultrasonic environment and keep it at that temperature for 80 h, and stir it magnetically during the heat preservation process; after the heat preservation is completed, cool it to room temperature, open the reactor, separate the solid and liquid phases, wash the solid phase with deionized water 3 times, and dry it at 100℃ for 2 h to obtain the additive particles; (4) Weigh each raw material component, and each component is as follows by weight: 100 parts of bauxite, 25 parts of the composite oxide layer coated particles, 5 parts of the additive particles, 5 parts of titanium dioxide powder, 3 parts of talc powder, and 3 parts of potassium feldspar powder; add bauxite, the composite oxide layer coated particles, the additive particles, titanium dioxide powder, talc powder, potassium feldspar powder, and water into a planetary ball mill for ball milling and mixing to obtain a mixed slurry; the ball-to-material mass ratio of the ball-milled mixture is ball:material:water = 1.8:1:0.9; the ball milling time is 12 hours and the rotation speed is 100 rpm; remove iron from the mixed slurry and then spray dry it to make powder particles; add deionized water to the powder particles, and the material-to-water mass ratio of the powder particles to deionized water is powder particles:deionized water = 9:1; continuously roll in a ball mill, gradually grow and form, to obtain a ball blank; (5) The spherical blank is dried at 110℃ for 20h; then it is placed in a kiln for sintering, which goes through three stages: preheating, high-temperature sintering and cooling: first, the temperature is raised to 600℃ at a heating rate of 10℃ / min and held for 30min, then the temperature is raised to 850℃ at a heating rate of 5℃ / min for preheating and held for 60min, then the temperature is raised to 1250℃ at a high-temperature sintering rate of 3℃ / min for 90min, then the temperature is lowered to 750℃ at a heating rate of 5℃ / min and held for 20min, then the temperature is lowered to 200℃ at a heating rate of 10℃ / min and held for 20min, and finally air-cooled to room temperature; the microcrystalline high-alumina spherical grinding functional ceramic material is obtained.

[0017] Example 3 A method for preparing a microcrystalline high-alumina ball grinding functional ceramic material, comprising the following steps: (1) Zirconium oxychloride octahydrate and glucose were added to deionized water. The ratio of zirconium oxychloride octahydrate to glucose to deionized water was 6g:14g:200mL. The mixture was stirred for 30 minutes until homogeneous. Then boric acid was added. After the addition was completed, the mixture was heated to 45°C in a water bath and kept warm. The mixture was stirred for 20 minutes. Then sodium citrate solution was added. The ratio of the amount of boric acid and sodium citrate solution added to the amount of zirconium oxychloride octahydrate added was 4g:15mL:6g. The concentration of sodium citrate in the sodium citrate solution was 25g / L, and the solvent was water. After the addition was completed, the mixture was kept warm at 45°C and stirred for 30 minutes. The mixture was then aged at room temperature for 24 hours. The mixture was then concentrated under reduced pressure and dried at 100°C for 24 hours to remove water. After drying, the mixture was calcined at 1200°C for 10 hours and then cooled to room temperature to obtain matrix particles. (2) Prepare a composite aqueous solution of lithium acetate and cerium acetate, wherein the concentration of lithium acetate is 24 g / L, the concentration of cerium acetate is 2.5 g / L, and the solvent is water; prepare an ethanol solution of tetraethyl silicate, wherein the mass percentage of tetraethyl silicate in the ethanol solution of tetraethyl silicate is 7%, and the solvent is ethanol; immerse the matrix particles in the composite aqueous solution of lithium acetate and cerium acetate, maintain the pressure at a negative pressure of 0.01 standard atmospheres for 10 min, then separate the solid and liquid phases, dry the solid phase at 100℃ for 15 min, calcine at 500℃ for 10 min, air cool to room temperature after calcination, and immerse the particles again in the ethanol solution of tetraethyl silicate. In an ethanol solution of tetraethyl silicate, the mixture is placed under a negative pressure of 0.01 atmospheres for 10 minutes, followed by solid-liquid separation. The solid phase is then dried at 100°C for 15 minutes, calcined at 500°C for 10 minutes, and air-cooled to room temperature. It is then immersed again in the composite aqueous solution of lithium acetate and cerium acetate. This process of immersion in the composite aqueous solution of lithium acetate and cerium acetate, under negative pressure, solid-liquid separation, drying, calcination, and air cooling, followed by immersion in an ethanol solution of tetraethyl silicate, under negative pressure, solid-liquid separation, drying, calcination, and air cooling constitutes one loading process. This loading process is repeated 10 times. The final calcination at 500°C for 1 hour ensures complete decomposition, yielding composite oxide-coated particles. (3) Prepare a composite aqueous solution of magnesium nitrate and barium nitrate in a reactor; the concentration of magnesium nitrate in the composite aqueous solution of magnesium nitrate and barium nitrate is 75 g / L, the concentration of barium nitrate is 60 g / L, and the solvent is water; prepare an aqueous solution of ammonium fluoride; the concentration of ammonium fluoride in the aqueous solution of ammonium fluoride is 55 g / L, and the solvent is water; then add the aqueous solution of ammonium fluoride to the reactor under stirring, the volume ratio of the aqueous solution of ammonium fluoride to the composite aqueous solution of magnesium nitrate and barium nitrate is 1:1; after the addition is completed, seal the reactor, heat it to 180℃ under ultrasonic environment and keep it at that temperature for 80 h, and stir it magnetically during the heat preservation process; after the heat preservation is completed, cool it to room temperature, open the reactor, separate the solid and liquid phases, wash the solid phase with deionized water 3 times, and dry it at 100℃ for 2 h to obtain the additive particles; (4) Weigh each raw material component, and each component is as follows by weight: 100 parts of bauxite, 25 parts of the composite oxide layer coated particles, 10 parts of the additive particles, 10 parts of titanium dioxide powder, 4 parts of talc powder, and 4 parts of potassium feldspar powder; add bauxite, the composite oxide layer coated particles, the additive particles, titanium dioxide powder, talc powder, potassium feldspar powder and water into a planetary ball mill for ball milling and mixing to obtain a mixed slurry; the ball-to-material mass ratio of the ball milling mixture is ball:material:water = 1.8:1:0.9; the ball milling time is 12 hours and the rotation speed is 100 rpm; remove iron from the mixed slurry and then spray dry to produce powder particles; add deionized water to the powder particles, and the material-to-water mass ratio of the powder particles to deionized water is powder particles:deionized water = 9:1; continuously roll in a ball mill, gradually grow and form, to obtain a ball blank; (5) The spherical blank is dried at 110℃ for 20h; then it is placed in a kiln for sintering, which goes through three stages: preheating, high-temperature sintering and cooling: first, the temperature is raised to 600℃ at a heating rate of 10℃ / min and held for 30min, then the temperature is raised to 850℃ at a heating rate of 5℃ / min for preheating and held for 60min, then the temperature is raised to 1300℃ at a high-temperature sintering rate of 3℃ / min for 60min, then the temperature is lowered to 750℃ at a heating rate of 5℃ / min and held for 20min, then the temperature is lowered to 200℃ at a heating rate of 10℃ / min and held for 20min, and finally air-cooled to room temperature; the microcrystalline high-alumina spherical grinding functional ceramic material is obtained.

[0018] Example 4 A method for preparing a microcrystalline high-alumina ball grinding functional ceramic material, comprising the following steps: (1) Zirconium oxychloride octahydrate and glucose were added to deionized water. The ratio of zirconium oxychloride octahydrate to glucose to deionized water was 7g:15g:200mL. The mixture was stirred for 30 minutes until homogeneous. Then boric acid was added. After the addition was completed, the mixture was heated to 45°C in a water bath and kept warm. The mixture was stirred for 20 minutes. Then sodium citrate solution was added. The ratio of the amount of boric acid and sodium citrate solution added to the amount of zirconium oxychloride octahydrate added was 4g:15mL:7g. The concentration of sodium citrate in the sodium citrate solution was 30g / L and the solvent was water. After the addition was completed, the mixture was kept warm at 45°C and stirred for 30 minutes. The mixture was then aged at room temperature for 24 hours. The mixture was then concentrated under reduced pressure and dried at 100°C for 24 hours to remove water. After drying, the mixture was heated to 1200°C and calcined for 8 hours. The mixture was then cooled to room temperature to obtain matrix particles. (2) Prepare a composite aqueous solution of lithium acetate and cerium acetate, wherein the concentration of lithium acetate is 26 g / L, the concentration of cerium acetate is 2.5 g / L, and the solvent is water; prepare an ethanol solution of tetraethyl silicate, wherein the mass percentage of tetraethyl silicate in the ethanol solution of tetraethyl silicate is 8%, and the solvent is ethanol; immerse the matrix particles in the composite aqueous solution of lithium acetate and cerium acetate, maintain the pressure at a negative pressure of 0.01 standard atmospheres for 10 min, then separate the solid and liquid phases, dry the solid phase at 100℃ for 15 min, calcine at 500℃ for 10 min, air cool to room temperature after calcination, and immerse the particles again in the ethanol solution of tetraethyl silicate. In an ethanol solution of tetraethyl silicate, the mixture is placed under a negative pressure of 0.01 atmospheres for 10 minutes, followed by solid-liquid separation. The solid phase is then dried at 100°C for 15 minutes, calcined at 500°C for 10 minutes, and air-cooled to room temperature. It is then immersed again in the composite aqueous solution of lithium acetate and cerium acetate. This process of immersion in the composite aqueous solution of lithium acetate and cerium acetate, under negative pressure, solid-liquid separation, drying, calcination, and air cooling, followed by immersion in an ethanol solution of tetraethyl silicate, under negative pressure, solid-liquid separation, drying, calcination, and air cooling constitutes one loading process. This loading process is repeated 10 times. The final calcination at 500°C for 1 hour ensures complete decomposition, yielding composite oxide-coated particles. (3) Prepare a composite aqueous solution of magnesium nitrate and barium nitrate in a reactor; the concentration of magnesium nitrate in the composite aqueous solution of magnesium nitrate and barium nitrate is 80 g / L, the concentration of barium nitrate is 60 g / L, and the solvent is water; prepare an aqueous solution of ammonium fluoride; the concentration of ammonium fluoride in the aqueous solution of ammonium fluoride is 60 g / L, and the solvent is water; then add the aqueous solution of ammonium fluoride to the reactor under stirring, the volume ratio of the aqueous solution of ammonium fluoride to the composite aqueous solution of magnesium nitrate and barium nitrate is 1:1; after the addition is completed, seal the reactor, heat it to 180℃ under ultrasonic environment and keep it at that temperature for 80 h, and stir it magnetically during the heat preservation process; after the heat preservation is completed, cool it to room temperature, open the reactor, separate the solid and liquid phases, wash the solid phase with deionized water 3 times, and dry it at 100℃ for 2 h to obtain the additive particles; (4) Weigh each raw material component, and each component is as follows by weight: 100 parts of bauxite, 30 parts of the composite oxide layer coated particles, 10 parts of the additive particles, 10 parts of titanium dioxide powder, 5 parts of talc powder, and 5 parts of potassium feldspar powder; add bauxite, the composite oxide layer coated particles, the additive particles, titanium dioxide powder, talc powder, potassium feldspar powder and water into a planetary ball mill for ball milling and mixing to obtain a mixed slurry; the ball-to-material mass ratio of the ball-milled mixture is ball:material:water = 2:1:1; the ball milling time is 12 hours and the rotation speed is 100 rpm; remove iron from the mixed slurry and then spray dry to produce powder particles; add deionized water to the powder particles, and the material-to-water mass ratio of the powder particles to deionized water is powder particles:deionized water = 9:1; continuously roll in a ball mill, gradually grow and form, to obtain a ball blank; (5) The spherical blank is dried at 110℃ for 20h; then it is placed in a kiln for sintering, which goes through three stages: preheating, high-temperature sintering and cooling: first, the temperature is raised to 600℃ at a heating rate of 10℃ / min and held for 30min, then the temperature is raised to 850℃ at a heating rate of 5℃ / min for preheating and held for 60min, then the temperature is raised to 1300℃ at a high-temperature sintering rate of 3℃ / min for 60min, then the temperature is lowered to 750℃ at a heating rate of 5℃ / min and held for 20min, then the temperature is lowered to 200℃ at a heating rate of 10℃ / min and held for 20min, and finally air-cooled to room temperature; the microcrystalline high-alumina spherical grinding functional ceramic material is obtained.

[0019] Comparative Example 1 A comparative method for preparing microcrystalline high-alumina spheroids includes the following steps: (1) Zirconium oxychloride octahydrate and glucose were added to deionized water. The ratio of zirconium oxychloride octahydrate to glucose to deionized water was 6g:13g:200mL. The mixture was stirred for 30 minutes until homogeneous. The mixture was heated to 45°C in a water bath and stirred for 20 minutes. Then, sodium citrate solution was added. The ratio of sodium citrate solution to zirconium oxychloride octahydrate was 10mL:6g. The concentration of sodium citrate in the sodium citrate solution was 25g / L, and the solvent was water. After the addition was completed, the mixture was stirred at 45°C for 30 minutes. The mixture was then aged at room temperature for 24 hours. The mixture was then concentrated under reduced pressure and dried at 100°C for 24 hours to remove water. After drying, the mixture was calcined at 1100°C for 10 hours and then cooled to room temperature to obtain the matrix particles of this comparative example. (2) Prepare a composite aqueous solution of lithium acetate and cerium acetate, wherein the concentration of lithium acetate is 24 g / L, the concentration of cerium acetate is 2 g / L, and the solvent is water; prepare an ethanol solution of tetraethyl silicate, wherein the mass percentage of tetraethyl silicate in the ethanol solution of tetraethyl silicate is 6%, and the solvent is ethanol; immerse the matrix particles in the composite aqueous solution of lithium acetate and cerium acetate, maintain the pressure at a negative pressure of 0.01 standard atmospheres for 10 min, then separate the solid and liquid phases, dry the solid phase at 100℃ for 15 min, calcine at 500℃ for 10 min, air cool to room temperature after calcination, and immerse the particles again in the ethanol solution of tetraethyl silicate. In an ethanol solution of ethyl acetate, the mixture is placed under a negative pressure of 0.01 atmospheres for 10 minutes, followed by solid-liquid separation. The solid phase is then dried at 100°C for 15 minutes, calcined at 500°C for 10 minutes, and air-cooled to room temperature. It is then immersed again in the composite aqueous solution of lithium acetate and cerium acetate. This process of immersion in the composite aqueous solution of lithium acetate and cerium acetate, under negative pressure, solid-liquid separation, drying, calcination, and air cooling, and immersion in an ethanol solution of tetraethyl silicate under negative pressure, solid-liquid separation, drying, calcination, and air cooling constitutes one loading process. This loading process is repeated 10 times. The final calcination at 500°C for 1 hour ensures complete decomposition, yielding composite oxide-coated particles. (3) Prepare a composite aqueous solution of magnesium nitrate and barium nitrate in a reactor; the concentration of magnesium nitrate in the composite aqueous solution of magnesium nitrate and barium nitrate is 75 g / L, the concentration of barium nitrate is 55 g / L, and the solvent is water; prepare an aqueous solution of ammonium fluoride; the concentration of ammonium fluoride in the aqueous solution of ammonium fluoride is 55 g / L, and the solvent is water; then add the aqueous solution of ammonium fluoride to the reactor under stirring, the volume ratio of the aqueous solution of ammonium fluoride to the composite aqueous solution of magnesium nitrate and barium nitrate is 1:1; after the addition is completed, seal the reactor, heat it to 180℃ under ultrasonic environment and keep it at that temperature for 80 h, and stir it magnetically during the heat preservation process; after the heat preservation is completed, cool it to room temperature, open the reactor, separate the solid and liquid phases, wash the solid phase with deionized water 3 times, and dry it at 100℃ for 2 h to obtain the additive particles; (4) Weigh each raw material component, and each component is as follows by weight: 100 parts of bauxite, 25 parts of the composite oxide layer coated particles, 5 parts of the additive particles, 5 parts of titanium dioxide powder, 3 parts of talc powder, and 3 parts of potassium feldspar powder; add bauxite, the composite oxide layer coated particles, the additive particles, titanium dioxide powder, talc powder, potassium feldspar powder, and water into a planetary ball mill for ball milling and mixing to obtain a mixed slurry; the ball-to-material mass ratio of the ball-milled mixture is ball:material:water = 1.8:1:0.9; the ball milling time is 12 hours and the rotation speed is 100 rpm; remove iron from the mixed slurry and then spray dry it to make powder particles; add deionized water to the powder particles, and the material-to-water mass ratio of the powder particles to deionized water is powder particles:deionized water = 9:1; continuously roll in a ball mill, gradually grow and form, to obtain a ball blank; (5) The spherical blank is dried at 110℃ for 20h; then it is placed in a kiln for sintering, going through three stages: preheating, high-temperature sintering and cooling: first, the temperature is raised to 600℃ at a heating rate of 10℃ / min and held for 30min, then the temperature is raised to 850℃ at a heating rate of 5℃ / min for preheating and held for 60min, then the temperature is raised to 1250℃ at a high-temperature sintering rate of 3℃ / min for 90min, then the temperature is lowered to 750℃ at a heating rate of 5℃ / min and held for 20min, then the temperature is lowered to 200℃ at a heating rate of 10℃ / min and held for 20min, and finally air-cooled to room temperature; the microcrystalline high-alumina spherical blank described in this comparative example is obtained.

[0020] Comparative Example 2 A comparative method for preparing microcrystalline high-alumina spheroids includes the following steps: (1) Zirconium oxychloride octahydrate and glucose were added to deionized water. The ratio of zirconium oxychloride octahydrate to glucose to deionized water was 6g:13g:200mL. The mixture was stirred for 30 minutes until homogeneous. Boric acid was then added. After the addition was completed, the mixture was heated to 45°C in a water bath and kept warm. The mixture was stirred for 20 minutes. Then, sodium citrate solution was added. The ratio of the amount of boric acid and sodium citrate solution added to the amount of zirconium oxychloride octahydrate added was 3g:10mL:6g. The concentration of sodium citrate in the sodium citrate solution was 25g / L, and the solvent was water. After the addition was completed, the mixture was kept warm at 45°C and stirred for 30 minutes. The mixture was then allowed to stand at room temperature for 24 hours. The mixture was then concentrated under reduced pressure and dried at 100°C for 24 hours to remove water. After drying, the mixture was heated to 1100°C and calcined for 10 hours. The mixture was then cooled to room temperature to obtain matrix particles. (2) Prepare an aqueous solution of lithium acetate, wherein the concentration of lithium acetate in the aqueous solution is 24 g / L, and the solvent is water; prepare an ethanol solution of tetraethyl silicate, wherein the mass percentage of tetraethyl silicate in the ethanol solution of tetraethyl silicate is 6%, and the solvent is ethanol; immerse the matrix particles in the aqueous solution of lithium acetate, maintain the pressure at a negative pressure of 0.01 standard atmospheres for 10 min, then separate the solid and liquid phases, dry the solid phase at 100℃ for 15 min, calcine it at 500℃ for 10 min, air cool it to room temperature after calcination, and then immerse it again in the ethanol solution of tetraethyl silicate. The particles were placed under a negative pressure of 0.01 atmospheres for 10 minutes, followed by solid-liquid separation. The solid phase was dried at 100°C for 15 minutes, calcined at 500°C for 10 minutes, and then air-cooled to room temperature. The particles were then immersed again in the aqueous solution of lithium acetate. This process of immersion in the aqueous solution of lithium acetate, holding under negative pressure, solid-liquid separation, drying, calcination, and air cooling, followed by immersion in the ethanol solution of tetraethyl orthosilicate, holding under negative pressure, solid-liquid separation, drying, calcination, and air cooling constituted one loading process. This loading process was repeated 10 times. The final calcination at 500°C for 1 hour was used for complete decomposition to obtain composite oxide-coated particles. (3) Prepare a composite aqueous solution of magnesium nitrate and barium nitrate in a reactor; the concentration of magnesium nitrate in the composite aqueous solution of magnesium nitrate and barium nitrate is 75 g / L, the concentration of barium nitrate is 55 g / L, and the solvent is water; prepare an aqueous solution of ammonium fluoride; the concentration of ammonium fluoride in the aqueous solution of ammonium fluoride is 55 g / L, and the solvent is water; then add the aqueous solution of ammonium fluoride to the reactor under stirring, the volume ratio of the aqueous solution of ammonium fluoride to the composite aqueous solution of magnesium nitrate and barium nitrate is 1:1; after the addition is completed, seal the reactor, heat it to 180℃ under ultrasonic environment and keep it at that temperature for 80 h, and stir it magnetically during the heat preservation process; after the heat preservation is completed, cool it to room temperature, open the reactor, separate the solid and liquid phases, wash the solid phase with deionized water 3 times, and dry it at 100℃ for 2 h to obtain the additive particles; (4) Weigh each raw material component, and each component is as follows by weight: 100 parts of bauxite, 25 parts of the composite oxide layer coated particles, 5 parts of the additive particles, 5 parts of titanium dioxide powder, 3 parts of talc powder, and 3 parts of potassium feldspar powder; add bauxite, the composite oxide layer coated particles, the additive particles, titanium dioxide powder, talc powder, potassium feldspar powder, and water into a planetary ball mill for ball milling and mixing to obtain a mixed slurry; the ball-to-material mass ratio of the ball-milled mixture is ball:material:water = 1.8:1:0.9; the ball milling time is 12 hours and the rotation speed is 100 rpm; remove iron from the mixed slurry and then spray dry it to make powder particles; add deionized water to the powder particles, and the material-to-water mass ratio of the powder particles to deionized water is powder particles:deionized water = 9:1; continuously roll in a ball mill, gradually grow and form, to obtain a ball blank; (5) The spherical blank is dried at 110℃ for 20h; then it is placed in a kiln for sintering, going through three stages: preheating, high-temperature sintering and cooling: first, the temperature is raised to 600℃ at a heating rate of 10℃ / min and held for 30min, then the temperature is raised to 850℃ at a heating rate of 5℃ / min for preheating and held for 60min, then the temperature is raised to 1250℃ at a high-temperature sintering rate of 3℃ / min for 90min, then the temperature is lowered to 750℃ at a heating rate of 5℃ / min and held for 20min, then the temperature is lowered to 200℃ at a heating rate of 10℃ / min and held for 20min, and finally air-cooled to room temperature; the microcrystalline high-alumina spherical blank described in this comparative example is obtained.

[0021] Comparative Example 3 A comparative method for preparing microcrystalline high-alumina spheroids includes the following steps: (1) Zirconium oxychloride octahydrate and glucose were added to deionized water. The ratio of zirconium oxychloride octahydrate to glucose to deionized water was 6g:13g:200mL. The mixture was stirred for 30 minutes until homogeneous. Boric acid was then added. After the addition was completed, the mixture was heated to 45°C in a water bath and kept warm. The mixture was stirred for 20 minutes. Then, sodium citrate solution was added. The ratio of the amount of boric acid and sodium citrate solution added to the amount of zirconium oxychloride octahydrate added was 3g:10mL:6g. The concentration of sodium citrate in the sodium citrate solution was 25g / L, and the solvent was water. After the addition was completed, the mixture was kept warm at 45°C and stirred for 30 minutes. The mixture was then allowed to stand at room temperature for 24 hours. The mixture was then concentrated under reduced pressure and dried at 100°C for 24 hours to remove water. After drying, the mixture was heated to 1100°C and calcined for 10 hours. The mixture was then cooled to room temperature to obtain matrix particles. (2) Prepare an aqueous solution of cerium acetate, wherein the concentration of cerium acetate in the aqueous solution is 2 g / L, and the solvent is water; prepare an ethanol solution of tetraethyl silicate, wherein the mass percentage of tetraethyl silicate in the ethanol solution of tetraethyl silicate is 6%, and the solvent is ethanol; immerse the matrix particles in the aqueous solution of cerium acetate, maintain pressure at a negative pressure of 0.01 standard atmospheres for 10 min, then separate the solid and liquid phases, dry the solid phase at 100℃ for 15 min, calcine at 500℃ for 10 min, air cool to room temperature after calcination, and immerse them again in the ethanol solution of tetraethyl silicate. The solid phase was held under negative pressure at 0.01 atmospheres for 10 minutes, then subjected to solid-liquid separation. The solid phase was dried at 100°C for 15 minutes, calcined at 500°C for 10 minutes, and air-cooled to room temperature. Then, it was immersed again in the aqueous solution of cerium acetate. The above process of immersion in the aqueous solution of cerium acetate, holding under negative pressure, solid-liquid separation, drying, calcination, and air cooling, followed by immersion in the ethanol solution of tetraethyl orthosilicate, holding under negative pressure, solid-liquid separation, drying, calcination, and air cooling constitutes one loading process. The above loading process was repeated for a total of 10 sets. The final calcination at 500°C for 1 hour was used for complete decomposition to obtain composite oxide layer coated particles. (3) Prepare a composite aqueous solution of magnesium nitrate and barium nitrate in a reactor; the concentration of magnesium nitrate in the composite aqueous solution of magnesium nitrate and barium nitrate is 75 g / L, the concentration of barium nitrate is 55 g / L, and the solvent is water; prepare an aqueous solution of ammonium fluoride; the concentration of ammonium fluoride in the aqueous solution of ammonium fluoride is 55 g / L, and the solvent is water; then add the aqueous solution of ammonium fluoride to the reactor under stirring, the volume ratio of the aqueous solution of ammonium fluoride to the composite aqueous solution of magnesium nitrate and barium nitrate is 1:1; after the addition is completed, seal the reactor, heat it to 180℃ under ultrasonic environment and keep it at that temperature for 80 h, and stir it magnetically during the heat preservation process; after the heat preservation is completed, cool it to room temperature, open the reactor, separate the solid and liquid phases, wash the solid phase with deionized water 3 times, and dry it at 100℃ for 2 h to obtain the additive particles; (4) Weigh each raw material component, and each component is as follows by weight: 100 parts of bauxite, 25 parts of the composite oxide layer coated particles, 5 parts of the additive particles, 5 parts of titanium dioxide powder, 3 parts of talc powder, and 3 parts of potassium feldspar powder; add bauxite, the composite oxide layer coated particles, the additive particles, titanium dioxide powder, talc powder, potassium feldspar powder, and water into a planetary ball mill for ball milling and mixing to obtain a mixed slurry; the ball-to-material mass ratio of the ball-milled mixture is ball:material:water = 1.8:1:0.9; the ball milling time is 12 hours and the rotation speed is 100 rpm; remove iron from the mixed slurry and then spray dry it to make powder particles; add deionized water to the powder particles, and the material-to-water mass ratio of the powder particles to deionized water is powder particles:deionized water = 9:1; continuously roll in a ball mill, gradually grow and form, to obtain a ball blank; (5) The spherical blank is dried at 110℃ for 20h; then it is placed in a kiln for sintering, going through three stages: preheating, high-temperature sintering and cooling: first, the temperature is raised to 600℃ at a heating rate of 10℃ / min and held for 30min, then the temperature is raised to 850℃ at a heating rate of 5℃ / min for preheating and held for 60min, then the temperature is raised to 1250℃ at a high-temperature sintering rate of 3℃ / min for 90min, then the temperature is lowered to 750℃ at a heating rate of 5℃ / min and held for 20min, then the temperature is lowered to 200℃ at a heating rate of 10℃ / min and held for 20min, and finally air-cooled to room temperature; the microcrystalline high-alumina spherical blank described in this comparative example is obtained.

[0022] Comparative Example 4 A comparative method for preparing microcrystalline high-alumina spheroids includes the following steps: (1) Zirconium oxychloride octahydrate and glucose were added to deionized water. The ratio of zirconium oxychloride octahydrate to glucose to deionized water was 6g:13g:200mL. The mixture was stirred for 30 minutes until homogeneous. Boric acid was then added. After the addition was completed, the mixture was heated to 45°C in a water bath and kept warm. The mixture was stirred for 20 minutes. Then, sodium citrate solution was added. The ratio of the amount of boric acid and sodium citrate solution added to the amount of zirconium oxychloride octahydrate added was 3g:10mL:6g. The concentration of sodium citrate in the sodium citrate solution was 25g / L, and the solvent was water. After the addition was completed, the mixture was kept warm at 45°C and stirred for 30 minutes. The mixture was then allowed to stand at room temperature for 24 hours. The mixture was then concentrated under reduced pressure and dried at 100°C for 24 hours to remove water. After drying, the mixture was heated to 1100°C and calcined for 10 hours. The mixture was then cooled to room temperature to obtain matrix particles. (2) Prepare an ethanol solution of tetraethyl silicate; the ethanol solution of tetraethyl silicate contains 6% tetraethyl silicate by mass and ethanol as the solvent; immerse the matrix particles in the ethanol solution of tetraethyl silicate, maintain pressure at 0.01 standard atmospheres for 10 min, then separate the solid and liquid phases, dry the solid phase at 100℃ for 15 min, calcine at 500℃ for 10 min, air cool to room temperature after calcination, and immerse them again in the ethanol solution of tetraethyl silicate; the above process of immersing in the ethanol solution of tetraethyl silicate, maintaining pressure under negative pressure, separating the solid and liquid phases, drying, calcining, and air cooling constitutes one loading process; repeat the above loading process for a total of 10 sets, and finally calcine at 500℃ for 1 h to fully decompose the particles and obtain the composite oxide layer coated particles. (3) Prepare a composite aqueous solution of magnesium nitrate and barium nitrate in a reactor; the concentration of magnesium nitrate in the composite aqueous solution of magnesium nitrate and barium nitrate is 75 g / L, the concentration of barium nitrate is 55 g / L, and the solvent is water; prepare an aqueous solution of ammonium fluoride; the concentration of ammonium fluoride in the aqueous solution of ammonium fluoride is 55 g / L, and the solvent is water; then add the aqueous solution of ammonium fluoride to the reactor under stirring, the volume ratio of the aqueous solution of ammonium fluoride to the composite aqueous solution of magnesium nitrate and barium nitrate is 1:1; after the addition is completed, seal the reactor, heat it to 180℃ under ultrasonic environment and keep it at that temperature for 80 h, and stir it magnetically during the heat preservation process; after the heat preservation is completed, cool it to room temperature, open the reactor, separate the solid and liquid phases, wash the solid phase with deionized water 3 times, and dry it at 100℃ for 2 h to obtain the additive particles; (4) Weigh each raw material component, and each component is as follows by weight: 100 parts of bauxite, 25 parts of the composite oxide layer coated particles, 5 parts of the additive particles, 5 parts of titanium dioxide powder, 3 parts of talc powder, and 3 parts of potassium feldspar powder; add bauxite, the composite oxide layer coated particles, the additive particles, titanium dioxide powder, talc powder, potassium feldspar powder, and water into a planetary ball mill for ball milling and mixing to obtain a mixed slurry; the ball-to-material mass ratio of the ball-milled mixture is ball:material:water = 1.8:1:0.9; the ball milling time is 12 hours and the rotation speed is 100 rpm; remove iron from the mixed slurry and then spray dry it to make powder particles; add deionized water to the powder particles, and the material-to-water mass ratio of the powder particles to deionized water is powder particles:deionized water = 9:1; continuously roll in a ball mill, gradually grow and form, to obtain a ball blank; (5) The spherical blank is dried at 110℃ for 20h; then it is placed in a kiln for sintering, going through three stages: preheating, high-temperature sintering and cooling: first, the temperature is raised to 600℃ at a heating rate of 10℃ / min and held for 30min, then the temperature is raised to 850℃ at a heating rate of 5℃ / min for preheating and held for 60min, then the temperature is raised to 1250℃ at a high-temperature sintering rate of 3℃ / min for 90min, then the temperature is lowered to 750℃ at a heating rate of 5℃ / min and held for 20min, then the temperature is lowered to 200℃ at a heating rate of 10℃ / min and held for 20min, and finally air-cooled to room temperature; the microcrystalline high-alumina spherical blank described in this comparative example is obtained.

[0023] Comparative Example 5 A comparative method for preparing microcrystalline high-alumina spheroids includes the following steps: (1) Zirconium oxychloride octahydrate and glucose were added to deionized water. The ratio of zirconium oxychloride octahydrate to glucose to deionized water was 6g:13g:200mL. The mixture was stirred for 30 minutes until homogeneous. Boric acid was then added. After the addition was completed, the mixture was heated to 45°C in a water bath and kept warm. The mixture was stirred for 20 minutes. Then, sodium citrate solution was added. The ratio of the amount of boric acid and sodium citrate solution added to the amount of zirconium oxychloride octahydrate added was 3g:10mL:6g. The concentration of sodium citrate in the sodium citrate solution was 25g / L, and the solvent was water. After the addition was completed, the mixture was kept warm at 45°C and stirred for 30 minutes. The mixture was then allowed to stand at room temperature for 24 hours. The mixture was then concentrated under reduced pressure and dried at 100°C for 24 hours to remove water. After drying, the mixture was heated to 1100°C and calcined for 10 hours. The mixture was then cooled to room temperature to obtain matrix particles. (2) Prepare a composite aqueous solution of lithium acetate and cerium acetate, wherein the concentration of lithium acetate is 24 g / L, the concentration of cerium acetate is 2 g / L, and the solvent is water; prepare an ethanol solution of tetraethyl silicate, wherein the mass percentage of tetraethyl silicate in the ethanol solution of tetraethyl silicate is 6%, and the solvent is ethanol; immerse the matrix particles in the composite aqueous solution of lithium acetate and cerium acetate, maintain the pressure at a negative pressure of 0.01 standard atmospheres for 10 min, then separate the solid and liquid phases, dry the solid phase at 100℃ for 15 min, calcine at 500℃ for 10 min, air cool to room temperature after calcination, and immerse the particles again in the ethanol solution of tetraethyl silicate. In an ethanol solution of ethyl acetate, the mixture is placed under a negative pressure of 0.01 atmospheres for 10 minutes, followed by solid-liquid separation. The solid phase is then dried at 100°C for 15 minutes, calcined at 500°C for 10 minutes, and air-cooled to room temperature. It is then immersed again in the composite aqueous solution of lithium acetate and cerium acetate. This process of immersion in the composite aqueous solution of lithium acetate and cerium acetate, under negative pressure, solid-liquid separation, drying, calcination, and air cooling, and immersion in an ethanol solution of tetraethyl silicate under negative pressure, solid-liquid separation, drying, calcination, and air cooling constitutes one loading process. This loading process is repeated 10 times. The final calcination at 500°C for 1 hour ensures complete decomposition, yielding composite oxide-coated particles. (3) Prepare a composite aqueous solution of magnesium nitrate and barium nitrate in a reactor; the concentration of magnesium nitrate in the composite aqueous solution of magnesium nitrate and barium nitrate is 75 g / L, the concentration of barium nitrate is 55 g / L, and the solvent is water; prepare an ammonia solution; the mass percentage of solute in the ammonia solution is 20%, and the solvent is water; then add the ammonia solution to the reactor under stirring, the volume ratio of the ammonia solution added to the composite aqueous solution of magnesium nitrate and barium nitrate is 1:1; after the addition is completed, seal the reactor, heat it to 180℃ under ultrasonic environment and keep it at that temperature for 80 h, and stir it magnetically during the heat preservation process; after the heat preservation is completed, cool it to room temperature, open the reactor, separate the solid and liquid phases, wash the solid phase three times with deionized water, and dry it at 100℃ for 2 h to obtain the additive particles; (4) Weigh each raw material component, and each component is as follows by weight: 100 parts of bauxite, 25 parts of the composite oxide layer coated particles, 5 parts of the additive particles, 5 parts of titanium dioxide powder, 3 parts of talc powder, and 3 parts of potassium feldspar powder; add bauxite, the composite oxide layer coated particles, the additive particles, titanium dioxide powder, talc powder, potassium feldspar powder, and water into a planetary ball mill for ball milling and mixing to obtain a mixed slurry; the ball-to-material mass ratio of the ball-milled mixture is ball:material:water = 1.8:1:0.9; the ball milling time is 12 hours and the rotation speed is 100 rpm; remove iron from the mixed slurry and then spray dry it to make powder particles; add deionized water to the powder particles, and the material-to-water mass ratio of the powder particles to deionized water is powder particles:deionized water = 9:1; continuously roll in a ball mill, gradually grow and form, to obtain a ball blank; (5) The spherical blank is dried at 110℃ for 20h; then it is placed in a kiln for sintering, going through three stages: preheating, high-temperature sintering and cooling: first, the temperature is raised to 600℃ at a heating rate of 10℃ / min and held for 30min, then the temperature is raised to 850℃ at a heating rate of 5℃ / min for preheating and held for 60min, then the temperature is raised to 1250℃ at a high-temperature sintering rate of 3℃ / min for 90min, then the temperature is lowered to 750℃ at a heating rate of 5℃ / min and held for 20min, then the temperature is lowered to 200℃ at a heating rate of 10℃ / min and held for 20min, and finally air-cooled to room temperature; the microcrystalline high-alumina spherical blank described in this comparative example is obtained.

[0024] Example 5 The equivalent wear of the microcrystalline high-alumina spheres prepared by the methods described in the above embodiments and comparative examples was tested according to the requirements of standard JC / T 848.1-2010, and the results are shown in Table 1.

[0025] Table 1 As shown in Table 1, the microcrystalline high-alumina ball grinding functional ceramic material prepared by the method described in this invention exhibits excellent wear resistance and has broad application prospects in modern industrial fields as a high-efficiency wear-resistant material. Comparison of Example 2 and various comparative examples shows that introducing the composite oxide layer coating particles and additive particles described in this invention into the traditional bauxite-based ceramic material can further reduce the equivalent wear of the microcrystalline high-alumina ball and improve its wear resistance. This may be because: this invention first prepares high-strength boron and zirconium hard matrix particles. By adding hard matrix particles into the ceramic matrix, grain boundaries can be effectively pinned, playing a second-phase strengthening role. Furthermore, the added zirconium undergoes phase transformation toughening during sintering, absorbing crack propagation energy and reducing the generation of microcracks during sintering. Subsequently, a Li-Ce-Si composite oxide layer is coated on the hard matrix particles, which easily forms a eutectic liquid phase with aluminum in the bauxite during sintering, filling the pores and cracks in the green body and significantly increasing the bulk density of the material. Meanwhile, the eutectic liquid phase can lower the sintering temperature, promote grain rearrangement and mass transfer, resulting in a more uniform microstructure and thus reducing wear. Furthermore, the introduced silicon can form trace amounts of silica-oxygen glass phase during high-temperature sintering, thereby promoting ceramic sintering, refining grains, and further improving the ceramic's wear resistance and reducing the coefficient of friction. The added additive particles are magnesium-barium composite fluorides with high-temperature softening and ductility; their addition to bauxite-based ceramic materials after sintering also helps improve the coefficient of friction of microcrystalline high-alumina spherical particles.

[0026] The technical solutions provided by the present invention have been described in detail above. For those skilled in the art, there will be changes in specific implementation methods and application scope based on the ideas of the embodiments of the present invention. Therefore, the content of this specification should not be construed as a limitation of the present invention.

Claims

1. A method for preparing a microcrystalline high-alumina ball grinding functional ceramic material, characterized in that the steps include: include: (1) Add zirconium oxychloride octahydrate and glucose to deionized water, stir evenly, then add boric acid. After the addition is complete, heat in a water bath, stir, add sodium citrate solution, stir evenly after the addition is complete, let stand and age, then concentrate under reduced pressure, dry, heat to 1100-1200℃ after drying, calcine, and air cool to room temperature to obtain matrix particles. (2) Prepare a composite aqueous solution of lithium acetate and cerium acetate, and prepare an ethanol solution of tetraethyl silicate; immerse the matrix particles in the composite aqueous solution of lithium acetate and cerium acetate, maintain pressure under negative pressure, then separate the solid and liquid phases, dry the solid phase, calcine, and air-cool to room temperature after calcination, then immerse them again in the ethanol solution of tetraethyl silicate, maintain pressure under negative pressure, then separate the solid and liquid phases again, dry the solid phase, calcine, air-cool to room temperature, and then immerse them again in the composite aqueous solution of lithium acetate and cerium acetate; the above process of immersing in the composite aqueous solution of lithium acetate and cerium acetate, maintaining pressure under negative pressure, separating the solid and liquid phases, drying, calcining, air-cooling, immersing in the ethanol solution of tetraethyl silicate, maintaining pressure under negative pressure, separating the solid and liquid phases, drying, calcining, and air-cooling constitutes one loading process; repeat the above loading process for more than 10 sets, and calcine for more than 1 hour in the last time to fully decompose the particles and obtain the composite oxide layer coated particles. (3) Prepare a composite aqueous solution of magnesium nitrate and barium nitrate in a reactor; prepare an aqueous solution of ammonium fluoride; then add the aqueous solution of ammonium fluoride to the reactor under stirring. After the addition is completed, seal the reactor and heat it to above 180°C under ultrasonic conditions for hydrothermal reaction. Stir magnetically during the heat preservation process. After the heat preservation is completed, cool it to room temperature, open the reactor, separate the solid and liquid, wash the solid phase, dry it, and obtain the additive particles. (4) Add bauxite, the composite oxide layer coated particles, the additive particles, titanium dioxide powder, talc powder, potassium feldspar powder and water to a planetary ball mill for ball milling and mixing to obtain a mixed slurry; remove iron from the mixed slurry and then spray dry it to make powder particles; add deionized water to the powder particles and continuously roll them in a ball mill to gradually grow and form them to obtain ball blanks; (5) The blank is dried and then sintered in a kiln to obtain the microcrystalline high-alumina ball grinding functional ceramic material.

2. The method for preparing a microcrystalline high-alumina ball grinding functional ceramic material according to claim 1, characterized in that, In step (1), the ratio of zirconium oxychloride octahydrate and glucose added to deionized water is zirconium oxychloride octahydrate: glucose: deionized water = 5-7g: 12-15g: 200mL; the ratio of the amount of boric acid and sodium citrate solution added to the amount of zirconium oxychloride octahydrate added is boric acid: sodium citrate solution: zirconium oxychloride octahydrate = 3-4g: 10-15mL: 5-7g, wherein the concentration of sodium citrate in the sodium citrate solution is 20-30g / L, and the solvent is water.

3. The method for preparing a microcrystalline high-alumina ball grinding functional ceramic material according to claim 1, characterized in that, In step (1), the static aging time is more than 24 hours; the calcination time is 8 to 12 hours.

4. The method for preparing a microcrystalline high-alumina ball grinding functional ceramic material according to claim 1, characterized in that, In step (2), the concentration of lithium acetate in the composite aqueous solution of lithium acetate and cerium acetate is 22-26 g / L, the concentration of cerium acetate is 2-2.5 g / L, and the solvent is water; in the ethanol solution of tetraethyl silicate, the mass percentage of tetraethyl silicate is 5%-8%, and the solvent is ethanol.

5. The method for preparing a microcrystalline high-alumina ball grinding functional ceramic material according to claim 1, characterized in that, In step (2), the calcination temperature is 500-550℃.

6. The method for preparing a microcrystalline high-alumina ball grinding functional ceramic material according to claim 1, characterized in that, In step (3), the concentration of magnesium nitrate in the composite aqueous solution of magnesium nitrate and barium nitrate is 70-80 g / L, the concentration of barium nitrate is 55-60 g / L, and the solvent is water; the concentration of ammonium fluoride in the aqueous solution of ammonium fluoride is 50-60 g / L, and the solvent is water; the volume ratio of the aqueous solution of ammonium fluoride added to the composite aqueous solution of magnesium nitrate and barium nitrate is 1:

1.

7. The method for preparing a microcrystalline high-alumina ball grinding functional ceramic material according to claim 1, characterized in that, In step (4), the components are as follows by weight: 100 parts of bauxite, 20-30 parts of the composite oxide layer coated particles, 5-10 parts of the additive particles, 5-10 parts of titanium dioxide powder, 2-5 parts of talc powder, and 2-5 parts of potassium feldspar powder.

8. The method for preparing a microcrystalline high-alumina ball grinding functional ceramic material according to claim 1, characterized in that, In step (4), the ball-to-material mass ratio of the ball milling mixture is ball:material:water = 1.6-2:1:0.8-1; the ball milling time is 12-20 hours and the rotation speed is 80-100 rpm; the material-to-water mass ratio of the powder particles to deionized water is powder particles:deionized water = 9:

1.

9. The method for preparing a microcrystalline high-alumina ball grinding functional ceramic material according to claim 1, characterized in that, In step (5), the spherical blank is dried at 110-120℃ for 20-24 hours; then it is placed in a kiln and undergoes three stages: preheating, high-temperature sintering and cooling. First, the temperature is increased to 600-650℃ at a rate of 10℃ / min and held for 30-40 minutes. Then, the temperature is increased to 850-900℃ at a rate of 5℃ / min for preheating and held for 60-80 minutes. Then, the temperature is increased to 1250-1300℃ at a rate of 3℃ / min for high-temperature sintering for 60-90 minutes. Then, the temperature is decreased to 750-800℃ at a rate of 5℃ / min and held for 10-20 minutes. After holding, the temperature is decreased to 200-250℃ at a rate of 10℃ / min and held for 10-20 minutes. Finally, it is air-cooled to room temperature.

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