CN112457005A - Composite preparation method of submillimeter-level zirconia ceramic microspheres - Google Patents
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Abstract
The invention discloses a composite preparation method of submillimeter-level zirconia ceramic microspheres, belonging to the technical field of ceramic materials.A zirconium oxide slurry is formed by adding an initiator and a light curing agent into a mixed solution of a propylene monomer, a cross-linking agent, a dispersing agent and yttrium-stabilized zirconia; injecting the zirconia slurry into oil bath liquid paraffin containing a catalyst, and simultaneously irradiating by adopting ultraviolet light to form a zirconia ceramic microbead green body, sintering the green body by adopting temperature programming, and forming the submillimeter-sized zirconia ceramic microbead after self-polishing; the invention adopts the composite molding technology of catalytic curing and UV curing, and the size of the prepared zirconia ceramic microspheres can reach a submillimeter level, and the zirconia ceramic microspheres have higher density and good wear resistance.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a composite preparation method of submillimeter-level zirconia ceramic microspheres.
Background
With the development of industrialization, high-performance grinding media are widely applied to the industries of mines, inorganic materials, electric power energy, chemical engineering and the like. According to the estimation, 500-600 million tons of ball grinding products are consumed globally every year, and the domestic consumption is over 200-250 million tons. Especially, the ceramic microspheres with the particle size of submillimeter level have wide market space. This is not only because of the large specific surface area of the ceramic microspheres and the high ball milling efficiency, but also because of the demand of the industrial product for the ultrafine grinding of the raw materials. In the grinding process of preparing the superfine powder, the powder product is required to have fine granularity, good grading effect, stable product quality, high production efficiency and strong controllability of the production process. Therefore, the selection of the type and quality of the grinding medium directly determines the physical and chemical properties of the product, and affects the efficiency of the mill and the production cost of the ultra-fine powder. In the production of ceramics, by means of the outstanding advantages of high strength, high hardness, excellent wear resistance and corrosion resistance, etc., zirconia ceramic balls are distinguished from a plurality of series of ceramic grinding ball stones and are favored by the ceramic industry.
At present, the zirconia ceramic microspheres are prepared by adopting the traditional gel injection molding technology, and the molding technology is also widely applied to Al2O3、ZrO2、SiC、AlN、Si3N4Etc. oxide or non-oxide precision ceramic systems. However, the ceramic microspheres prepared by the gel casting molding process have insufficiently compact structure and poor wear resistance, and cannot be used for preparing submillimeter-level zirconia ceramic microspheres with the particle size of less than 0.3 mm.
Disclosure of Invention
The invention provides a composite preparation method of submillimeter-level zirconia ceramic microspheres, which solves the problems that in the prior art, the zirconia ceramic microspheres are not compact in structure and not up to standard in particle size, and meanwhile, the size of the zirconia ceramic microspheres can be controlled, and the preparation efficiency is improved.
The invention provides a composite preparation method of submillimeter-level zirconia ceramic microspheres, which comprises the following steps:
step 1, preparation of slurry
Dissolving a propylene monomer, a cross-linking agent and a dispersing agent in a water solvent to form a mixed solution, and adjusting the pH value of the mixed solution to 8-10; adding yttrium-stabilized zirconia into the mixed solution, uniformly dispersing, adding a defoaming agent, and stirring; adding an initiator and a light curing agent into the zirconia slurry, and stirring to form uniform and stable zirconia slurry;
step 2, preparing zirconia ceramic microsphere green body
Injecting the zirconia slurry obtained in the step 1 into oil bath liquid paraffin containing a catalyst, and stirring at 50-80 ℃ to form zirconia ceramic microspheres; simultaneously irradiating the zirconia ceramic microspheres by using an ultraviolet lamp to prepare a zirconia ceramic microsphere green body;
step 3, sintering of the green compact
And (3) cleaning and drying the zirconia ceramic microbead green body prepared in the step (2), heating to 1520-1550 ℃ by adopting a program, sintering, and self-polishing to obtain the submillimeter-level zirconia ceramic microbead.
Preferably, in the step 1, the propylene monomer is one or a mixture of acrylamide, hydroxyethyl acrylate and hydroxypropyl acrylate; the cross-linking agent is N-N' -methylene bisacrylamide; the initiator is one or a mixture of ammonium persulfate, sodium persulfate and potassium persulfate; the light curing agent is one or a mixture of a plurality of benzophenone derivatives, benzil derivatives and alkyl aryl ketone derivatives.
Preferably, the mass ratio of the propylene monomer to the cross-linking agent is 1: 0.1-0.125; the mass ratio of the propylene monomer to the initiator is 1: 0.2-0.25; the mass ratio of the propylene monomer to the light curing agent is 1: 0.3-0.375.
Preferably, in the step 1, the yttrium-stabilized zirconia is 3-8 mol% yttrium oxide-stabilized zirconia; the mass ratio of the propylene monomer to the yttrium-stabilized zirconia is 1: 6-8.75.
Preferably, in the step 1, the dispersant is one or a mixture of polyacrylic acid, citric acid and oxalic acid; the defoaming agent is a surfactant containing alcohols or ethers; the mass ratio of the propylene monomer to the dispersing agent is 1: 0.2-0.25, and the mass ratio of the propylene monomer to the defoaming agent is 1: 0.1-0.125.
Preferably, in step 2, the catalyst is tetramethylethylenediamine or N, N-dimethylaniline; the mass ratio of the propylene monomer to the catalyst is 1: 0.1-0.125.
Preferably, in the step 2, the power of the ultraviolet lamp is 100-300W.
Preferably, in step 2, the preparation method of the zirconia ceramic microspheres specifically comprises: the method comprises the following steps of dropwise adding zirconia slurry into liquid paraffin containing a catalyst through a titration device, dispersing the zirconia slurry dropwise added into the paraffin into zirconia ceramic microspheres under the action of centrifugal force under the stirring condition, wherein the titration device comprises a titration bottle for containing the zirconia slurry, and a hose with a plurality of pinholes is connected with the titration bottle and is provided with a switch.
Preferably, in step 3, the programmed temperature rise specifically is: raising the temperature to 400 ℃ after 130min, and preserving the heat for 2-3 h at 400 ℃; raising the temperature to 600 ℃ within 100min, and preserving the heat for 2-3 h at 600 ℃; raising the temperature to 1200 ℃ within 120min, and keeping the temperature at 1200 ℃ for 2-3 h; raising the temperature to 1520-1550 ℃ in 160-175 min, and preserving the temperature for 2-3 h.
Preferably, in the step 3, the size of the zirconia ceramic micro-beads is 0.1-0.3 mm.
Compared with the prior art, the invention has the beneficial effects that:
(1) adding an initiator and a light curing agent into a mixed solution of a propylene monomer, a cross-linking agent, a dispersing agent and yttrium-stabilized zirconia to form zirconia slurry; injecting the zirconia slurry into oil bath liquid paraffin containing a catalyst, and simultaneously irradiating by adopting ultraviolet light to form a zirconia ceramic microbead green body, sintering the green body by adopting temperature programming, and forming the submillimeter-sized zirconia ceramic microbead after self-polishing; the mechanism is as follows:
due to the difference of the surface tension of the zirconia slurry and the liquid paraffin, molecules of the two-phase interface layer are subjected to two-phase asymmetric acting force, so that the interface layer presents a spherical surface, and the zirconia ceramic microspheres are formed.
The addition of the catalyst improves the reaction rate of initiating agent for initiating free radical polymerization and copolymerization of alkene and diene monomers, and the photoinitiator can absorb the energy of light and split into active free radicals after being irradiated by ultraviolet light, so as to initiate the chain polymerization of the propylene monomers and the cross-linking agent, further improve the polymerization degree of organic matters, achieve the purpose of better controlling the curing rate of the microspheres, and further adjust the morphological structure of the microspheres.
(2) Compared with the prior art, the method has the advantages that the in-situ curing reaction of the microspheres is simultaneously carried out in the process of forming the zirconia ceramic microspheres, the zirconia ceramic microspheres with higher density are obtained, and the wear rate of the microspheres is less than 5 ppm/hr.
(3) The invention can lead the particle diameter of the zirconia ceramic micro-bead to reach the sub-millimeter level and be less than 0.3 mm.
Detailed Description
In order to make the technical solutions of the present invention better understood and enable those skilled in the art to practice the present invention, the following embodiments are further described, but the present invention is not limited to the following embodiments.
The following test methods and detection methods, unless otherwise specified, are conventional methods; the reagents and starting materials are all commercially available, unless otherwise specified.
Example 1
A composite preparation method of submillimeter-level zirconia ceramic microspheres comprises the following steps:
step 1: dissolving 5g of acrylamide, 0.5g of N-N' -methylene bisacrylamide and 1g of citric acid in 30g of deionized water, electrically stirring to form a solution, and simultaneously dropwise adding ammonia water to adjust the pH value of the solution to 8; adding 30g of 3 mol% yttrium-stabilized zirconia into the solution, continuing stirring for 1h, adding 0.5g of isopropanol after uniform dispersion, and stirring for 1 h; 1g of ammonium persulfate and 1.5g of 2-hydroxy-2, 2-dimethylacetophenone are added into the zirconia slurry, and the mixture is stirred for 10min to form uniform and stable zirconia slurry.
Step 2: 0.5g of tetramethylethylenediamine was dropped into a beaker of 500ml of liquid paraffin, and the beaker was placed in an oil bath at 50 ℃. Putting the zirconia slurry prepared in the step 1 into a titration bottle, simultaneously connecting a hose with a plurality of pinholes with the titration bottle, hanging the titration bottle at a height of 1m from a beaker heated by an oil bath, opening a hose switch, dripping the zirconia slurry into paraffin with a catalyst from the pinholes under the action of gravity, simultaneously electrically stirring, and dispersing the dripped zirconia slurry into smaller droplets under the action of centrifugal force. And simultaneously irradiating the microspheres by using a 100W ultraviolet lamp to enable the ammonium persulfate, the 2-hydroxy-2, 2-dimethylacetophenone, the acrylamide and the N-N' -methylene bisacrylamide to perform a curing reaction to form a zirconia ceramic microbead green compact.
And step 3: collecting the zirconia ceramic microbead green compact from the paraffin in the step 2, washing the green compact three times by adopting absolute ethyl alcohol, and removing the paraffin and residual powder on the surface of the green compact; putting the washed zirconia ceramic microbead green body into an electric heating drying oven to be dried for 3 hours at the temperature of 90 ℃; then putting the green body into an SJJ-16 type electric furnace, raising the temperature to 400 ℃ after 130min, and preserving the temperature for 2h at 400 ℃; raising the temperature to 600 ℃ within 100min, and keeping the temperature at 600 ℃ for 2 h; raising the temperature to 1200 ℃ within 120min, and keeping the temperature at 1200 ℃ for 2 h; raising the temperature to 1520 ℃ within 160min, then preserving the heat for 2h, and finally naturally cooling to room temperature to obtain a zirconia ceramic microbead blank;
and 4, step 4: performing self-polishing on the blank of the zirconia ceramic microspheres obtained in the step 3 to obtain the zirconia ceramic microspheres, wherein the size of the zirconia ceramic microspheres is 0.2-0.23 mm, and the density of the zirconia ceramic microspheres is 6.02g/cm through detection3The abrasion rate was 3.9 ppm/hr.
Example 2
A composite preparation method of submillimeter-level zirconia ceramic microspheres comprises the following steps:
step 1: dissolving 8g of hydroxyethyl acrylate, 1g of cross-linking agent N-N' -methylene bisacrylamide and 2g of dispersant polyacrylic acid in 50g of deionized water, electrically stirring to form a solution, and simultaneously dropwise adding ammonia water to adjust the pH value of the solution to 10; adding 70g of 8 mol% yttrium-stabilized zirconia into the solution, continuing stirring for 1h, adding 1g of defoamer isopropanol after uniform dispersion, and stirring for 1 h; 2g of initiator potassium persulfate and 3g of Basff Irgacure 2959 light curing agent are added into the zirconia slurry, and the mixture is stirred for 30min to form uniform and stable zirconia slurry.
Step 2: 1g of N, N-dimethylaniline as a catalyst was dropped into a beaker containing 500ml of liquid paraffin, and the beaker was placed in an oil bath at 55 ℃. Putting the zirconia slurry prepared in the step 1 into a titration bottle, simultaneously connecting a hose with a plurality of pinholes with the titration bottle, hanging the titration bottle at a height of 1m from a beaker heated by water bath, opening a hose switch, dripping the zirconia slurry into paraffin with a catalyst from the pinholes under the action of gravity, simultaneously electrically stirring, and dispersing the dripped zirconia slurry into smaller droplets under the action of centrifugal force. And simultaneously irradiating the microspheres by using a 300W ultraviolet lamp to perform a curing reaction on potassium persulfate, the Pasteur Irgacure 2959 light curing agent, hydroxyethyl acrylate and N-N' -methylene bisacrylamide to form a zirconia ceramic microbead green body.
And step 3: collecting the zirconia ceramic microbead green compact from the paraffin in the step 2, washing the green compact three times by adopting absolute ethyl alcohol, and removing the paraffin and residual powder on the surface of the green compact; putting the washed zirconia ceramic microbead green body into an electric heating drying oven to be dried for 3 hours at the temperature of 90 ℃; then putting the green body into an SJJ-16 type electric furnace, raising the temperature to 400 ℃ after 130min, and preserving the temperature for 3h at 400 ℃; raising the temperature to 600 ℃ within 100min, and preserving the heat at 600 ℃ for 3 h; raising the temperature to 1200 ℃ within 120min, and preserving the heat for 3h at 1200 ℃; raising the temperature to 1550 ℃ in 175min, then preserving the temperature for 3h, and finally naturally cooling to room temperature to obtain the zirconia ceramic microbead blank.
And 4, step 4: performing self-polishing on the blank of the zirconia ceramic microspheres obtained in the step 3 to obtain the zirconia ceramic microspheres, wherein the size of the zirconia ceramic microspheres is 0.18-0.22 mm, and the density of the zirconia ceramic microspheres is 6.05g/cm through detection3The abrasion rate was 4.1 ppm/hr.
Example 3
A preparation method of submillimeter-level zirconia ceramic microspheres comprises the following steps:
step 1: dissolving 5g of hydroxypropyl acrylate, 0.5g of cross-linking agent N-N' -methylene bisacrylamide and 1g of dispersing agent oxalic acid in 50g of deionized water, electrically stirring to form a solution, and simultaneously dropwise adding ammonia water to adjust the pH value of the solution to 10; adding 30g of 3 mol% yttrium-stabilized zirconia into the solution, continuing stirring for 1h, adding 0.5g of defoamer isopropanol after uniform dispersion, and stirring for 1 h; 1g of initiator sodium persulfate and 819DW 1.5g of light curing agent are added into the zirconia slurry and stirred for 30min to form uniform and stable zirconia slurry.
Step 2: 1g of N, N-dimethylaniline as a catalyst was dropped into a beaker containing 500ml of liquid paraffin, and the beaker was placed in an oil bath at 80 ℃. Putting the zirconia slurry prepared in the step 1 into a titration bottle, simultaneously connecting a hose with a plurality of pinholes with the titration bottle, hanging the titration bottle at a height of 1m from a beaker heated by water bath, opening a hose switch, dripping the zirconia slurry into paraffin with a catalyst from the pinholes under the action of gravity, simultaneously electrically stirring, and dispersing the dripped zirconia slurry into smaller droplets under the action of centrifugal force. And simultaneously irradiating the microspheres by using a 300W ultraviolet lamp to perform a curing reaction on sodium persulfate, a light curing agent 819DW, hydroxypropyl acrylate and N-N' -methylene bisacrylamide to form a zirconia ceramic microbead green body.
And step 3: collecting the zirconia ceramic microbead green compact from the paraffin in the step 2, washing the green compact three times by adopting absolute ethyl alcohol, and removing the paraffin and residual powder on the surface of the green compact; putting the washed zirconia ceramic microbead green body into an electric heating drying oven to be dried for 3 hours at the temperature of 90 ℃; then putting the green body into an SJJ-16 type electric furnace, raising the temperature to 400 ℃ after 130min, and preserving the temperature for 3h at 400 ℃; raising the temperature to 600 ℃ within 100min, and preserving the heat at 600 ℃ for 3 h; raising the temperature to 1200 ℃ within 120min, and preserving the heat for 3h at 1200 ℃; raising the temperature to 1550 ℃ in 175min, then preserving the temperature for 3h, and finally naturally cooling to room temperature to obtain the zirconia ceramic microbead blank.
And 4, step 4: performing self-polishing on the blank of the zirconia ceramic microspheres obtained in the step 3 to obtain the zirconia ceramic microspheres, wherein the size of the zirconia ceramic microspheres is 0.15-0.24 mm, and the density of the zirconia ceramic microspheres is 6.08g/cm through detection3The abrasion rate was 3.8 ppm/hr.
In order to further illustrate the effect of the invention, the invention is also provided with a comparative example which is concretely as follows:
comparative example 1
A composite preparation method of submillimeter-level zirconia ceramic microspheres comprises the following steps:
step 1: dissolving 5g of monomer polyacrylamide, 0.5g of cross-linking agent N-N' -methylene bisacrylamide and 1g of dispersing agent citric acid in 30g of deionized water, electrically stirring to form a solution, and simultaneously dropwise adding ammonia water to adjust the pH value of the solution to 10; adding 30g of 3 mol% yttrium-stabilized zirconia into the solution, continuing stirring for 1h, adding 0.5g of defoamer isopropanol after uniform dispersion, and stirring for 1 h; and adding 1g of initiator ammonium persulfate into the zirconia slurry, and stirring for 10min to form uniform and stable zirconia slurry.
Step 2: 0.5g of tetramethylethylenediamine as a catalyst was dropped into a beaker of 500ml of liquid paraffin, and the beaker was placed in an oil bath at 50 ℃. Putting the zirconia slurry prepared in the step 1 into a titration bottle, simultaneously connecting a hose with a plurality of pinholes with the titration bottle, hanging the titration bottle at a height of 1m from a beaker heated by an oil bath, opening a hose switch, dripping the zirconia slurry into paraffin with a catalyst from the pinholes under the action of gravity, simultaneously electrically stirring, and dispersing the dripped zirconia slurry into smaller droplets under the action of centrifugal force. Due to the difference of the surface tension of the liquid drops and the paraffin, the dispersed liquid drops automatically form balls in the paraffin and are solidified to form a zirconia ceramic microbead green compact.
And step 3: collecting the zirconia ceramic microbead green compact from the paraffin in the step 2, washing the green compact three times by adopting absolute ethyl alcohol, and removing the paraffin and residual powder on the surface of the green compact; putting the washed zirconia ceramic microbead green body into an electric heating drying oven to be dried for 3 hours at the temperature of 90 ℃; then putting the green body into an SJJ-16 type electric furnace, raising the temperature to 400 ℃ after 130min, and preserving the temperature for 2h at 400 ℃; raising the temperature to 600 ℃ within 100min, and keeping the temperature at 600 ℃ for 2 h; raising the temperature to 1200 ℃ within 120min, and keeping the temperature at 1200 ℃ for 2 h; and raising the temperature to 1520 ℃ within 160min, then preserving the temperature for 3h, and finally naturally cooling to room temperature to obtain the zirconia ceramic microbead blank.
And 4, step 4: self-polishing the blank of the zirconia ceramic microspheres obtained in the fourth step to obtain the zirconia ceramic microspheres, wherein the size of the zirconia ceramic microspheres is 0.25-0.38 mm, and the density of the zirconia ceramic microspheres is 5.73g/cm through detection3The abrasion rate was 7.9 ppm/hr.
The results of comparing the test data of example 1, example 2, example 3 and comparative example are shown in table 1:
TABLE 1
| Size of microsphere | Density of microspheres | Rate of wear | |
| Example 1 | 0.2～0.23mm | 6.02g/cm3 | 3.9ppm/hr |
| Example 2 | 0.18～0.22mm | 6.05g/cm3 | 4.1ppm/hr |
| Example 3 | 0.15～0.24mm | 6.08g/cm3 | 3.8ppm/hr |
| Comparative example 1 | 0.25～0.38mm | 5.73g/cm3 | 7.9ppm/hr |
As can be seen from Table 1, the zirconia ceramic microspheres prepared in examples 1, 2 and 3 of the present invention have a size of less than 0.3mm, a better uniformity and a density of more than 6g/cm3The abrasion rate is lower than 5 ppm/hr; in comparative example 1, the size, density and wear rate of zirconia ceramic microspheres failed to reach the values in the examples, so the zirconia ceramic microspheres prepared by the invention have good performance and reached the industrial researchThe requirements of the grinding medium.
In summary, according to the composite preparation method of the submillimeter-sized zirconia ceramic microspheres provided by the invention, by utilizing the difference of the surface tensions of the zirconia slurry and the liquid paraffin, molecules of two interface layers are subjected to two-phase asymmetric acting force to enable the interface layers to present spherical surfaces, so that the zirconia ceramic microspheres are formed; the polymerization degree of the organic matter is improved by adopting a composite molding technology of catalytic curing and ultraviolet curing, so that the curing rate and the curing degree of the microspheres are controlled; the problems that in the prior art, the zirconia ceramic microspheres are not compact in structure and not up to standard in particle size are effectively solved, and meanwhile, the size of the zirconia ceramic microspheres can be controlled, and the preparation efficiency is improved.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A composite preparation method of submillimeter-level zirconia ceramic microspheres is characterized by comprising the following steps:
step 1, preparation of slurry
Dissolving a propylene monomer, a cross-linking agent and a dispersing agent in a water solvent to form a mixed solution, and adjusting the pH value of the mixed solution to 8-10; adding yttrium-stabilized zirconia into the mixed solution, uniformly dispersing, adding a defoaming agent, and stirring; adding an initiator and a light curing agent into the zirconia slurry, and stirring to form uniform and stable zirconia slurry;
step 2, preparing zirconia ceramic microsphere green body
Injecting the zirconia slurry obtained in the step 1 into oil bath liquid paraffin containing a catalyst, and stirring at 50-80 ℃ to form zirconia ceramic microspheres; simultaneously irradiating the zirconia ceramic microspheres by using an ultraviolet lamp to prepare a zirconia ceramic microsphere green body;
step 3, sintering of the green compact
And (3) cleaning and drying the zirconia ceramic microbead green body prepared in the step (2), heating to 1520-1550 ℃ by adopting a program, sintering, and self-polishing to obtain the submillimeter-level zirconia ceramic microbead.
2. The composite preparation method of the submillimeter-sized zirconia ceramic microspheres according to claim 1, wherein in the step 1, the propylene monomer is one or a mixture of acrylamide, hydroxyethyl acrylate and hydroxypropyl acrylate; the cross-linking agent is N-N' -methylene bisacrylamide; the initiator is one or a mixture of ammonium persulfate, sodium persulfate and potassium persulfate; the light curing agent is one or a mixture of a plurality of benzophenone derivatives, benzil derivatives and alkyl aryl ketone derivatives.
3. The composite preparation method of the submillimeter-sized zirconia ceramic microspheres according to claim 2, wherein the mass ratio of the propylene monomer to the cross-linking agent is 1: 0.1-0.125; the mass ratio of the propylene monomer to the initiator is 1: 0.2-0.25; the mass ratio of the propylene monomer to the light curing agent is 1: 0.3-0.375.
4. The composite preparation method of the submillimeter-sized zirconia ceramic microbeads according to claim 1, characterized in that in step 1, the yttrium-stabilized zirconia is 3-8 mol% yttrium oxide-stabilized zirconia; the mass ratio of the propylene monomer to the yttrium-stabilized zirconia is 1: 6-8.75.
5. The composite preparation method of submillimeter-sized zirconia ceramic microspheres according to claim 1, wherein in the step 1, the dispersant is one or a mixture of polyacrylic acid, citric acid and oxalic acid; the defoaming agent is a surfactant containing alcohols or ethers; the mass ratio of the propylene monomer to the dispersing agent is 1: 0.2-0.25, and the mass ratio of the propylene monomer to the defoaming agent is 1: 0.1-0.125.
6. The composite preparation method of submillimeter-sized zirconia ceramic microbeads according to claim 1, characterized in that in step 2, the catalyst is tetramethylethylenediamine or N, N-dimethylaniline; the mass ratio of the propylene monomer to the catalyst is 1: 0.1-0.125.
7. The composite preparation method of the submillimeter-sized zirconia ceramic microspheres according to claim 1, wherein in the step 2, the power of the ultraviolet lamp is 100-300W.
8. The composite preparation method of the submillimeter-sized zirconia ceramic microspheres according to claim 1, wherein in the step 2, the preparation method of the zirconia ceramic microspheres specifically comprises the following steps: and dropwise adding the zirconia slurry into liquid paraffin containing a catalyst through a titration device, and dispersing the zirconia slurry dropwise added into the paraffin into zirconia ceramic microspheres under the action of centrifugal force at 50-80 ℃ under the stirring condition.
9. The composite preparation method of submillimeter-sized zirconia ceramic microbeads according to claim 1, characterized in that in step 3, the temperature programming specifically comprises: raising the temperature to 400 ℃ after 130min, and preserving the heat for 2-3 h at 400 ℃; raising the temperature to 600 ℃ within 100min, and preserving the heat for 2-3 h at 600 ℃; raising the temperature to 1200 ℃ within 120min, and keeping the temperature at 1200 ℃ for 2-3 h; raising the temperature to 1520-1550 ℃ in 160-175 min, and preserving the temperature for 2-3 h.
10. The composite preparation method of submillimeter-sized zirconia ceramic microspheres according to claim 1, wherein in the step 3, the zirconia ceramic microspheres have a size of 0.1-0.3 mm.
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