阅读说明：本技术 一种非浸渍法制备覆膜耐磨陶瓷微球的方法及耐磨陶瓷微球 (Method for preparing coated wear-resistant ceramic microspheres by non-impregnation method and wear-resistant ceramic microspheres ) 是由 郑保昌 卫义成 史伟 钟雪琴 于 2021-01-27 设计创作，主要内容包括：本发明提供了一种非浸渍法制备覆膜耐磨陶瓷微球的方法。先采用滚制成型法得到预制球坯,接着将预制球坯的表面滚覆包覆一层热固型的有机高分子包覆层,通过控制有机高分子的加入量及滚制包覆的滚动速率进而控制包覆层的膜厚,包覆完成后进行加热固化,得到满足冷等静压工艺条件的覆膜陶瓷球坯,最后于冷等静压机中进行压制,得到复合陶瓷坯体,最后进行烧结和整形,得到烧结球坯。本发明能生产＜Φ1mm的陶瓷微球,具有滚制成型法的高产量、滴球成型法的高致密性的优点。同时还具有作业环境友好,覆膜可控的优点。(The invention provides a method for preparing a coated wear-resistant ceramic microsphere by a non-impregnation method. Firstly, obtaining a prefabricated ball blank by adopting a rolling forming method, then rolling and coating the surface of the prefabricated ball blank with a thermosetting organic polymer coating layer, controlling the film thickness of the coating layer by controlling the adding amount of organic polymers and the rolling speed of the rolling coating, heating and curing after the coating is finished to obtain a coated ceramic ball blank meeting the cold isostatic pressing process conditions, finally pressing in a cold isostatic pressing machine to obtain a composite ceramic blank, and finally sintering and shaping to obtain a sintered ball blank. The invention can produce ceramic microspheres with the diameter less than 1mm, and has the advantages of high yield of a roll forming method and high compactness of a dropping ball forming method. Meanwhile, the method also has the advantages of friendly operation environment and controllable film coating.)

1. a method for preparing coated wear-resistant ceramic microspheres by a non-impregnation method is characterized by comprising the following steps: the method comprises the following steps:

1) preparing a rolling ball blank: adding ceramic ball seeds into a rolling forming machine, and adding ball raw materials in the process of rolling the ceramic ball seeds in the rolling forming machine to obtain a rolling ball blank;

2) rolling: adding the rolled ball blank and the organic monomer powder into a rolling forming machine for rolling coating and curing to obtain a ceramic ball blank coated with an organic ball shell;

3) isostatic pressing treatment: carrying out isostatic pressing treatment on the ceramic ball blank coated with the organic ball shell in a cold isostatic press to obtain an organic monomer composite ceramic blank;

4) drying: drying the organic monomer composite ceramic blank body, and removing the organic monomer in the organic monomer composite ceramic blank body to obtain a ceramic blank body;

5) and (3) sintering: placing the ceramic body in a sintering machine for sintering treatment to obtain a sintered ball body;

preferably, the method further comprises the steps of:

6) shaping the sintered ball blank obtained in the step 5) to obtain the wear-resistant ceramic microspheres.

2. The method of claim 1, wherein: the ceramic ball seeds are one or more of alumina ball seeds, zirconia ball seeds, silicon nitride ball seeds and silicon carbide ball seeds; and/or

The raw material of the sphere is one or more of alumina powder, zirconia powder, silicon nitride powder and silicon carbide powder; and/or

The organic monomer powder is thermosetting organic monomer powder, preferably one or more of epoxy resin, phenol resin, silane cross-linked styrene and phenolic resin;

preferably, the ceramic balls are zirconia balls, and the raw materials of the balls are a mixture of alumina powder, zirconia powder, zirconium oxychloride, lanthanum fluoride and titanium fluoride; the organic monomer is phenol resin.

3. The method of claim 2, wherein: the ceramic ball is a zirconia ball, the ball is made of a mixture of alumina powder, zirconia powder, zirconium oxychloride, lanthanum fluoride and titanium fluoride, and the mixture ratio of the components is as follows:

15-35 wt% of alumina, preferably 18-30 wt%;

30-50 wt% of zirconium oxide, preferably 33-45 wt%;

12-25 wt%, preferably 15-20 wt% of zirconium oxychloride;

2-12 wt% of lanthanum fluoride, preferably 5-10 wt%;

titanium fluoride is 1 to 10 wt%, preferably 3 to 8 wt%.

4. The method according to any one of claims 1-3, wherein: each raw material component in the sphere raw material is nano-scale powder, the particle size of which is less than or equal to 800nm, preferably less than or equal to 500 nm;

preferably, the zirconia is nano zirconia stabilized with a phase stabilizer; the phase stabilizer is one or more of magnesium oxide, calcium oxide, yttrium oxide, scandium oxide and cerium oxide which are compounded together; the content of the phase stabilizer is 3-20 wt% of the added amount of the zirconia, preferably 5-15 wt%;

or the phase stabilizer is one of a magnesium oxide-yttrium oxide composite stabilizer and a calcium oxide-yttrium oxide composite stabilizer; the content of the composite stabilizer is 5-15 wt% of the added amount of zirconia, and is preferably 8-12%.

5. The method of claim 4, wherein: the step 1) is specifically as follows: firstly, stirring alumina, zirconia, lanthanum fluoride and titanium fluoride in proportion (preferably stirring for 5-50min, more preferably 10-30min) to obtain a dry mixture; then dissolving zirconium oxychloride in water to obtain a wet material; the dry mixed material and the wet mixed material are separately contained for standby use to obtain a spherical raw material;

then putting the ceramic ball into a rolling forming machine, starting the rolling forming machine and adjusting the rotating speed of the rolling forming machine to be 15-60r/min (preferably 20-45 r/min); then adding dry materials and wet materials in the rolling process for rolling; obtaining a rolled ball blank after rolling;

preferably, the adding rate of the dry mixture is 1-20% of the mass of the seeds to be thrown per minute, and preferably 2-10%;

preferably, the wet material is a saturated aqueous solution of zirconium oxychloride; the adding rate of the wet material is that the adding amount per minute is 0.5-10% of the mass of the ball seeds, and the adding rate is preferably 0.8-3%.

6. The method according to claim 4 or 5, characterized in that: the step 2) is specifically as follows: putting the dried rolled ball blank into a rolling forming machine, starting the rolling forming machine and adjusting the rotating speed of the rolling forming machine to be 20-60r/min (preferably 25-45 r/min); then adding organic monomer powder (preferably epoxy resin) in the rolling process to carry out rolling coating; curing (preferably heating to 100-; obtaining a ceramic ball blank coated with an organic ball shell;

preferably, the addition rate of the organic monomer powder is 10 to 300g/min, preferably 30 to 150 g/min.

7. The method of claim 6, wherein: the step 3) is specifically as follows: putting the ceramic ball blank coated with the organic ball shell into a cold isostatic press (preferably putting the ceramic ball blank coated with the organic ball shell into a net sleeve and then putting the ceramic ball blank into the cold isostatic press) and carrying out isostatic pressing treatment for 1-10min (preferably 3-8min) at the pressure of 100-600MPa (preferably 150-500 MPa); after isostatic pressing treatment is finished, an organic monomer composite ceramic blank is obtained; and/or

The step 4) is specifically as follows: drying the organic monomer composite ceramic blank (preferably drying at 450-800 ℃ for 2-8h, more preferably drying at 500-700 ℃ for 3-6h) to obtain the ceramic blank.

8. The method of claim 7, wherein: the step 5) is specifically as follows: placing the ceramic body into a sintering machine, and sintering the ceramic body at the temperature of 1300-1500 ℃ for 1-4h (preferably at the temperature of 1350-1450 ℃) at the heating rate of 5-120 ℃/h (preferably 10-80 ℃/h) to obtain a sintered ball body; and/or

The step 6) is specifically as follows: shaping, polishing the surface and inspecting the sintered ball blank to obtain the wear-resistant ceramic microspheres;

preferably, the sintering temperature rise rate is 5-120 ℃/h, preferably 8-60 ℃/h.

9. The method according to any one of claims 6-8, wherein: in the step 2), adding a proper amount of hydrogen peroxide while adding the wet material; the adding amount of the hydrogen peroxide is 0.3 to 1.5 times, preferably 0.5 to 2 times of the adding amount of the zirconium oxychloride; and/or

In the step 3), the thickness of the solidified shell layer of the ball blank with the solidified shell layer is 3-30 μm, preferably 5-20 μm; and/or

In the step 6), the grain size of the wear-resistant ceramic microspheres is less than or equal to 1mm, preferably less than or equal to 0.8 mm.

10. An abrasion-resistant ceramic microsphere, characterized in that: the wear resistant ceramic microspheres are obtained by a process according to any one of claims 1 to 9; preferably, the particle size of the wear-resistant ceramic microspheres is less than or equal to 1mm, and preferably less than or equal to 0.8 mm.

Technical Field

The invention relates to preparation of ceramic microspheres, in particular to a method for preparing coated wear-resistant ceramic microspheres by a non-impregnation method and wear-resistant ceramic microspheres prepared by the method, and belongs to the technical field of preparation of ceramic microspheres.

Background

The ceramic microspheres have extremely wide application, and are generally applied to the industries such as military industry, medicine, chemical industry, environmental protection, nuclear technology and the like. The composite material is suitable for reinforcing materials and filling materials of various media (such as metal or polymer matrix composite materials), can improve certain performances of the matrix material, such as reinforcement, wear resistance, abrasion resistance, hardness improvement, chemical corrosion resistance, weather resistance and the like, and has a very wide application prospect. With the expansion of the requirements of powder grinding for entering submicron and nanometer scales, the small-size requirement of the ceramic wear-resistant microspheres (less than phi 1mm) is increasing. The key is to manufacture a high-density and high-strength ceramic ball blank.

At present, the method for manufacturing the ceramic ball mainly comprises the following steps: dry pressing, rolling, dropping balls, etc.

Dry pressing method: and (3) putting the ceramic powder added with the binder into a dry pressing die to press a ball blank, putting the pressed ball blank into an isostatic pressing die to seal, raising the density of the green blank through isostatic pressing, and then performing post sintering, shaping and the like to obtain the ceramic ball. This method can only produce microspheres > Φ 2 mm.

And (3) rolling: putting prefabricated ball seeds in a rolling disc, then continuously adding water and ceramic powder in the ball seed rolling process to enable the ball seeds to grow to a certain size to obtain a rolled ball blank, and carrying out post sintering, shaping and other processes on the ball blank to obtain the ceramic microspheres. The method can prepare the microspheres with the diameter less than 1mm, but has extremely high requirements on powder and process, the manufactured ball blank has low compactness (particularly for manufacturing silicon nitride, silicon carbide and the like), poor wear resistance and high ball crushing rate in the using process.

A dropping ball method: dropping the ceramic slurry into a specific solvent through a dropping head, spheroidizing the slurry dropping ball in the solvent due to surface tension and continuously dehydrating, collecting at the bottom to obtain a ceramic ball blank, and sintering the ceramic ball blank to obtain the ceramic microsphere. The ceramic microspheres manufactured by the method have good sphericity and high density, the sphere diameter is controlled by the size of the dripper, but the method is used for producing a sphere blank singly, and the production efficiency is extremely low.

In the prior art, a rolling forming method is generally adopted to obtain a prefabricated ball blank, then the prefabricated ball blank is immersed into an organic solvent for organic matter wrapping, after coating treatment, the ball blank is put into a cold isostatic press for pressing to obtain a pressed ball blank, and finally the pressed ball blank is sintered and shaped to obtain a ceramic ball blank. However, the impregnation method generally selects thermoplastic organic matters (such as organic silica gel, paraffin mixture and the like), the organic matters have high heating volatility and certain environmental protection problems, meanwhile, the impregnation method cannot accurately control the thickness of the wrapping film layer, the later glue discharging and degreasing are difficult due to the too high thickness, and the film layer leaks water when the later isostatic pressing is caused due to the insufficient thickness.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a method for preparing film-coated ceramic microspheres by a non-impregnation method. Firstly, obtaining a prefabricated ball blank by adopting a rolling forming method, then rolling and coating the surface of the prefabricated ball blank with a thermosetting organic polymer coating layer, controlling the film thickness of the coating layer by controlling the adding amount of organic polymers and the rolling speed of the rolling coating, heating and curing after the coating is finished to obtain a coated ball blank meeting the isostatic pressing process conditions, finally placing the ball blank into a cold isostatic pressing machine for pressing to obtain a pressed ball blank, and sintering and shaping the pressed ball blank to obtain a ceramic ball blank. The invention can produce the microsphere with the diameter less than 1mm, and has the advantages of high yield of the roll forming method and high compactness of the dropping ball forming method. Meanwhile, the method also has the advantages of friendly operation environment and controllable film coating.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

in accordance with a first embodiment of the present invention, a method for preparing coated ceramic microspheres in a non-impregnation process is provided.

A method for preparing coated wear-resistant ceramic microspheres by a non-impregnation method comprises the following steps:

1) preparing a rolling ball blank: adding the ceramic ball seeds into a rolling forming machine, and adding the ball body raw material during the rolling process of the ceramic ball seeds in the rolling forming machine to obtain a rolling ball blank.

2) Rolling: and adding the rolled ball blank and the organic monomer powder into a rolling forming machine for rolling coating and curing to obtain the ceramic ball blank coated with the organic ball shell.

3) Isostatic pressing treatment: and (3) carrying out isostatic pressing treatment on the ceramic ball blank coated with the organic ball shell in a cold isostatic press to obtain the organic monomer composite ceramic blank.

4) Drying: and drying the organic monomer composite ceramic body, and removing the organic monomer in the organic monomer composite ceramic body to obtain the ceramic body.

5) And (3) sintering: and placing the ceramic body in a sintering machine for sintering treatment to obtain a sintered ball body.

Preferably, the method further comprises the steps of:

6) shaping the sintered ball blank obtained in the step 5) to obtain the wear-resistant ceramic microspheres.

Preferably, the ceramic ball seeds are one or more of alumina ball seeds, zirconia ball seeds, silicon nitride ball seeds and silicon carbide ball seeds.

Preferably, the sphere raw material is one or more of alumina powder, zirconia powder, silicon nitride powder and silicon carbide powder.

Preferably, the organic monomer powder is thermosetting organic monomer powder, preferably one or more of epoxy resins, phenol resins, silane-crosslinked styrenes, and phenolic resins.

Preferably, the ceramic balls are zirconia balls, and the raw material of the balls is a mixture of alumina powder, zirconia powder, zirconium oxychloride, lanthanum fluoride and titanium fluoride. The organic monomer is phenol resin.

Preferably, the ceramic balls are zirconia balls, the raw materials of the balls are a mixture of alumina powder, zirconia powder, zirconium oxychloride, lanthanum fluoride and titanium fluoride, and the mixture ratio of each component is as follows:

15-35 wt.%, preferably 18-30 wt.% of alumina.

Zirconia is 30 to 50 wt%, preferably 33 to 45 wt%.

12 to 25 wt%, preferably 15 to 20 wt% of zirconium oxychloride.

2-12 wt% of lanthanum fluoride, preferably 5-10 wt%;

titanium fluoride is 1 to 10 wt%, preferably 3 to 8 wt%.

Preferably, each raw material component in the sphere raw material is nano-scale powder, and the particle size of the nano-scale powder is less than or equal to 800nm, preferably less than or equal to 500 nm.

Preferably, the zirconia is nano zirconia stabilized with a phase stabilizer. The phase stabilizer is one or more of magnesium oxide, calcium oxide, yttrium oxide, scandium oxide and cerium oxide. The content of the phase stabilizer is 3 to 20 wt%, preferably 5 to 15 wt% of the added amount of zirconia.

Or the phase stabilizer is one of a magnesium oxide-yttrium oxide composite stabilizer and a calcium oxide-yttrium oxide composite stabilizer. The content of the composite stabilizer is 5-15 wt% of the added amount of zirconia, and is preferably 8-12%.

Preferably, step 1) is specifically: firstly, stirring the alumina, the zirconia, the lanthanum fluoride and the titanium fluoride according to the proportion (preferably stirring for 5-50min, more preferably stirring for 10-30min) to obtain a dry mixture. Then dissolving zirconium oxychloride in water to obtain a wet material. The dry mixed material and the wet mixed material are separately contained for standby use to obtain the sphere raw material.

Then putting the ceramic ball balls into a rolling forming machine, starting the rolling forming machine and adjusting the rotating speed of the rolling forming machine to be 15-60r/min (preferably 20-45 r/min). Then adding dry mixture and wet mixture in the rolling process for rolling. And obtaining a rolled ball blank after rolling.

Preferably, the dry mixture is added at a rate of 1-20%, preferably 2-10%, of the mass of the seeds added per minute.

Preferably, the wet material is a saturated aqueous solution of zirconium oxychloride. The adding rate of the wet material is that the adding amount per minute is 0.5-10% of the mass of the ball seeds, and the adding rate is preferably 0.8-3%.

Preferably, step 2) is specifically: and putting the dried rolling ball blank into a rolling forming machine, starting the rolling forming machine and adjusting the rotating speed of the rolling forming machine to be 20-60r/min (preferably 25-45 r/min). Then adding organic monomer powder (preferably epoxy resin) to carry out rolling coating in the rolling process. Curing (preferably heating to 100-. Obtaining the ceramic ball blank with the organic ball shell coating.

Preferably, the addition rate of the organic monomer powder is 10 to 300g/min, preferably 30 to 150 g/min. (100 kg of dried ball blank is taken as a reference base number, and the adjustment can be reasonably carried out according to the actual working condition).

Preferably, step 3) is specifically: and (3) placing the ceramic ball blank coated with the organic ball shell into a cold isostatic press (preferably placing the ceramic ball blank coated with the organic ball shell into a net sleeve and then placing the net sleeve into the cold isostatic press), and carrying out isostatic pressing treatment at the pressure of 100-600MPa (preferably 150-500MPa) for 1-10min (preferably 3-8 min). And (4) after isostatic pressing treatment, obtaining an organic monomer composite ceramic blank.

Preferably, the step 4) is specifically: drying the organic monomer composite ceramic blank (preferably drying at 450-800 ℃ for 2-8h, more preferably drying at 500-700 ℃ for 3-6h) to obtain the ceramic blank.

Preferably, the step 5) is specifically as follows: putting the ceramic body into a sintering machine, and sintering the ceramic body at the temperature of 1300-1500 ℃ for 1-4h (preferably at the temperature of 1350-1450 ℃) at the heating rate of 5-120 ℃/h (preferably 10-80 ℃/h) to obtain a sintered ball body.

Preferably, step 6) is specifically: and shaping, polishing the surface and inspecting the sintered ball blank to obtain the wear-resistant ceramic microspheres.

Preferably, the sintering temperature rise rate is 5-120 ℃/min, preferably 8-60 ℃/min.

Preferably, in the step 2), a proper amount of hydrogen peroxide is added while the wet material is added. The adding amount of the hydrogen peroxide is 0.3 to 1.5 times, preferably 0.5 to 2 times of the adding amount of the zirconium oxychloride.

Preferably, in step 3), the thickness of the solidified shell layer of the spherical blank with the solidified shell layer is 3-30 μm, preferably 5-20 μm.

Preferably, in step 6), the particle size of the wear-resistant ceramic microspheres is less than or equal to 1mm, and preferably less than or equal to 0.8 mm.

In accordance with a second embodiment of the present invention, there is provided a wear resistant ceramic microsphere.

An abrasion resistant ceramic microsphere prepared according to the method of the first embodiment.

Preferably, the particle size of the wear-resistant ceramic microspheres is less than or equal to 1mm, and preferably less than or equal to 0.8 mm.

In the prior art, the method for manufacturing the ceramic balls mainly comprises the following steps: dry pressing, rolling, dropping balls, etc. Wherein the dry pressing method can only manufacture microspheres with the diameter of more than phi 2 mm. The rolling method has extremely high requirements on powder and process, the manufactured ball blank has low compactness (particularly for manufacturing silicon nitride, silicon carbide and the like), the wear resistance is poor, and the ball breaking rate is high in the using process. The dropping ball method is used for producing ball blanks singly, and the production method has extremely low efficiency. Meanwhile, in the prior art, a ceramic ball blank is generally coated by an impregnation method, namely, a prefabricated ball blank is immersed into an organic solvent for organic matter coating, the ball blank is placed into a cold isostatic press for pressing after the coating treatment is finished, a pressed ball blank is obtained, and finally the pressed ball blank is sintered and shaped, so that the ceramic ball blank is obtained. However, the impregnation method generally selects thermoplastic organic matters (such as organic silica gel, paraffin mixture and the like), the organic matters have high heating volatility and certain environmental protection problems, meanwhile, the impregnation method cannot accurately control the thickness of the wrapping film layer, the later glue discharging and degreasing are difficult due to the too high thickness, and the film layer leaks water when the later isostatic pressing is caused due to the insufficient thickness.

According to the invention, a rolling forming method is adopted to obtain a prefabricated ball blank, then a thermosetting organic polymer coating layer is coated on the surface of the prefabricated ball blank in a rolling way, the film thickness of the coating layer is controlled by controlling the adding amount of the organic polymer and the rolling speed of the rolling coating, heating and curing are carried out after the coating is finished to obtain a coated ball blank meeting the isostatic pressing process conditions, finally the ball blank is put into a cold isostatic pressing machine for pressing to obtain a pressed ball blank, and the pressed ball blank is sintered and shaped to obtain a ceramic ball blank. The invention can produce the microsphere with the diameter less than 1mm, and has the advantages of high yield of the roll forming method and high compactness of the dropping ball forming method. Meanwhile, the method also has the advantages of friendly operation environment and controllable film coating.

In the invention, the initial mixture comprises a dry mixture and a wet mixture, wherein the dry mixture is a mixture of nano-scale alumina, zirconia, lanthanum fluoride and titanium fluoride; the wet material is an aqueous solution of zirconium oxychloride. The method is characterized in that an aqueous solution of zirconium oxychloride (also called zirconium oxychloride) is used as a wet material, on one hand, the zirconium oxychloride is easy to dissolve in water, and can form a sol solution of zirconium oxide after hydrolysis, and the sol solution after hydrolysis of zirconium oxychloride replaces the traditional water, and because the adsorbability, the cohesiveness and the like of the sol are far greater than those of water, when the dry material is rolled to prepare a rolled ball blank, the compactness and the balling performance of the ball blank can be better, the wear resistance of the ball blank is improved, and the ball crushing rate is reduced. On the other hand, the final product of the hydrolysis of the zirconium oxychloride is zirconium oxide, and the zirconium oxide is one of the raw materials of the invention, namely, the water solution of the zirconium oxychloride replaces water to be used as a wetting agent, so that the compactness and the balling property of the ball blank are greatly improved without introducing new substances. Moreover, after the zirconium oxychloride is added, the ratio of the zirconium oxide in the dry mixture can be reduced, so that the relative dispersion and mixing of the dry mixture are more uniform, meanwhile, the mixing proportion of the dry material and the wet material is further balanced, and the problem of poor balling performance caused by over-drying or over-wetting of the whole ball-making mixture is avoided. Further, in order to make the hydrolysis of zirconium oxychloride more complete, a proper amount of hydrogen peroxide (generally, the amount of hydrogen peroxide is 0.5-5 times, preferably 1-4 times, the mass of the added zirconium oxychloride) can be added while the aqueous solution of zirconium oxychloride is added, and the hydrogen peroxide can consume the byproducts of the hydrolysis of zirconium oxychloride, so that the hydrolysis of zirconium oxychloride is more rapid and complete. The more zirconium oxychloride is hydrolyzed, the faster the polycondensation reaction proceeds, the smaller the size of the sol particles, the more uniform the distribution, the faster the viscosity of the sol increases, and the shorter the sol-gel time.

In the invention, the mixed material is also doped with lanthanum fluoride. On the one hand, the doped lanthanum fluoride with proper amount can form a stable and uniformly distributed hard skeleton in the structure of the zirconia ceramic particles, so that the strength and the thermal stability of the zirconia ceramic microspheres can be greatly improved, and meanwhile, the radiation resistance of the zirconia ceramic back plate can be further improved. The application range of the zirconia ceramic microspheres is enlarged.

In the invention, the mixture is further doped with titanium fluoride, and a proper amount of titanium fluoride is doped, so that the wear resistance and the chemical stability of the zirconia ceramic microspheres can be greatly improved, and simultaneously, the titanium fluoride forms alternate composite phases in the zirconia particle structure, so that the phase change toughening of the zirconia ceramic is enhanced. Meanwhile, titanium fluoride can form a compact oxide film at high temperature, so that the wear resistance and the oxidation resistance of the zirconia ceramic microspheres are further improved.

In the invention, stable zirconium oxide, lanthanum fluoride and titanium fluoride are interpenetrated and crosslinked in a sol system formed by hydrolysis of zirconium oxychloride to obtain a mixture which is uniformly distributed, has higher compactness and has no density gradient. The mixture is shaped and rolled in a rolling forming machine and dried (residual moisture, hydrogen peroxide, gel and the like are removed) to obtain a rolling ball blank. And then adding the blank and thermosetting organic monomer powder into a rolling forming machine for rolling to ensure that the surface of the blank is coated with a thermosetting organic monomer layer, and heating and curing to form an organic coating film layer. The roll-coated organic film layer can completely cover the surface of the ball blank, and the thickness of the coated film layer is uniform and controllable. And then carrying out isostatic pressing treatment on the ball blank coated with the thermosetting organic film layer (namely the solidified shell layer) in a cold isostatic press, wherein the uniform and complete organic film layer is coated, so that the phenomenon of water leakage of the film layer during high-pressure hydrostatic pressing can be greatly avoided, the ball blank can bear larger hydrostatic pressing treatment, and higher compactness is obtained. Meanwhile, the thickness of the rolled film layer is controllable, so that the proper thickness can effectively prevent water seepage of the film layer under high pressure, and the phenomenon of difficult glue removal and degreasing in the subsequent sintering process can be avoided. And finally, sintering the ball blank with the static pressure treatment thickness. Zirconium oxychloride and a zirconia sol system obtained by the hydrolysis of zirconium oxychloride can be converted into stable zirconia by sintering, and a composite system of lanthanum fluoride and titanium fluoride reinforcing phases doped in the zirconia ceramic particles can be further enhanced. Through sintering treatment, the organic film layer on the surface of the ball blank can be removed, and the process of degumming and degreasing the ball blank is realized. Further improving the hardness, strength, compactness, wear resistance and the like of the ceramic microsphere sintered ball blank to the maximum extent.

In the present invention, pure zirconia is a monoclinic phase at room temperature, and changes to a tetragonal phase when the temperature is raised to about 1173 ℃ and to a cubic phase when the temperature is raised to 2370 ℃ and changes to a liquid phase at 2690 ℃. When the material is cooled from high temperature to room temperature, orthorhombic crystals are converted into monoclinic crystals through phase transition temperature, and the sintered finished product contains microcracks due to severe change of the volume of the monoclinic crystals, so that the material is often unusable. Since zirconia does not exist in a cubic phase (fluorite crystal structure) at room temperature, the doped phase stabilizer can greatly increase the temperature range in which zirconia stably exists in a cubic phase. In the invention, the phase stabilizer is one of magnesium oxide, calcium oxide and yttrium oxide. The content of the phase stabilizer is 3 to 20 wt%, preferably 5 to 15 wt% (generally, when magnesium oxide is used as the phase stabilizer, it is added in an amount of 15 to 20 wt%, when calcium oxide is used as the phase stabilizer, it is added in an amount of 3 to 10 wt%, and when yttrium oxide is used as the phase stabilizer, it is added in an amount of 8 to 13 wt%). Or the phase stabilizer is one of a magnesium oxide-yttrium oxide composite stabilizer and a calcium oxide-yttrium oxide composite stabilizer. The content of the composite stabilizer is 5 to 15% by weight, preferably 8 to 12% (generally, when magnesia-yttria is used as the composite stabilizer, the mass ratio of magnesia to yttria is generally 1:0.2 to 1. when calcia-yttria is used as the composite stabilizer, the mass ratio of calcia to yttria is generally 1:0.2 to 0.5).

In the invention, when rolling to prepare the rolled ball blank, the rotating speed of the rolling forming machine is 15-60r/min (preferably 20-45 r/min). Then adding dry mixture (the adding rate of the dry mixture is 1-20% of the mass of the seeds added per minute, preferably 2-10%) and wet mixture (the adding rate of the wet mixture is 0.5-10% of the mass of the seeds added per minute, preferably 0.8-3%) in the rolling process for rolling. And (3) drying the rolled ball material after the rolling is finished (preferably drying at 50-120 ℃ for 10-800min, and more preferably drying at 60-90 ℃ for 50-600min) to obtain a rolled ball blank. The rolling rotating speed is controlled to determine that the added materials can be uniformly dispersed to all ball blanks, and the growth speed of the ball blanks is ensured to be consistent. Meanwhile, the adding rate of the materials determines the growth speed of the ball blank, and further the rolled ball blank with uniform particle size distribution is obtained.

In the present invention, the rotational speed of the roll former is adjusted to 20-60r/min (preferably 25-45r/min) during the roll coating process. Then adding organic monomer powder (the adding rate of the organic monomer powder is 10-300g/min, preferably 30-150g/min per 100kg of the dried ball blank) in the rolling process for rolling coating. Curing (preferably heating to 100-250 ℃ and preserving heat for 10-120min, more preferably heating to 150-200 ℃ and preserving heat for 30-60min) after the coating is finished to obtain the ball blank with a curing shell layer. The rolling rotation speed is controlled to determine that the added organic monomers can be uniformly dispersed on the surfaces of all the ball billets, and the thickness growth speed of the organic matters on the surfaces of the ball billets is ensured to be consistent. Meanwhile, the adding rate of the materials determines the growth speed of the organic matters on the ball blank and controls the thickness of the organic layer.

In the invention, the ball blank with the curing shell layer is put into a cold isostatic press (preferably, the ball blank with the curing shell layer is put into a net sleeve (the net sleeve is used as a container of the ball blank to prevent the ball blank from moving everywhere in an isostatic pressure liquid medium, and simultaneously, the ball blank is convenient for being quickly collected after the isostatic pressure treatment is finished), then the ball blank is put into the cold isostatic press to be subjected to the isostatic pressure treatment for 1-10min (preferably 3-8min) under the condition of 100-minus one MPa (preferably, 150-minus one MPa), after the isostatic pressure treatment is finished, the ball material is dried according to a glue discharging and degreasing curve (preferably, the ball blank is dried for 2-8h under the condition of 450-minus one 800 ℃, more preferably, the ball blank is dried for 3-6h under the condition of 500-minus one 700 ℃) to obtain a ceramic blank, wherein the glue discharging and degreasing curve refers to firstly heat the ball blank from room temperature to 100-minus one 200 ℃ at a constant speed for 3-10 h, then raising the temperature from 200 ℃ at 100-.

In the invention, the ceramic body is placed into a sintering machine, and then the ceramic body is sintered for 1-4h (preferably sintered for 2-3h at 1350-1450 ℃) at 1300-120 ℃/h (preferably 10-80 ℃/h) heating rate to obtain the sintered ball body. And then shaping, polishing the surface and inspecting the sintered ball blank to obtain the ceramic microspheres.

In the invention, the grain diameter of the prepared ceramic microspheres is less than or equal to 1mm, preferably less than or equal to 0.8 mm.

Compared with the prior art, the invention has the following beneficial technical effects:

1. the method comprises the steps of taking alumina, zirconia, lanthanum fluoride and titanium fluoride as initial raw materials, uniformly mixing and pelletizing in the presence of a zirconium oxychloride aqueous solution, protecting by rolling and coating a thermosetting organism shell layer, and performing ultrahigh pressure cold isostatic pressing pretreatment to obtain a blank body, wherein the blank body has no density gradient and high compactness. The blank is sintered, and the ceramic microspheres are obtained after degumming and degreasing, and have the advantages of good density, high strength, strong wear resistance, uniform granularity and high yield.

2. The invention adopts a sol system obtained by hydrolyzing zirconium oxychloride as a wet material system, thereby greatly improving the mixing degree and balling property of raw materials of each component and the compactness of a subsequent ultra-high static pressure blank. Meanwhile, the sol system further provides an excellent place for the extension and crosslinking of reinforcing phases such as lanthanum fluoride and titanium fluoride in a zirconia matrix phase, and greatly promotes the reinforcing effect of the magnetic force of the lanthanum fluoride and the titanium fluoride on the performances of the zirconia ceramic in the aspects of wear resistance, impact resistance, high toughness and the like.

3. The invention adopts thermosetting type (including but not limited to epoxy resins, phenol resins and silane crosslinked styrene) organic polymer coating materials, the coating is carried out on the surface of a rolled ball blank in a rolling device in a rolling way, the thickness of the film is controlled by controlling the adding amount of the organic polymer, and the coating is heated and cured after the coating is finished, so as to obtain the coated ceramic ball blank meeting the isostatic pressing process conditions. The method has the advantages of friendly operation environment and controllable film covering.

4. The invention adopts a rolling forming method to obtain a prefabricated ball blank, then the prefabricated ball blank and a thermosetting organic monomer are rolled and wrapped, pressed in an isostatic press to obtain a pressed ball blank, and the pressed ball blank is sintered and shaped to obtain the ceramic microsphere. The invention can produce microspheres with the diameter less than 1 mm. The invention has the advantages of high yield of the roll forming method and high compactness of the dropping ball forming method.

Drawings

FIG. 1 is a process flow diagram of the present invention.

Detailed Description

The technical solution of the present invention is illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.

A method for preparing coated wear-resistant ceramic microspheres by a non-impregnation method comprises the following steps:

1) preparing a rolling ball blank: adding the ceramic ball seeds into a rolling forming machine, and adding the ball body raw material during the rolling process of the ceramic ball seeds in the rolling forming machine to obtain a rolling ball blank.

2) Rolling: and adding the rolled ball blank and the organic monomer powder into a rolling forming machine for rolling coating and curing to obtain the ceramic ball blank coated with the organic ball shell.

3) Isostatic pressing treatment: and (3) carrying out isostatic pressing treatment on the ceramic ball blank coated with the organic ball shell in a cold isostatic press to obtain the organic monomer composite ceramic blank.

4) Drying: and drying the organic monomer composite ceramic body, and removing the organic monomer in the organic monomer composite ceramic body to obtain the ceramic body.

5) And (3) sintering: and placing the ceramic body in a sintering machine for sintering treatment to obtain a sintered ball body.

Preferably, the method further comprises the steps of:

6) shaping the sintered ball blank obtained in the step 5) to obtain the wear-resistant ceramic microspheres.

Preferably, the ceramic ball seeds are one or more of alumina ball seeds, zirconia ball seeds, silicon nitride ball seeds and silicon carbide ball seeds.

Preferably, the sphere raw material is one or more of alumina powder, zirconia powder, silicon nitride powder and silicon carbide powder.

Preferably, the organic monomer powder is thermosetting organic monomer powder, preferably one or more of epoxy resins, phenol resins, silane-crosslinked styrenes, and phenolic resins.

Preferably, the ceramic balls are zirconia balls, and the raw material of the balls is a mixture of alumina powder, zirconia powder, zirconium oxychloride, lanthanum fluoride and titanium fluoride. The organic monomer is phenol resin.

Preferably, the ceramic balls are zirconia balls, the raw materials of the balls are a mixture of alumina powder, zirconia powder, zirconium oxychloride, lanthanum fluoride and titanium fluoride, and the mixture ratio of each component is as follows:

15-35 wt.%, preferably 18-30 wt.% of alumina.

Zirconia is 30 to 50 wt%, preferably 33 to 45 wt%.

12 to 25 wt%, preferably 15 to 20 wt% of zirconium oxychloride.

2-12 wt% of lanthanum fluoride, preferably 5-10 wt%;

titanium fluoride is 1 to 10 wt%, preferably 3 to 8 wt%.

Preferably, each raw material component in the sphere raw material is nano-scale powder, and the particle size of the nano-scale powder is less than or equal to 800nm, preferably less than or equal to 500 nm.

Preferably, the zirconia is nano zirconia stabilized with a phase stabilizer. The phase stabilizer is one or more of magnesium oxide, calcium oxide, yttrium oxide, scandium oxide and cerium oxide. The content of the phase stabilizer is 3 to 20 wt%, preferably 5 to 15 wt% of the added amount of zirconia.

Or the phase stabilizer is one of a magnesium oxide-yttrium oxide composite stabilizer and a calcium oxide-yttrium oxide composite stabilizer. The content of the composite stabilizer is 5-15 wt% of the added amount of zirconia, and is preferably 8-12%.

Preferably, step 1) is specifically: firstly, stirring the alumina, the zirconia, the lanthanum fluoride and the titanium fluoride according to the proportion (preferably stirring for 5-50min, more preferably stirring for 10-30min) to obtain a dry mixture. Then dissolving zirconium oxychloride in water to obtain a wet material. The dry mixed material and the wet mixed material are separately contained for standby use to obtain the sphere raw material.

Then putting the ceramic ball balls into a rolling forming machine, starting the rolling forming machine and adjusting the rotating speed of the rolling forming machine to be 15-60r/min (preferably 20-45 r/min). Then adding dry mixture and wet mixture in the rolling process for rolling. And obtaining a rolled ball blank after rolling.

Preferably, the dry mixture is added at a rate of 1-20%, preferably 2-10%, of the mass of the seeds added per minute.

Preferably, the wet material is a saturated aqueous solution of zirconium oxychloride. The adding rate of the wet material is that the adding amount per minute is 0.5-10% of the mass of the ball seeds, and the adding rate is preferably 0.8-3%.

Preferably, step 2) is specifically: and putting the dried rolling ball blank into a rolling forming machine, starting the rolling forming machine and adjusting the rotating speed of the rolling forming machine to be 20-60r/min (preferably 25-45 r/min). Then adding organic monomer powder (preferably epoxy resin) to carry out rolling coating in the rolling process. Curing (preferably heating to 100-. Obtaining the ceramic ball blank with the organic ball shell coating.

Preferably, the addition rate of the organic monomer powder is 10 to 300g/min, preferably 30 to 150 g/min. (100 kg of dried ball blank is taken as a reference base number, and the adjustment can be reasonably carried out according to the actual working condition).

Preferably, step 3) is specifically: and (3) placing the ceramic ball blank coated with the organic ball shell into a cold isostatic press (preferably placing the ceramic ball blank coated with the organic ball shell into a net sleeve and then placing the net sleeve into the cold isostatic press), and carrying out isostatic pressing treatment at the pressure of 100-600MPa (preferably 150-500MPa) for 1-10min (preferably 3-8 min). And (4) after isostatic pressing treatment, obtaining an organic monomer composite ceramic blank.

Preferably, the step 4) is specifically: drying the organic monomer composite ceramic blank (preferably drying at 450-800 ℃ for 2-8h, more preferably drying at 500-700 ℃ for 3-6h) to obtain the ceramic blank.

Preferably, the step 5) is specifically as follows: putting the ceramic body into a sintering machine, and sintering the ceramic body at the temperature of 1300-1500 ℃ for 1-4h (preferably at the temperature of 1350-1450 ℃) at the heating rate of 5-120 ℃/h (preferably 10-80 ℃/h) to obtain a sintered ball body.

Preferably, step 6) is specifically: and shaping, polishing the surface and inspecting the sintered ball blank to obtain the wear-resistant ceramic microspheres.

Preferably, the sintering temperature rise rate is 5-120 ℃/min, preferably 8-60 ℃/min.

Preferably, in the step 2), a proper amount of hydrogen peroxide is added while the wet material is added. The adding amount of the hydrogen peroxide is 0.3 to 1.5 times, preferably 0.5 to 2 times of the adding amount of the zirconium oxychloride.

Preferably, in step 3), the thickness of the solidified shell layer of the spherical blank with the solidified shell layer is 3-30 μm, preferably 5-20 μm.

Preferably, in step 6), the particle size of the wear-resistant ceramic microspheres is less than or equal to 1mm, and preferably less than or equal to 0.8 mm.

Example 1

28kg of alumina, 42kg of zirconia, 6kg of lanthanum fluoride, lanthanum fluoride and 4kg of titanium fluoride are mixed and stirred for 10min to obtain a dry mixture. 20kg of zirconium oxychloride was dissolved in water to obtain a wet material.

Then 10kg of zirconia ceramic ball is put into a rolling forming machine, the rolling forming machine is started, and the rotating speed of the rolling forming machine is adjusted to be 25 r/min. Then dry mixture (dry mixture adding rate of 150g/min) and wet mixture (wet mixture adding rate of 75g/min) are added in the rolling process for rolling. And drying the rolled ball material at 70 ℃ for 600min after rolling is finished to obtain a rolled ball blank.

And then putting the dried rolled ball blank into a rolling forming machine, starting the rolling forming machine and adjusting the rotating speed of the rolling forming machine to be 30 r/min. Then adding organic monomer powder (bisphenol A type epoxy resin) at the speed of 80g/min in the rolling process for rolling coating. After the coating is finished, heating to 170 ℃ and preserving the heat for 45 min. Obtaining the ball blank with a solidified shell layer.

And then, putting the ball blank with the solidified shell layer into a net sleeve, and then putting the net sleeve into a cold isostatic press to perform isostatic pressing treatment for 4min under 500 Mpa. And after the isostatic pressing treatment is finished, drying the ball material for 4 hours at 500 ℃ to obtain a ceramic blank.

And finally, putting the ceramic body into a sintering machine, and sintering the ceramic body at 1400 ℃ for 3h to obtain a sintered ball body. And then shaping, polishing the surface and inspecting the sintered ball blank to obtain the ceramic microsphere I.

Example 2

27kg of alumina, 40kg of zirconia, 6kg of lanthanum fluoride and 4kg of titanium fluoride were mixed and stirred for 10min to obtain a dry mixture. 23kg of zirconium oxychloride was dissolved in water to obtain a wet material.

Then 10kg of alumina ceramic ball is put into a rolling forming machine, the rolling forming machine is started, and the rotating speed of the rolling forming machine is adjusted to be 25 r/min. Then dry materials (the adding speed of the dry materials is 150g/min) and wet materials (the adding speed of the wet materials is 75g/min) and 5kg of hydrogen peroxide are added in the rolling process for rolling. And after rolling is finished, drying the rolled ball material at 80 ℃ for 500min to obtain a rolled ball blank.

And then putting the dried rolled ball blank into a rolling forming machine, starting the rolling forming machine and adjusting the rotating speed of the rolling forming machine to be 30 r/min. Then adding organic monomer powder (bisphenol A type epoxy resin) at the speed of 80g/min in the rolling process for rolling coating. After the coating is finished, heating to 180 ℃ and preserving the heat for 45 min. Obtaining the ball blank with a solidified shell layer.

And then, putting the ball blank with the solidified shell layer into a net sleeve, and then putting the net sleeve into a cold isostatic press to perform isostatic pressing treatment for 5min under 500 Mpa. And after the isostatic pressing treatment is finished, drying the ball material at 550 ℃ for 4 hours to obtain a ceramic blank.

And finally, putting the ceramic body into a sintering machine, and sintering the ceramic body at 1400 ℃ for 3h to obtain a sintered ball body. And then shaping, polishing the surface and inspecting the sintered ball blank to obtain the ceramic microsphere II.

Example 3

27kg of alumina, 40kg of zirconia, 6kg of lanthanum fluoride and 4kg of titanium fluoride were mixed and stirred for 10min to obtain a dry mixture. 23kg of zirconium oxychloride was dissolved in water to obtain a wet material.

Then 10kg of alumina ceramic ball is put into a rolling forming machine, the rolling forming machine is started, and the rotating speed of the rolling forming machine is adjusted to be 25 r/min. Then dry materials (the adding speed of the dry materials is 160g/min) and wet materials (the adding speed of the wet materials is 70g/min) and 6kg of hydrogen peroxide are added in the rolling process for rolling. And drying the rolled ball material at 80 ℃ for 400min after rolling to obtain a rolled ball blank.

And then putting the dried rolled ball blank into a rolling forming machine, starting the rolling forming machine and adjusting the rotating speed of the rolling forming machine to be 32 r/min. Then adding organic monomer powder (phenol resin) at a speed of 75g/min during rolling to carry out rolling coating. After coating, heating to 175 ℃ and keeping the temperature for 40 min. Obtaining the ball blank with a solidified shell layer.

And then, putting the ball blank with the solidified shell layer into a net sleeve, and then putting the net sleeve into a cold isostatic press to perform isostatic pressing treatment at 550Mpa for 4.5 min. And after the isostatic pressing treatment is finished, drying the ball material at 580 ℃ for 3.5 hours to obtain a ceramic blank.

And finally, putting the ceramic body into a sintering machine, and sintering the ceramic body at 1350 ℃ for 4h to obtain a sintered ball body. And then shaping, polishing the surface and inspecting the sintered ball blank to obtain the ceramic microsphere III.

Example 4

27kg of alumina, 40kg of zirconia, 6kg of lanthanum fluoride and 4kg of titanium fluoride were mixed and stirred for 10min to obtain a dry mixture. 23kg of zirconium oxychloride was dissolved in water to obtain a wet material.

Then 10kg of alumina ceramic ball is put into a rolling forming machine, the rolling forming machine is started, and the rotating speed of the rolling forming machine is adjusted to be 25 r/min. Then dry materials (the adding rate of the dry materials is 170g/min) and wet materials (the adding rate of the wet materials is 75g/min) and 8kg of hydrogen peroxide are added in the rolling process for rolling. And after rolling is finished, drying the rolled ball material at 85 ℃ for 450min to obtain a rolled ball blank.

And then putting the dried rolling ball blank into a rolling forming machine, starting the rolling forming machine and adjusting the rotating speed of the rolling forming machine to be 28 r/min. Then adding organic monomer powder (silane cross-linked styrene) at a speed of 72g/min during rolling for rolling coating. After coating, heating to 170 ℃ and preserving heat for 35 min. Obtaining the ball blank with a solidified shell layer.

And then, putting the ball blank with the solidified shell layer into a net sleeve, and then putting the net sleeve into a cold isostatic press to perform isostatic pressing treatment for 4min under 550 Mpa. And after the isostatic pressing treatment is finished, drying the ball material at 550 ℃ for 3.5 hours to obtain a ceramic blank.

And finally, putting the ceramic body into a sintering machine, and sintering the ceramic body at 1380 ℃ for 3 hours to obtain a sintered ball body. And then shaping, polishing the surface and inspecting the sintered ball blank to obtain the ceramic microsphere IV.

Example 5

Dry blend was obtained by mixing and stirring 20kg of alumina, 45kg of zirconia, 6kg of lanthanum fluoride, 4kg of titanium fluoride for 10 min. 15kg of water was weighed as a wet material.

Then 10kg of alumina ceramic ball is put into a rolling forming machine, the rolling forming machine is started, and the rotating speed of the rolling forming machine is adjusted to be 28 r/min. Then dry blend (addition rate of dry blend: 165g/min) and wet blend (addition rate of wet blend: 70g/min) were added during rolling for rolling. And drying the rolled ball material at 80 ℃ for 400min after rolling to obtain a rolled ball blank.

And then putting the dried rolling ball blank into a rolling forming machine, starting the rolling forming machine and adjusting the rotating speed of the rolling forming machine to be 33 r/min. Then adding organic monomer powder (phenol resins) at the speed of 75g/min during rolling to carry out rolling coating. After coating, heating to 175 ℃ and keeping the temperature for 40 min. Obtaining the ball blank with a solidified shell layer.

And then, putting the ball blank with the solidified shell layer into a net sleeve, and then putting the net sleeve into a cold isostatic press to perform isostatic pressing treatment at 580Mpa for 3.5 min. And after the isostatic pressing treatment is finished, drying the ball material at 550 ℃ for 3 hours to obtain a ceramic blank.

And finally, placing the ceramic body into a sintering machine, and sintering the ceramic body at 1390 ℃ for 3h to obtain a sintered ball body. And then shaping, polishing the surface and inspecting the sintered ball blank to obtain the ceramic microsphere V.

Example 6

28kg of alumina, 42kg of zirconia, 6kg of lanthanum fluoride and 4kg of titanium fluoride were mixed and stirred for 10min to obtain a dry mixture. 20kg of zirconium oxychloride was dissolved in water to obtain a wet material.

Then 10kg of zirconia ceramic ball is put into a rolling forming machine, the rolling forming machine is started, and the rotating speed of the rolling forming machine is adjusted to be 30 r/min. Then dry materials (the adding rate of the dry materials is 170g/min) and wet materials (the adding rate of the wet materials is 78g/min) and 6kg of hydrogen peroxide are added in the rolling process for rolling. And after rolling is finished, drying the rolled ball material at 80 ℃ for 40min to obtain a rolled ball blank.

Then the dried rolled ball blanks were immersed in paraffin for 30 min. And then putting the ball blank coated with the paraffin into a cold isostatic press for isostatic pressing treatment at 500Mpa for 4 min. And after the isostatic pressing treatment is finished, drying the ball material at 550 ℃ for 3 hours to obtain a ceramic blank.

And finally, placing the ceramic body into a sintering machine, and sintering the ceramic body at 1390 ℃ for 3h to obtain a sintered ball body. And then shaping, polishing the surface and inspecting the sintered ball blank to obtain the ceramic microsphere VI.

Example 7

And (3) putting 10kg of zirconia ceramic ball into a rolling forming machine, starting the rolling forming machine and adjusting the rotating speed of the rolling forming machine to be 28 r/min. Then 80kg of zirconia (addition rate of 180g/min) and 20kg of water (addition rate of 75g/min) were added during the rolling. And after rolling is finished, drying the rolled ball material at 80 ℃ for 40min to obtain a rolled ball blank.

And then putting the dried rolled ball blank into a rolling forming machine, starting the rolling forming machine and adjusting the rotating speed of the rolling forming machine to be 30 r/min. Then adding organic monomer powder (phenol resins) at the speed of 75g/min during rolling to carry out rolling coating. After coating, heating to 175 ℃ and keeping the temperature for 40 min. Obtaining the ball blank with a solidified shell layer.

And then, putting the ball blank with the solidified shell layer into a net sleeve, and then putting the net sleeve into a cold isostatic press to perform isostatic pressing treatment for 4min under 500 Mpa. And after the isostatic pressing treatment is finished, drying the ball material at 550 ℃ for 3.5 hours to obtain a ceramic blank.

And finally, putting the ceramic body into a sintering machine, and sintering the ceramic body at 1400 ℃ for 3.5h to obtain a sintered ball body. And then shaping, polishing the surface and inspecting the sintered ball blank to obtain the ceramic microsphere VII.

Effect test comparison table: