CN102584279A - Preparation method of zirconium oxide hollow spheres - Google Patents
Preparation method of zirconium oxide hollow spheres Download PDFInfo
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- CN102584279A CN102584279A CN2012100139212A CN201210013921A CN102584279A CN 102584279 A CN102584279 A CN 102584279A CN 2012100139212 A CN2012100139212 A CN 2012100139212A CN 201210013921 A CN201210013921 A CN 201210013921A CN 102584279 A CN102584279 A CN 102584279A
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Abstract
The invention relates to the preparation technology of fire resistant materials and discloses a preparation method of zirconium oxide hollow spheres. The preparation method comprises the steps of: mixing a solid ceramic powder material with a solvent according to a certain proportion to prepare uniform and stable ceramic slurry; with polystyrene spheres as templates, fully soaking a plurality of the polystyrene spheres in the ceramic slurry; and enabling the ceramic slurry mixed with the polystyrene spheres to pass through a screen, filtering out excessive slurry, repeatedly covering the surfaces of the polystyrene spheres with the ceramic slurry, then drying the polystyrene spheres with the ceramic slurry of a certain thickness, removing plastics and sintering at a high temperature, wherein in the process of sintering at a high temperature, the polystyrene spheres are fully volatilized through high temperature combustion and hollow structures are left, so that the zirconium oxide ceramic hollow spheres are obtained. According to the preparation method of zirconium oxide hollow spheres, the problem of easy breakage of hollow spheres in the prior art is solved, and the sizes of the polystyrene spheres can be selected according to the sizes of the required hollow spheres; and the preparation method is simple in process and easy for industrial popularization.
Description
Technical field
The present invention relates to a kind of preparation method of refractory materials, relate in particular to a kind of preparation method of zirconium white matter hollow ball.
Background technology
Ceramic hollow ball is mainly used and the inner lining of kiln lagging material, and the hollow ball of aluminum oxide, zirconium white matter, mullite has been developed in the light heat insulation material field at present, and has obtained using widely.Zirconium white hollow ball and goods thereof, characteristics such as it is little to have volume density, and thermal capacitance is little, and thermal conductivity is low can increase substantially the kiln service efficiency as the inner lining of kiln material, shorten the production cycle.Zirconium white hollow ball product life-time service temperature can reach 2200 ℃, has characteristics such as corrosion-resistant, good thermal shock stability.Used for refractory material hollow ball preparation method commonly used does at present; Raw material is placed the special hot stove of direct current or three-phase alternating current electric arc ore deposit that relates to manufacturing; Behind high melt, carry out turndown winding-up, utilize in air, catch a cold under capillary effect contraction and obtain hollow ball of melt; " a kind of preparation method of high-strength alumina hollow ball " (publication No. CN101792317A) introduced a kind of method for preparing alumina hollow ball through the electric-arc heating injection method like patent; Patent " preparation method of corundum bollow ball " (publication number CN 1789197A) is through introducing the additive of adjustment melt viscosity; Utilize arc melting; The high-pressure air blowing process is prepared high-strength corundum matter hollow ball, and patent " novel refractory heat-isolating hollow ball and preparation method thereof " (patent No. 96116116.7) provides a kind of novel hollow ball preparation method.
Yet when adopting direct current or three-phase alternating current ore deposit hot stove electric smelting blowing process to prepare ceramic hollow ball; If melt viscosity control is improper; The hollow ball ball wall of then preparing is thinner; Intensity is low, in moulding process and vibration casting process hollow bulbus cordis breakage takes place easily, and then has influence on the use properties of goods.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of zirconium white matter hollow ball, it can be solved the problems of the technologies described above, and it is simple to have technology, be easy to the characteristics of industrialization promotion.The method of main employing disappearance mould prepares the hollow structure of hollow ball.
The present invention adopts following technical scheme for accomplishing the foregoing invention task:
A kind of preparation method of zirconium white matter hollow ball is mixed and made into uniform and stable ceramic size with solid ceramic powder and solvent with certain proportion; With the polystyrene sphere is template; PS has the irreversible characteristic of heat expansion as macromolecular material, discharges its activity through thermal pretreatment, can in sintering process, no longer expand and avoids causing blank cracking; Fully be immersed in several polystyrene spheres in the ceramic size; The ceramic size that is mixed with polystyrene sphere is passed through screen cloth; Leach redundant sizing agent; Through repeatedly polystyrene sphere being immersed in the ceramic size; Polystyrene sphere until making the surface have the certain thickness uniform sizing material reaches desired size, and the polystyrene sphere that is stained with ceramic size is carried out drying, at last dried polystyrene sphere is carried out plastic removal, high temperature sintering; In the process of high temperature sintering,, polystyrene sphere obtains zirconium white matter ceramic hollow ball thereby staying hollow structure through the volatilization of high temperature plastic removal.
A kind of preparation method of zirconium white matter hollow ball, described monoclinic zirconia powder is a main raw material, and granularity is not more than 300 orders, and described magnesia powder is a stablizer.
The component of said solid ceramic powder and weight percent are: monoclinic zirconia powder 80 ~ 99.5 wt%, magnesia powder 0.5 ~ 20 wt%;
A kind of preparation method of zirconium white matter hollow ball; The solid ceramic powder is mixed with 50 ~ 85 wt%:15 ~ 50 wt% part by weight with solvent; Add ball milling 2 ~ 10h in the planetary ball mill, the slurry behind the ball milling is got rid of until bubble through vacuum outgas, processes uniform and stable ceramic size.
A kind of preparation method of zirconium white matter hollow ball, the temperature during plastic removal is 200 ~ 600 ℃, the time is not less than 2h; After plastic removal is accomplished, the furnace temperature of high temperature firing furnace is risen to 1650 ~ 1750 ℃ carry out sintering and make the thin-walled ceramic crucible, sintering time is 5 ~ 10h.
A kind of preparation method of zirconium white matter hollow ball, said solvent composition is: water, thickening material, auxiliary rheological agents, sticker, dispersion agent.
A kind of preparation method of zirconium white matter hollow ball, auxiliary rheological agents in the solvent and thickening material can be Xylo-Mucines, hydroxypropyl level sodium cellulosate, polyoxyethylene glycol, one or more in the USP Kosher, the thixotropy and raising viscosity in order to improve ceramic size respectively.
A kind of preparation method of zirconium white matter hollow ball, the sticker in the solvent can be a PVAC polyvinylalcohol, Xylo-Mucine CMC, silicon sol, aluminium colloidal sol, dextrin, one or more in the spent pulping liquor.
A kind of preparation method of zirconium white matter hollow ball is characterized in that: the dispersion agent in the solvent can be a ZX-I, Macrogol 2000, polymine (PEI), methylene radical acrylic amine, one or more in the polymethyl methacrylate.
The component of said solvent and weight percent are: auxiliary rheological agents and thickening material proportional range are 1:2 ~ 1:7.5, and whole add-on is 0.03 ~ 0.2 wt%, sticker 0.9 ~ 2.0 wt%, dispersion agent 0.07 ~ 0.3 wt%, water 97.5 ~ 99.0 wt%.
Ceramic hollow ball is mainly used and the inner lining of kiln lagging material, and the hollow ball of aluminum oxide, zirconium white matter, mullite has been developed in the light heat insulation material field at present, and has obtained using widely.Zirconium white hollow ball and goods thereof, characteristics such as it is little to have volume density, and thermal capacitance is little, and thermal conductivity is low can increase substantially the kiln service efficiency as the inner lining of kiln material, shorten the production cycle.The known technology that component selection of zirconium white matter and assembly, preparation method etc. generally adopt for enterprise; The present invention only relates to the preparation method who proposes a kind of zirconium white matter hollow ball.
The preparation method of a kind of zirconium white matter hollow ball that the present invention proposes; Solved prior art hollow bulbus cordis damaged problem has taken place easily; And can be according to the size of the size Selection polystyrene sphere of required hollow ball, it is simple to have technology, is easy to the characteristics of industrialization promotion.
Embodiment
Embodiment 1
With the solid ceramic powder by mass percentage: monoclinic zirconia powder (350 order) 90 wt%, fine magnesium oxide micro-powder 10wt%, the ratio thorough mixing is processed uniform ceramic powder.
With ceramic powder, dispersion agent, sticker PVA (6wt% concentration), CMC, water, press 82wt%, 0.06wt%, 2.0 wt%, 0.015%, the ratio of 15.925wt% is mixed, and joins in the planetary ball mill, and ball milling 4h makes the ceramic size of stable homogeneous.
Adopt impeller; Polystyrene sphere and ceramic size thorough mixing is even; The slurry that is mixed with polystyrene sphere leaches redundant sizing agent, repeatedly repeatedly through screen cloth; Polystyrene sphere until making the surface have the certain thickness uniform sizing material reaches desired size, the p-poly-phenyl ethene bead drying treatment of jetting.The biscuit that drying is good is sent into and is carried out sintering in the high temperature firing furnace, is warming up to 600 ℃ with the temperature rise rate of 60 ℃/h, and insulation 2h is warming up to 1700 ℃ then rapidly, under this temperature, is incubated 5h, naturally cools to room temperature, can obtain zirconium white matter ceramic hollow ball.
Embodiment 2
With the solid ceramic powder by mass percentage: monoclinic zirconia powder (500 order) 88 wt%, fine magnesium oxide micro-powder 12wt%, the ratio thorough mixing is processed uniform ceramic powder.
With ceramic powder, dispersion agent, sticker PVA (6wt% concentration), CMC, water, press 80wt%, 0.09wt%, 0.5 wt%, 0.1wt%, the ratio of 19.31wt% is mixed, and joins in the planetary ball mill, and ball milling 6h makes the ceramic size of stable homogeneous.
Adopt impeller; Polystyrene sphere and ceramic size thorough mixing is even; The slurry that is mixed with polystyrene sphere leaches redundant sizing agent, repeatedly repeatedly through screen cloth; Polystyrene sphere until making the surface have the certain thickness uniform sizing material reaches desired size, the p-poly-phenyl ethene bead drying treatment of jetting.The biscuit that drying is good is sent into and is carried out sintering in the high temperature firing furnace, is warming up to 600 ℃ with the temperature rise rate of 60 ℃/h, and insulation 4h is warming up to 1700 ℃ then rapidly, under this temperature, is incubated 10h, naturally cools to room temperature, can obtain zirconium white matter ceramic hollow ball.
Embodiment 3
With the solid ceramic powder by mass percentage: monoclinic zirconia powder (350 order) 95 wt%, fine magnesium oxide micro-powder 5 wt%, the ratio thorough mixing is processed uniform ceramic powder.
With ceramic powder, dispersion agent, sticker PVA (6wt% concentration), CMC, water, press 85wt%, 0.25 wt%, 0.15wt%, 0.2 wt%, the ratio of 14.4wt% is mixed, and joins in the planetary ball mill, and ball milling 4h makes the ceramic size of stable homogeneous.
Adopt impeller; Polystyrene sphere and ceramic size thorough mixing is even; The slurry that is mixed with polystyrene sphere leaches redundant sizing agent, repeatedly repeatedly through screen cloth; Polystyrene sphere until making the surface have the certain thickness uniform sizing material reaches desired size, the p-poly-phenyl ethene bead drying treatment of jetting.The biscuit that drying is good is sent into and is carried out sintering in the high temperature firing furnace, is warming up to 600 ℃ with the temperature rise rate of 40 ℃/h, and insulation 3h is warming up to 1680 ℃ then rapidly, under this temperature, is incubated 7h, naturally cools to room temperature, can obtain zirconium white matter ceramic hollow ball.
Embodiment 4
With the solid ceramic powder by mass percentage: monoclinic zirconia powder (350 order) 92 wt%, fine magnesium oxide micro-powder 8 wt%, the ratio thorough mixing is processed uniform ceramic powder.
With ceramic powder, dispersion agent, sticker PVA (6wt% concentration), CMC, water, press 87wt%, 0.10 wt%, 0.8 wt%, 0.03wt%, the ratio of 12.07wt% is mixed, and joins in the planetary ball mill, and ball milling 7h makes the ceramic size of stable homogeneous.
Adopt impeller; Polystyrene sphere and ceramic size thorough mixing is even; The slurry that is mixed with polystyrene sphere leaches redundant sizing agent, repeatedly repeatedly through screen cloth; Polystyrene sphere until making the surface have the certain thickness uniform sizing material reaches desired size, the p-poly-phenyl ethene bead drying treatment of jetting.The biscuit that drying is good is sent into and is carried out sintering in the high temperature firing furnace, is warming up to 600 ℃ with the temperature rise rate of 80 ℃/h, and insulation 6h is warming up to 1750 ℃ then rapidly, under this temperature, is incubated 8h, naturally cools to room temperature, can obtain zirconium white matter ceramic hollow ball.
Embodiment 5
With the solid ceramic powder by mass percentage: monoclinic zirconia powder (350 order) 95 wt%, fine magnesium oxide micro-powder 5wt%, the ratio thorough mixing is processed uniform ceramic powder.
With ceramic powder, dispersion agent, sticker PVA (6wt% concentration), CMC, water, press 85wt%, 0.25 wt%, 0.6 wt%, 0.12wt%, the ratio of 14.03wt% is mixed, and joins in the planetary ball mill, and ball milling 4h makes the ceramic size of stable homogeneous.
Adopt impeller; Polystyrene sphere and ceramic size thorough mixing is even; The slurry that is mixed with polystyrene sphere leaches redundant sizing agent, repeatedly repeatedly through screen cloth; Polystyrene sphere until making the surface have the certain thickness uniform sizing material reaches desired size, the p-poly-phenyl ethene bead drying treatment of jetting.The biscuit that drying is good is sent into and is carried out sintering in the high temperature firing furnace, is warming up to 600 ℃ with the temperature rise rate of 40 ℃/h, and insulation 3h is warming up to 1680 ℃ then rapidly, under this temperature, is incubated 7h, naturally cools to room temperature, can obtain zirconium white matter ceramic hollow ball.
Claims (9)
1. the preparation method of a high-purity zirconia matter hollow ball is characterized in that: solid ceramic powder and solvent are mixed and made into uniform and stable ceramic size with certain proportion; With the polystyrene sphere is template, fully is immersed in several polystyrene spheres in the ceramic size; The ceramic size that is mixed with polystyrene sphere is passed through screen cloth; Leach redundant sizing agent; Through repeatedly polystyrene sphere being immersed in the ceramic size; Have the uniform slurry of certain thickness until the polystyrene sphere surface, the polystyrene sphere that is stained with ceramic size is carried out drying, at last dried polystyrene sphere is carried out plastic removal, burns till; Sintering temperature in the process of high temperature sintering, obtains zirconium white matter ceramic hollow ball thereby the ball of PS material stays hollow structure through the mistake of high temperature burning between 1650 ~ 1750 ℃.
2. the preparation method of a kind of zirconium white matter hollow ball according to claim 1 is characterized in that: described monoclinic zirconia powder is a main raw material, and granularity is not more than 300 orders, and described magnesia powder is a stablizer.
3. the preparation method of a kind of zirconium white matter hollow ball according to claim 1 is characterized in that: the component of said solid ceramic powder and weight percent are: monoclinic zirconia powder 80 ~ 99.5 wt%, magnesia powder 0.5 ~ 20 wt%.
4. the preparation method of a kind of zirconium white matter hollow ball according to claim 1 is characterized in that: said solvent composition is: water, thickening material, auxiliary rheological agents, sticker, dispersion agent.
5. the preparation method of a kind of zirconium white matter hollow ball according to claim 1; It is characterized in that: auxiliary rheological agents in the solvent and thickening material can be Xylo-Mucines; Hydroxypropyl level sodium cellulosate; Polyoxyethylene glycol, one or more in the USP Kosher, thixotropy and raising viscosity respectively in order to improve ceramic size.
6. the preparation method of a kind of zirconium white matter hollow ball according to claim 1 is characterized in that: the sticker in the solvent can be a PVAC polyvinylalcohol, Xylo-Mucine CMC, silicon sol, aluminium colloidal sol, dextrin, one or more in the spent pulping liquor.
7. the preparation method of a kind of zirconium white matter hollow ball according to claim 1; It is characterized in that: the dispersion agent in the solvent can be a ZX-I, Macrogol 2000, polymine (PEI); The methylene radical acrylic amine, one or more in the polymethyl methacrylate.
8. the preparation method of a kind of zirconium white matter hollow ball according to claim 1; It is characterized in that: with solid ceramic powder and solvent by weight proportion 50 ~ 85 wt%:15 ~ 50 wt% mix; Ball milling is until the powder homodisperse in the adding planetary ball mill; Obtain good fluidity, disperse the slurry of homogeneous; Slurry behind the ball milling is got rid of until bubble through vacuum outgas, processes uniform and stable ceramic size.
9. the preparation method of a kind of zirconium white matter hollow ball according to claim 1 is characterized in that: the temperature during plastic removal is 200 ~ 600 ℃, and the time is not less than 2h; After plastic removal is accomplished, the furnace temperature of high temperature firing furnace is risen to 1650 ~ 1750 ℃ carry out sintering and make zirconium white matter hollow ball, sintering time is 5 ~ 10h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103058656A (en) * | 2013-02-05 | 2013-04-24 | 山东国瓷功能材料股份有限公司 | Method for preparing micron-sized hollow zirconium oxide balls |
| CN106928475A (en) * | 2017-02-13 | 2017-07-07 | 广东国利先进复合材料研发有限公司 | A kind of preparation method of Kafra fiber hollow ball |
| CN109265152A (en) * | 2018-08-24 | 2019-01-25 | 清华大学 | The preparation method of ceramic hollow ball |
| CN110183244A (en) * | 2019-06-19 | 2019-08-30 | 长安大学 | A kind of hollow mullite spheroidal material and preparation method thereof |
| CN112745128A (en) * | 2020-12-31 | 2021-05-04 | 松山湖材料实验室 | Method for producing ceramic preform |
| CN113912414A (en) * | 2021-10-28 | 2022-01-11 | 韶关学院 | Method for preparing mullite porous heat-insulating material by using coal gangue |
| CN116120044A (en) * | 2022-12-22 | 2023-05-16 | 宜兴市隆昌耐火材料有限公司 | Energy-saving wear-resistant zirconia-corundum composite hollow sphere casting material |
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| CN101269959A (en) * | 2008-04-28 | 2008-09-24 | 天津大学 | Compact zirconia ceramics with thermal shock resistance and preparation method thereof |
| CN101274246A (en) * | 2007-12-26 | 2008-10-01 | 中国科学院上海硅酸盐研究所 | Sol-gel method for preparing earth silicon/titanic oxide hollow microballoon |
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| CN101274246A (en) * | 2007-12-26 | 2008-10-01 | 中国科学院上海硅酸盐研究所 | Sol-gel method for preparing earth silicon/titanic oxide hollow microballoon |
| CN101269959A (en) * | 2008-04-28 | 2008-09-24 | 天津大学 | Compact zirconia ceramics with thermal shock resistance and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058656A (en) * | 2013-02-05 | 2013-04-24 | 山东国瓷功能材料股份有限公司 | Method for preparing micron-sized hollow zirconium oxide balls |
| CN106928475A (en) * | 2017-02-13 | 2017-07-07 | 广东国利先进复合材料研发有限公司 | A kind of preparation method of Kafra fiber hollow ball |
| CN109265152A (en) * | 2018-08-24 | 2019-01-25 | 清华大学 | The preparation method of ceramic hollow ball |
| CN110183244A (en) * | 2019-06-19 | 2019-08-30 | 长安大学 | A kind of hollow mullite spheroidal material and preparation method thereof |
| CN110183244B (en) * | 2019-06-19 | 2022-06-03 | 长安大学 | Hollow mullite spherical material and preparation method thereof |
| CN112745128A (en) * | 2020-12-31 | 2021-05-04 | 松山湖材料实验室 | Method for producing ceramic preform |
| CN113912414A (en) * | 2021-10-28 | 2022-01-11 | 韶关学院 | Method for preparing mullite porous heat-insulating material by using coal gangue |
| CN116120044A (en) * | 2022-12-22 | 2023-05-16 | 宜兴市隆昌耐火材料有限公司 | Energy-saving wear-resistant zirconia-corundum composite hollow sphere casting material |
| CN116120044B (en) * | 2022-12-22 | 2024-01-19 | 宜兴市隆昌耐火材料有限公司 | Energy-saving wear-resistant zirconia-corundum composite hollow sphere casting material |
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