CN1562887A - Composite powder of zirconia in high square phase and alumina and preparation method - Google Patents
Composite powder of zirconia in high square phase and alumina and preparation method Download PDFInfo
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- CN1562887A CN1562887A CN 200410029885 CN200410029885A CN1562887A CN 1562887 A CN1562887 A CN 1562887A CN 200410029885 CN200410029885 CN 200410029885 CN 200410029885 A CN200410029885 A CN 200410029885A CN 1562887 A CN1562887 A CN 1562887A
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Abstract
High density low viscosity pulp material and powder material with high content of tetragonal phase zirconium oxide are required by the invention. Surface of zirconium oxide is covered by a layer of aluminium oxide by heterogeneous precipitation, then they are processed by heating to make aluminium oxide solidifying at surface of zirconium oxide. The tetragonal phase content in zirconium oxide powder is increased to increase utilized ratio of zirconium oxide in ceramics prodn. Heating process is used to compose larger particle to reduce absorbing water quantity of the surface, thus to increase solid phase content of low viscosity pulp material. Growing of zirconium oxide in high temp. is restained by covering a layer of aluminium oxide, it is beneficial to generate fine-grained ceramics of zirconium oxide and aluminium.
Description
Technical field
The present invention relates to a kind of Zirconia-alumina composite powder for preparing ceramic usefulness and preparation method thereof, specifically, the present invention relates to high Zirconia-alumina composite powder of a kind of cubic phase content of the alumina-coated for preparing high-intensity high-tenacity pottery usefulness and preparation method thereof.
Background technology
High-performance zirconia must adopt fine powder and suitable Technology.At present, quality oxide zirconium based ceramic powder material is by the preparation of basic zirconium chloride (the water-soluble salt that contains yttrium or the cerium) precipitator method, is prepared into the zirconium white powder through thermal treatment then.Between the 30-100 nanometer, tetragonal phase zirconium oxide content is fit to dry-press process through granulation about 50% by the powder particle size of this method preparation, and the ceramics strength of its pressureless sintering is at 600～800MPa, and fracture toughness property is at 10～12 MPam
1/2Perhaps use coprecipitation method preparations such as basic zirconium chloride (the water-soluble salt that contains yttrium or cerium) and aluminum soluble salt, be prepared into zirconium white and aluminum oxide composite powder through thermal treatment then, ceramic performance dry-pressing formed, pressureless sintering is better than preceding a kind of method.The high tenacity pottery requires crystal grain tiny, the second phase crystal grain is close with basic grain size, usually must adopt special production technique (as sintering hot pressing) just can reach above-mentioned requirements, as preparing ceramics strength at 1000～1600MPa with hot pressed sintering, fracture toughness property is at 14～18MPam
1/2, but production cost height can not be made the product of complicated shape.Utilize second to strengthen flexible nano ceramics technology mutually and increased substantially the strength of materials in recent years, but toughness of material is not significantly increased, and will uses Fast Sintering equipment, can not make the product of complicated shape.The nineties in last century, the development of ceramic wet forming technique is rapid, and the stupalith for preparing complicated shape for low cost has been established the technology basis.One of its gordian technique is preparation high density, low viscous slurry.With the gel-casting technology is example, and this processing unit is simple, and the blank density height of moulding, intensity is big, shrinking percentage is less, and ceramic product reliability height is with existing more research of pottery and application such as the aluminum oxide of this method preparation and silicon nitrides.But because high-performance zirconia base pottery uses nanopowder, high density, low viscous pulp preparation difficulty, relevant research is less.
The nano zircite powder is because its bigger specific surface area, thereby has the bigger surface adsorption water yield, and assembles easily and make the zirconium white grain growth, and granularity increases, and has reduced the content of tetragonal phase zirconium oxide.The volume fraction maximum of zirconium white powder can only reach 25～28% during the preparation low viscosity slurry, can not satisfy the wet moulding requirement of high solid phase, low viscosity slurry.
Summary of the invention
The high tetragonal phase zirconium oxide powder of needs when preparing pottery with high density, low viscosity slurry in order to satisfy, the invention solves problems such as the cubic phase content that the zirconium white powder exists in the prior art is low, the surface adsorption water yield is big, propose a kind of high tetragonal phase zirconium oxide-aluminum oxide composite powder and preparation method thereof.
High tetragonal phase zirconium oxide of the present invention-aluminum oxide composite powder is made up of the component that comprises following weight per-cent: zirconium white 74～96%, yttrium oxide 2～6%, aluminum oxide 2～20%; Powder particle size is 100～200nm, and alumina-coated is on zirconic surface, and wherein tetragonal phase zirconium oxide accounts for the 70-90% of zirconium white total amount.
The preparation method of high tetragonal phase zirconium oxide of the present invention-aluminum oxide composite powder may further comprise the steps:
(1) raw material powdered zirconium oxide and water are made into suspension according to weight ratio 1: 1～3 mixing stirrings; It is 20～60% the aqueous solution that aluminium salt is made into weight percent concentration; The two is mixed stirring obtain zirconium white-aluminium salt mixed solution; Described raw material zirconium white fine powder particle diameter is 30～70nm, contains weight percent 4.37～6.04% yttrium oxide;
(2) under agitation, ammoniacal liquor slowly being splashed in zirconium white-aluminium salt mixed solution that step (2) obtains, is 8～10 until the pH of mixed solution value, and is to keep 0～2 hour under 8～10 the condition in the pH value, filters, and washing is to neutral, and suction filtration obtains powder;
(3) the powder drying that step (2) is obtained is heat-treated then and is made the aluminium hydroxide that is coated on the powdered zirconium oxide surface be decomposed into aluminum oxide, obtains the Zirconia-alumina composite powder of high cubic phase.
Described particle diameter is that the raw material powdered zirconium oxide that contains weight percent 4.37～6.04% yttrium oxide of 30～70nm is a market product.
The preferred aluminum chloride of described aluminium salt or its hydrate, aluminum nitrate or its hydrate, Tai-Ace S 150 or its hydrate, two or more mixture in them.
Described heat treating method preferably kept 0.5～3 hour under 900～1200 ℃ of temperature.The heat-up rate that is more preferably with 100 ℃/h is warming up to 200～300 ℃, keeps 0～2 hour at 200～300 ℃, rises to 900～1200 ℃ and kept 0.5～3 hour with same heat-up rate then.The water yield and the crystal water of surface adsorption can be removed the generation aluminum oxide down at 200～300 ℃, under 900～1200 ℃, aluminum oxide and zirconium white be formed composition particles.
High tetragonal phase zirconium oxide-aluminum oxide the composite powder of the present invention's preparation is used to prepare the high-intensity high-tenacity zirconia-based ceramics.For example can use injectiong coagulation shaping technology and pressureless sintering method to obtain the high-intensity high-tenacity zirconia-based ceramics, concrete preparation process is as follows:
(1) acrylamide, linking agent being made into weight percent by weight 20: 0.8～1.2 is 14% water base premixed liquid;
(2) will be that the water base premixed liquid of zirconium white powder, dispersion agent and the step (1) of 70-90% mixes according to weight ratio 100: 1～1.8: 25～28 by the tetragonal phase zirconium oxide content on alumina-coated powdered zirconium oxide surface, and grind and make slurry;
(3) slurry that step (2) is obtained vacuumizes the aqueous solution that adds solidifying agent after the degasification, slurry and weight percent are that the weight ratio of 1% aqueous solution of curing agent is 100: 0.5～1, casting at room temperature, solidify down at 60～80 ℃, dry back pre-burning binder removal, descended normal pressure-sintered 1～3 hour at 1500～1700 ℃ then, obtain the high-intensity high-tenacity zirconia-based ceramics.
The preferred N of described linking agent, N-methylene diacrylamine, described dispersion agent optimization polypropylene acid ammonium, described solidifying agent initiator system of ammonium persulfate.
The present invention utilizes the non-homogeneous phase deposition principle, coats one deck alumina layer in the zirconium surface that contains yttrium oxide, makes it generate aluminum oxide by thermal treatment then and is cemented in zirconium surface.Because outer oxide aluminium produces effect of contraction to the internal layer zirconium white, has suppressed crystal conversion, has improved the cubic phase content of zirconium white powder, the utilization ratio of zirconium white powder is improved.The cubic phase content that contains the raw material powdered zirconium oxide of weight percent 5.21% yttrium oxide is about 51% o'clock of zirconium white total amount, and cubic phase content is about 80% of zirconium white total amount in the powder that the present invention makes.Aluminium oxide-zirconium oxide grain graininess after the thermal treatment simultaneously increases, when the particle diameter of raw material powdered zirconium oxide is about 30～50nm, the powder particle size that the present invention makes is increased to 100～200nm, reduced the surface adsorption water yield, it is electrical that aluminum oxide has changed zirconium surface, thereby improved the consistency with dispersion agent.Can reach 35～40% by solid volume fraction in the low viscosity slurry of powder preparation of the present invention, and overcome the shortcoming of annotating body drying condition strictness when congealing into type preparation pottery, coat one deck alumina layer simultaneously and suppressed zirconium white grain growth under the high temperature effectively, the cubic phase content of zirconium white powder increases, pressureless sintering can obtain the pottery of high-toughness high-strength, intensity is 700～1000MPa, and toughness reaches 15～17MPam
1/2
Embodiment
Adopt the mode of embodiment to further specify high tetragonal phase zirconium oxide powder of the present invention and preparation method thereof below, but the present invention is not limited to these embodiment.
Embodiment 1
With particle diameter is that the powdered zirconium oxide 100g that contains 5.21% (weight ratio) yttrium oxide of 30～50nm joins to stir in the 200g water and is mixed with suspension; Al (NO with 36.76g
3)
310H
2It is 20% the aqueous solution that O is made into mass percent concentration; With the two mixing, under agitation slow titration ammoniacal liquor, the pH value slowly is adjusted to 8～10, Al (NO in this process from 3～4
3)
3Generate Al (OH)
3Homogeneously precipitate in zirconic surface, keep the pH value at 8～10 times 1 hour, filter, the washing powder is to neutral, heat-treat after suction filtration, the drying, heat-up rate is 100 ℃/h, 280 ℃ of insulations 0.5 hour, continue to be warming up to 1050 ℃ then, be incubated 2 hours, obtain high tetragonal phase zirconium oxide of the present invention-aluminum oxide composite powder, particle diameter is 100-200nm, tetragonal phase zirconium oxide content is about the 75-80% of zirconium white total amount, and the zirconia content that contains weight percent 5.21% yttrium oxide is 95%, and alumina content is 5%.
Embodiment 2
With particle diameter is that the powdered zirconium oxide 100g that contains the 3mol% yttrium oxide of 30～50nm joins to stir in the 200g water and is mixed with suspension; AlCl with 94.7g
36H
2It is 40% the aqueous solution that O is made into mass percent concentration; With the two mixing, under agitation slow titration ammoniacal liquor, the pH value slowly is adjusted to 8～10, AlCl in this process
3Generate Al (OH)
3Homogeneously precipitate in zirconic surface, keep the pH value, filter at 8～10 times 1 hour, the washing powder is heat-treated after suction filtration, the drying to neutral, and heat-up rate is 100 ℃/h, 280 ℃ of insulations 0.5 hour, continue to be warming up to 1150 ℃ then, be incubated 2 hours, obtain high tetragonal phase zirconium oxide powder of the present invention, particle diameter is 100-200nm, tetragonal phase zirconium oxide content is about the 75-80% of zirconium white total amount, and the zirconia content that contains 5.21% yttrium oxide is 80%, and alumina content is 20%.
Claims (6)
1. one kind high tetragonal phase zirconium oxide-aluminum oxide composite powder is characterized in that it is made up of the component that comprises following weight per-cent: zirconium white 74～96%, yttrium oxide 2～6%, aluminum oxide 2～20%; Powder particle size is 100～200nm, and alumina-coated is on zirconic surface, and wherein tetragonal phase zirconium oxide accounts for the 70-90% of zirconium white total amount.
2. high tetragonal phase zirconium oxide according to claim 1-aluminum oxide composite powder is characterized in that it is made by following preparation method:
(1) raw material powdered zirconium oxide and water are made into suspension according to weight ratio 1: 1～3 mixing stirrings; It is 20～60% the aqueous solution that aluminium salt is made into weight percent concentration; The two is mixed stirring obtain zirconium white-aluminium salt mixed solution; Described raw material zirconium white fine powder particle diameter is 30～70nm, contains weight percent 4.37～6.04% yttrium oxide;
(2) under agitation, ammoniacal liquor slowly being splashed in zirconium white-aluminium salt mixed solution that step (2) obtains, is 8～10 until the pH of mixed solution value, and is to keep 0～2 hour under 8～10 the condition in the pH value, filters, and washing is to neutral, and suction filtration obtains powder;
(3) the powder drying that step (2) is obtained is heat-treated then and is made the aluminium hydroxide that is coated on the powdered zirconium oxide surface be decomposed into aluminum oxide, obtains the Zirconia-alumina composite powder of high cubic phase.
3. the preparation method of the described high tetragonal phase zirconium oxide of claim 1-aluminum oxide composite powder is characterized in that it may further comprise the steps:
(1) raw material powdered zirconium oxide and water are made into suspension according to weight ratio 1: 1～3 mixing stirrings; It is 20～60% the aqueous solution that aluminium salt is made into weight percent concentration; The two is mixed stirring obtain zirconium white-aluminium salt mixed solution; Described raw material zirconium white fine powder particle diameter is 30～70nm, contains weight percent 4.37～6.04% yttrium oxide;
(2) under agitation, ammoniacal liquor slowly being splashed in zirconium white-aluminium salt mixed solution that step (2) obtains, is 8～10 until the pH of mixed solution value, and is to keep 0～2 hour under 8～10 the condition in the pH value, filters, and washing is to neutral, and suction filtration obtains powder;
(3) the powder drying that step (2) is obtained is heat-treated then and is made the aluminium hydroxide that is coated on the powdered zirconium oxide surface be decomposed into aluminum oxide, obtains the Zirconia-alumina composite powder of high cubic phase.
4. preparation method according to claim 3 is characterized in that described aluminium salt is aluminum chloride or its hydrate, aluminum nitrate or its hydrate, Tai-Ace S 150 or its hydrate, two or more mixture in them.
5. preparation method according to claim 3 is characterized in that the heat treating method described in the step (4) is for to keep 0.5～3 hour under 900～1200 ℃ of temperature.
6. preparation method according to claim 3, it is characterized in that the heat treating method described in the step (4) is: the heat-up rate with 100 ℃/h is warming up to 200～300 ℃, kept 0～2 hour at 200～300 ℃, rise to 900～1200 ℃ and kept 0.5～3 hour with same heat-up rate then.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100372969C (en) * | 2004-09-03 | 2008-03-05 | 湖北葛店开发区地大纳米材料制造有限公司 | Nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides and its production method |
| CN101870587A (en) * | 2009-04-24 | 2010-10-27 | 中国科学院福建物质结构研究所 | Nano nonoclinic phase zirconium oxide material and synthesis method thereof |
| CN102245008A (en) * | 2010-05-10 | 2011-11-16 | 陈惠敏 | Circuit noise inhibiting method and inhibiting object thereof |
| CN101538154B (en) * | 2009-04-28 | 2012-01-25 | 上海景文材料科技发展有限公司 | Spontaneous hydro-thermal method for preparing special composite nano ceramic powder for ceramic tooth |
| CN101318824B (en) * | 2008-06-30 | 2012-02-22 | 中国科学院上海硅酸盐研究所 | Yttrium coated stable zirconium oxide powder, preparation and application thereof |
| CN102603272A (en) * | 2012-03-08 | 2012-07-25 | 江汉大学 | Ceramic material and preparation method thereof |
| CN109093061A (en) * | 2018-09-19 | 2018-12-28 | 北京仁创砂业铸造材料有限公司 | Ceramsite sand and preparation method thereof, cold-box sand and its curing process |
| CN114524456A (en) * | 2022-03-29 | 2022-05-24 | 赛科络纳米新材料(苏州)有限公司 | Nano zirconium oxide material and synthetic method thereof |
| CN114829304A (en) * | 2019-12-24 | 2022-07-29 | 关东电化工业株式会社 | Coated zirconia fine particles and method for producing same |
| CN116751077A (en) * | 2023-06-28 | 2023-09-15 | 浙江大学 | Method for preparing alumina micro-nano structural layer on zirconia surface based on secondary precipitation-heat treatment, product and application thereof |
| CN116854466A (en) * | 2023-06-28 | 2023-10-10 | 成都三环科技有限公司 | Ceramic ferrule and preparation method and application thereof |
| CN116751077B (en) * | 2023-06-28 | 2024-05-14 | 浙江大学 | Method for preparing alumina micro-nano structural layer on zirconia surface based on secondary precipitation-heat treatment, product and application thereof |
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- 2004-03-31 CN CN 200410029885 patent/CN1257132C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100372969C (en) * | 2004-09-03 | 2008-03-05 | 湖北葛店开发区地大纳米材料制造有限公司 | Nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides and its production method |
| CN101318824B (en) * | 2008-06-30 | 2012-02-22 | 中国科学院上海硅酸盐研究所 | Yttrium coated stable zirconium oxide powder, preparation and application thereof |
| CN101870587A (en) * | 2009-04-24 | 2010-10-27 | 中国科学院福建物质结构研究所 | Nano nonoclinic phase zirconium oxide material and synthesis method thereof |
| CN101870587B (en) * | 2009-04-24 | 2013-05-01 | 中国科学院福建物质结构研究所 | Nano nonoclinic phase zirconium oxide material and synthesis method thereof |
| CN101538154B (en) * | 2009-04-28 | 2012-01-25 | 上海景文材料科技发展有限公司 | Spontaneous hydro-thermal method for preparing special composite nano ceramic powder for ceramic tooth |
| CN102245008B (en) * | 2010-05-10 | 2015-06-03 | 陈惠敏 | Circuit noise inhibiting method and inhibiting object thereof |
| WO2011140962A1 (en) * | 2010-05-10 | 2011-11-17 | Chen Huimin | Structure for noise suppression in electronic devices and method thereof |
| CN102245008A (en) * | 2010-05-10 | 2011-11-16 | 陈惠敏 | Circuit noise inhibiting method and inhibiting object thereof |
| CN102603272A (en) * | 2012-03-08 | 2012-07-25 | 江汉大学 | Ceramic material and preparation method thereof |
| CN109093061A (en) * | 2018-09-19 | 2018-12-28 | 北京仁创砂业铸造材料有限公司 | Ceramsite sand and preparation method thereof, cold-box sand and its curing process |
| CN114829304A (en) * | 2019-12-24 | 2022-07-29 | 关东电化工业株式会社 | Coated zirconia fine particles and method for producing same |
| CN114524456A (en) * | 2022-03-29 | 2022-05-24 | 赛科络纳米新材料(苏州)有限公司 | Nano zirconium oxide material and synthetic method thereof |
| CN116751077A (en) * | 2023-06-28 | 2023-09-15 | 浙江大学 | Method for preparing alumina micro-nano structural layer on zirconia surface based on secondary precipitation-heat treatment, product and application thereof |
| CN116854466A (en) * | 2023-06-28 | 2023-10-10 | 成都三环科技有限公司 | Ceramic ferrule and preparation method and application thereof |
| CN116854466B (en) * | 2023-06-28 | 2024-03-15 | 成都三环科技有限公司 | Ceramic ferrule and preparation method and application thereof |
| CN116751077B (en) * | 2023-06-28 | 2024-05-14 | 浙江大学 | Method for preparing alumina micro-nano structural layer on zirconia surface based on secondary precipitation-heat treatment, product and application thereof |
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