CN111204802A - Preparation method of black yttrium-stabilized zirconia powder - Google Patents
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Abstract
The invention belongs to the technical field of new inorganic materials, and particularly relates to a preparation method of black yttrium-stabilized zirconia powder. Mixing a zirconium oxychloride solution and a yttrium trichloride solution in proportion, adding an organic acid to generate gel, adding an ammonia water solution to neutralize and precipitate, washing, filtering and dechlorinating, calcining a filter cake to prepare precursor powder, adding a coloring agent and a binding agent, carrying out ball milling, sanding and crushing, adding a binding agent and a release agent, uniformly mixing, and then carrying out spray granulation and drying to prepare the yttrium-stabilized zirconia powder. The preparation method of the black yttrium-stabilized zirconia powder has the advantages of simple and convenient process, high yield, good stability of the produced powder, uniform particle size distribution, good fluidity, stable shrinkage rate, 1350 ℃ of sintering temperature, 100 ℃ lower than the temperature for producing zirconia ceramics generally, easy molding, high green strength, good processability, high strength, good toughness, good stability and the like.
Description
Technical Field
The invention belongs to the technical field of new inorganic materials, and particularly relates to a preparation method of black yttrium-stabilized zirconia powder.
Background
In recent years, the zirconium industry in China is rapidly developed, the capacity is the first in the world, the technical level is also ascending in advanced ranks in the world, namely zirconium oxide (ZrO)2) The catalyst is widely applied to the aspects of ceramics, electronics, jewelry, metallurgical industry, catalysts, medical treatment, automobile exhaust purification and the like. The zirconium series of products starting from zirconia are known as one of the most promising high-new materials of the 21 st century.
The preparation method of the black yttrium-stabilized zirconia powder recorded in the prior art comprises the following steps: the disadvantage of this method is that the mixing of the colorant and zirconia precursor is not uniform, which results in difficult forming, unfit green body, pinhole on the surface of the ceramic product, non-uniform color, reduced performance (mainly strength and toughness), poor stability, and limits the application of black yttrium-stabilized zirconia in precision ceramic products.
Patent CN 107628643 discloses a method for preparing a nano black yttrium-stabilized zirconia powder, comprising the following steps of: (0.8-1): (10-12), mixing, heating to 90-110 ℃, and keeping the temperature for 1-3 hours; adding vegetable gum, then adding at least one of ethylenediamine tetraacetic acid or citric acid, and stirring for 3-5h to generate a colloidal solution; adding an ammonia water solution, stirring for 8-10h until the pH value is 10.0-11.0, generating a white precipitate, and then standing and aging for 24-48 h; washing and filtering the precipitate, and then carrying out spray drying and airflow crushing to obtain precursor powder; calcining for 5-7 hours at the temperature of 450-600 ℃ to obtain the nano yttrium-stabilized zirconia powder. The method has long production period, and the ceramic product prepared by the powder has poor aging resistance.
Patent CN 108975394 discloses a yttrium-doped zirconia powder and a preparation method thereof, comprising the following steps: heating the mixed solution of zirconium acetate, yttrium acetate and trifluoroacetic acid to 42-50 ℃, and then carrying out reduced pressure distillation to obtain gel; and B: pyrolyzing the gel at 260-350 ℃ in an oxygen environment to obtain a precursor of yttrium-doped zirconia; and C: calcining the precursor of yttrium-doped zirconia in a water vapor environment. The method has the defects of difficult raw material purchase and high energy consumption in the preparation process.
Disclosure of Invention
The purpose of the invention is: provides a preparation method of black yttrium-stabilized zirconia powder. The black yttrium-stabilized zirconia powder prepared by the method has the advantages of uniform pigment distribution, good stability, suitability for dry pressing and isostatic pressing, high green strength, good machinability and low sintering temperature, and the produced ceramic product has the characteristics of high strength, good toughness, soft and uniform color, good stability and the like.
The preparation method of the black yttrium-stabilized zirconia powder comprises the following steps:
(1) mixing a zirconium oxychloride solution and a yttrium trichloride solution, and adding an organic acid solution to prepare a gel solution; adding inorganic base for neutralization, treating a neutralization product, and calcining to prepare precursor powder;
(2) and (2) adding a coloring agent and a binding agent into the precursor powder obtained in the step (1) to obtain a dry material, adding water into the dry material, grinding to obtain slurry, adding a binding agent and a release agent into the slurry, and granulating to obtain the black yttrium-stabilized zirconia powder.
Wherein:
the zirconium oxychloride solution in the step (1) is calculated by the mass of the solute zirconia, and the yttrium trichloride solution is calculated by the mass of the solute yttria, in terms of the mass of zirconia: yttrium oxide ═ 12.33: 1-25.32: 1, were mixed.
The organic acid in the step (1) is one of 2,4, 5-trimethoxybenzoic acid or citric acid solution with the mass fraction of 20%; the adding amount of the organic acid is 10 percent of the total mass of the two oxides of the zirconium oxide and the yttrium oxide by the solute.
Heating the mixture in the step (1) to 135-145 ℃, and preserving the heat for 11-13 hours to prepare the gel solution.
The inorganic base in the step (1) is one of ammonia water or sodium hydroxide solution, and preferably ammonia water.
Washing the neutralized product on a plate and frame filter, filtering for dechlorination, putting the filter cake into a sagger, and calcining at 1100-1130 ℃ for 4-6 hours to prepare precursor powder.
The colorant in the step (2) is Fe2O3、MnO2、Co3O4NiO and Cr2O3A mixture of (a).
The bonding agent in the step (2) is Al2O3。
The adhesive in the step (2) is a mixture of polyvinyl alcohol, polyethylene glycol, glycerol and polyacrylamide, wherein: the polyvinyl alcohol is a mixture of polyvinyl alcohol PVA17-99 and PVA 17-88.
The release agent in the step (2) is a mixture of water-soluble wax emulsion and sodium carboxymethyl cellulose.
The dry material is a mixture of precursor powder, a coloring agent and a binder; the chemical composition of the dry material is as follows by mass percent: y is2O33.8～7.5％、Fe2O30.6～1.4％、MnO20.4～0.9％、Al2O30.2～0.5％、Co3O41.0～1.5％、NiO 0.5～1.5％，Cr2O30.5 to 1.5%, and the balance being zirconia containing hafnium oxide. Wherein the hafnium oxide is less than 2% by mass of the hafnium oxide-containing zirconium oxide.
After adding water into the dry material in the step (2), firstly, grinding the dry material in a ball mill until D50 is 1.20-1.40 mu m, stopping grinding, putting the slurry into a sand mill, grinding the slurry until D50 is 0.30-0.80 mu m, and then adding a bonding agent and a release agent.
The black yttrium stabilized zirconia powder is a mixture of dry materials, a bonding agent and a release agent; the black yttrium-stabilized zirconia powder comprises the following raw materials in percentage by mass: polyvinyl alcohol PVA 17-990.8-1.0%, polyvinyl alcohol PVA 17-880.4-0.5%, polyethylene glycol PEG-4000.3-0.5%, glycerol 0.1-0.2%, water-soluble wax emulsion 0.2%, ammonium polyacrylate 0.1-0.2%, and sodium carboxymethylcellulose 0.2-0.4%.
And (3) stirring the slurry in the step (2) for 24 hours, uniformly mixing the slurry with the adhesive and the release agent, and then performing spray granulation and drying, wherein the inlet temperature of a spray drying tower is 230 ℃ and 250 ℃, and the outlet temperature is 130 ℃ and 140 ℃, so as to obtain the yttrium-stabilized zirconia powder with the average particle size of 70-90 μm.
The preparation method of the black yttrium-stabilized zirconia powder comprises the steps of mixing a zirconium oxychloride solution and a yttrium trichloride solution in proportion, adding an organic acid to generate gel, adding ammonia water or a sodium hydroxide solution to neutralize and precipitate, washing, filtering and dechlorinating, calcining a filter cake to prepare precursor powder, adding a coloring agent, a binding agent and the like to perform ball milling, sanding and crushing, adding an organic additive such as a binding agent, a release agent and the like to uniformly mix, and performing spray granulation and drying to prepare the yttrium-stabilized zirconia powder.
As a preferred technical scheme, the preparation method of the black yttrium-stabilized zirconia powder comprises the following steps:
(1) preparation of precursor powder
Mixing zirconium oxychloride solution and yttrium trichloride solution according to the ratio of zirconium oxide and yttrium oxide contained in the mixture of 12.33: 1-25.32: 1, adding a certain amount of organic acid solution, heating to 140 ℃ in a high-pressure reaction kettle, preserving the temperature for 12 hours to form gel solution, adding ammonia water for neutralization, washing a neutralization product on a plate and frame filter, filtering for dechlorination, filling a filter cake into a sagger, and calcining for 5 hours at 1100 ℃ to produce precursor powder.
(2) Preparation of black yttrium-stabilized zirconium powder
Adding Fe into precursor powder2O30.60～1.40％、MnO20.40～0.90％、Co3O41.00～1.50％、NiO0.50～1.50％、Cr2O30.50～1.50％、Al2O30.20-0.50%, adding pure water according to the ratio of the dry material to the pure water of 1:1, crushing the mixture in a ball mill until the D50 is about 1.30 mu m, transferring the mixture to a sand mill until the D50 is 0.30-0.80 mu m, transferring the milled slurry to a stirring tank, adding dissolved polyvinyl alcohol PVA17-99 (added according to the solid content of 0.8-1.0%), PVA17-88 (added according to the solid content of 0.4-0.5%), polyethylene glycol PEG-400 (added according to the solid content of 0.3-0.5%), glycerol(added according to the solid content of 0.1-0.2%), water-soluble wax emulsion (added according to the solid content of 0.2%), ammonium polyacrylate (added according to the solid content of 0.1-0.2%) and sodium carboxymethylcellulose (CNC added according to the solid content of 0.2-0.4%), stirring for 24 hours, uniformly mixing, and then carrying out spray granulation and drying, wherein the average particle size of the granulated particles is 70-90 mu m.
The black yttrium-stabilized zirconium powder prepared by the preparation method of the black yttrium-stabilized zirconium oxide powder has the specific surface area of 6.5-9.0 m2(ii) a bulk density of 1.15 to 1.35g/ml3And a sintered density of more than 6.02g/ml at 1350 DEG C3Flexural strength of not less than 80kg/mm2The shrinkage at 1350 ℃ is about 78 percent, and the L value is less than 3.5 in color difference measurement.
The black yttrium-stabilized zirconium powder prepared by the preparation method of the black yttrium-stabilized zirconium oxide powder is yttrium-stabilized zirconium oxide powder which can be used for manufacturing black ceramic products such as mobile phone back plates, watch cases, electronic components and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method of the black yttrium-stabilized zirconia powder has the advantages of simple and convenient process, high yield, good stability of the produced powder, uniform particle size distribution, good fluidity and stable shrinkage rate, the sintering temperature is 1350 ℃ when the ceramic product is manufactured, the sintering temperature is 100 ℃ lower than the temperature of the common zirconia ceramic product, the forming is easy, the green strength is high, the processability is good, and the black ceramic product manufactured by the powder has the characteristics of high strength, good toughness, soft and uniform color, good stability and the like.
(2) The preparation method of the black yttrium-stabilized zirconia powder solves the problems that the coloring effect of a pigment is influenced by overhigh sintering temperature, the stability is poor, the color is not uniform, the black zirconia ceramic product is easy to break and the like in the prior art.
(3) The black yttrium-stabilized zirconia powder prepared by the preparation method of the black yttrium-stabilized zirconia powder can be used for producing black ceramic products such as mobile phone back plates, watch cases, electronic components and the like in a dry pressing or isostatic pressing mode and has the characteristics of low sintering temperature, high strength, good toughness, no defect on the surface, soft, uniform color, good stability and the like.
Drawings
FIG. 1 is a flow chart of a process for preparing yttrium-stabilized zirconia powder.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The preparation method of black yttrium-stabilized zirconia powder with 2.1mol of yttrium oxide content described in this example 1 comprises the following steps:
① preparation of zirconium oxychloride octahydrate solution
Weighing zirconium oxychloride octahydrate (ZrOCl) with zirconium oxide content of 36.00%2·8H2O)2138kg, which is dissolved in 10690L pure water and uniformly stirred, wherein the zirconia concentration of the solution is 6.0 percent;
② preparation of yttrium trichloride solution
Adding 30.4kg of yttrium oxide into 98kg of hydrochloric acid solution with the concentration of 30.00%, stirring and dissolving, and adding 40L of pure water, wherein the concentration of yttrium trichloride in the solution is converted into 18.0% of yttrium oxide;
③ injecting the prepared zirconium oxychloride octahydrate solution and yttrium trichloride solution into a neutralization kettle, mixing, adding 400kg of 20.0% organic acid, heating to 140 deg.C, keeping the temperature for 12hr, cooling to room temperature, adding 2700kg of 30.0% ammonia water solution to generate hydroxide precipitate, stirring the hydroxide precipitate uniformly, injecting into a plate-and-frame filter, washing with pure water until the chloride ion content of filtrate is less than 0.005%, and press-filtering;
④ putting the filter cake into a corundum sagger, putting the corundum sagger into a kiln, and calcining for 5 hours at 1130 ℃ to produce precursor powder;
⑤ mixing 95.9kg of precursor powder and 1.2kg of Fe2O3、0.5kg MnO2、0.4kg Al2O3、1.0kg Co3O4、0.5kg NiO、0.5kg Cr2O3Adding into ball mill, adding 100L pure water, pulverizing until the median particle diameter (D50) is about 1.30 μm, stopping pulverizing, feeding into sand mill, and further grindingUntil the median particle size is about 0.5 μm, transferring to a stirring tank, adding dissolved polyvinyl alcohol PVA17-99 about 0.9kg (based on solid content, the same below), PVA17-88 about 0.5kg, polyethylene glycol PEG-400 about 0.3kg, glycerol about 0.2kg, water-soluble wax emulsion 0.2kg, ammonium polyacrylate 0.2kg, and sodium carboxymethylcellulose 0.3kg, stirring for 24 hr, mixing, spray granulating, drying, spray drying at inlet temperature 235 + -5 deg.C, outlet temperature 135 + -5 deg.C, and granulating particle size of 70 μm.
The black yttrium-stabilized zirconium powder produced by the step has the yttrium oxide content of 3.80 percent and the specific surface area of 7.6m2G, bulk density 1.28g/ml3Sintered density at 1350 ℃ of 6.04g/ml3Flexural strength of 110kg/mm2The shrinkage rate is 77.9 percent at 1350 ℃, and the color difference test L value is 2.7, so that the method is suitable for producing the black mobile phone back plate by dry pressing.
Example 2
The preparation method of black yttrium-stabilized zirconia powder with 2.6mol of yttrium oxide content in embodiment 2 comprises the following steps:
① preparation of zirconium oxychloride octahydrate solution
Weighing zirconium oxychloride octahydrate (ZrOCl) with zirconium oxide content of 36.00%2·8H2O)2118kg, dissolved in 10590m3Stirring the mixture evenly in pure water, wherein the concentration of zirconium oxide in the solution is 6.0 percent;
② preparation of yttrium trichloride solution
Adding 37.36kg of yttrium oxide into 110kg of hydrochloric acid solution with the concentration of 30.00%, stirring and dissolving, and adding 60L of pure water, wherein the concentration of yttrium trichloride in the solution is converted into 18.0% of yttrium oxide;
③ injecting the prepared zirconium oxychloride octahydrate solution and yttrium trichloride solution into a neutralization kettle, mixing, adding 400kg of 20.0% organic acid, heating to 145 ℃, keeping the temperature for 12hr, cooling to room temperature, adding 2700kg of 30.0% ammonia water solution to generate hydroxide precipitate, stirring the hydroxide precipitate uniformly, injecting into a plate-and-frame filter, washing with pure water until the content of chloride ions in filtrate is less than 0.005%, and press-filtering;
④ putting the filter cake into a corundum sagger, putting the corundum sagger into a kiln, and calcining for 5 hours at 1125 ℃ to produce precursor powder;
⑤ precursor powder 95.9kg, Fe 0.7kg2O3、0.8kgMnO2、0.3kgAl2O3、1.1kg Co3O4、0.7kgNiO、0.5kgCr2O3Adding into a ball mill, adding 100L pure water, pulverizing, grinding to median particle diameter (D50) of about 1.30 μm, stopping pulverizing, feeding into a sand mill, grinding to median particle diameter of about 0.5 μm, transferring into a stirring tank, adding dissolved polyvinyl alcohol PVA17-99 about 0.8kg (based on solid content, the same below), PVA17-88 about 0.4kg, polyethylene glycol PEG-400 about 0.3kg, glycerol about 0.1kg, water soluble wax emulsion 0.2kg, ammonium polyacrylate 0.1kg, and carboxymethylcellulose sodium 0.3kg, stirring for 24 hr, mixing, spray granulating, drying, spray drying at inlet temperature of 240 + -5 deg.C, outlet temperature of 135 + -5 deg.C, and granulating particle diameter of 70 μm.
The black yttrium-stabilized zirconium powder produced by the step has the yttrium oxide content of 4.67 percent and the specific surface area of 7.8m2G, bulk density 1.25g/ml3Sintered density at 1350 ℃ of 6.04g/ml3Flexural strength 95kg/mm2The 1350 ℃ shrinkage rate is 77.9 percent, and the color difference test L value is 2.8, so that the method is suitable for producing intelligent wearing products such as watchcases and watchbands by dry pressing.
Example 3
The preparation method of black yttrium-stabilized zirconia powder with 3.2mol of yttrium oxide content in this embodiment 3 comprises the following steps:
① preparation of zirconium oxychloride octahydrate solution
Weighing zirconium oxychloride octahydrate (ZrOCl) with zirconium oxide content of 36.00%2·8H2O)2096kg, which is dissolved in 10477L pure water and stirred uniformly, wherein the concentration of zirconia in the solution is 6.0 percent;
② preparation of yttrium trichloride solution
Adding 45.6kg of yttrium oxide into 130kg of hydrochloric acid solution with the concentration of 30.00%, stirring and dissolving, and adding 78L of pure water, wherein the concentration of yttrium trichloride in the solution is converted into 18.0% of yttrium oxide;
③ injecting the prepared zirconium oxychloride octahydrate solution and yttrium trichloride solution into a neutralization kettle, mixing, adding 400kg of 20.0% organic acid, heating to 135 deg.C, keeping the temperature for 13hr, cooling to room temperature, adding 2700kg of 30.0% ammonia water solution to generate hydroxide precipitate, stirring the hydroxide precipitate uniformly, injecting into a plate-and-frame filter, washing with pure water until the chloride ion content of filtrate is less than 0.005%, and press-filtering;
④ putting the filter cake into a corundum sagger, putting the corundum sagger into a kiln, and calcining for 6 hours at 1120 ℃ to produce precursor powder;
⑤ A mixture of 95.9kg yttrium-stabilized zirconia, 0.7kg Fe2O3、0.6kg MnO2、0.3kg Al2O3、1.3kg Co3O4、0.7kg NiO、0.5kg Cr2O3Adding into a ball mill, adding 100L pure water, pulverizing, grinding to median particle diameter (D50) of about 1.40 μm, stopping pulverizing, feeding into a sand mill, grinding to median particle diameter of about 0.6 μm, transferring into a stirring tank, adding dissolved polyvinyl alcohol PVA17-99 about 0.8kg (based on solid content, the same below), PVA17-88 about 0.4kg, polyethylene glycol PEG-400 about 0.3kg, glycerol about 0.1kg, water soluble wax emulsion 0.2kg, ammonium polyacrylate 0.1kg, and carboxymethylcellulose sodium 0.2kg, stirring for 24 hr, mixing, spray granulating, drying, spray drying at inlet temperature 235 + -5 deg.C, outlet temperature 135 + -5 deg.C, and granulating particle diameter of 75 μm.
The black yttrium-stabilized zirconium powder produced by the step has the yttrium oxide content of 5.70 percent and the specific surface area of 8.2m2(g), bulk density 1.30g/ml3Sintered density at 1350 ℃ of 6.04g/ml3Flexural strength 90kg/mm2The shrinkage rate is 77.8 percent at 1350 ℃, and the color difference test L value is 3.0, so that the method is suitable for producing black precise electronic ceramic elements.
Claims (8)
1. A preparation method of black yttrium-stabilized zirconia powder is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing a zirconium oxychloride solution and a yttrium trichloride solution, and adding an organic acid solution to prepare a gel solution; adding inorganic base for neutralization, treating a neutralization product, and calcining to prepare precursor powder;
(2) adding a coloring agent and a binding agent into the precursor powder to obtain a dry material, adding water into the dry material, grinding to obtain slurry, adding a binding agent and a release agent into the slurry, and granulating to obtain the black yttrium-stabilized zirconia powder.
2. The method of claim 1, wherein the black yttrium-stabilized zirconia powder is prepared by: the zirconium oxychloride solution in the step (1) is calculated by the mass of the solute zirconia, and the yttrium trichloride solution is calculated by the mass of the solute yttria, in terms of the mass of zirconia: yttrium oxide ═ 12.33: 1-25.32: 1, were mixed.
3. The method of claim 1, wherein the black yttrium-stabilized zirconia powder is prepared by: the organic acid in the step (1) is one of 2,4, 5-trimethoxybenzoic acid or citric acid solution with the mass fraction of 20%; the addition amount of the organic acid is 10% of the total mass of the two oxides of zirconium oxide and yttrium oxide based on the mass of the solute.
4. The method of claim 1, wherein the black yttrium-stabilized zirconia powder is prepared by: heating the mixture in the step (1) to 135-145 ℃, and preserving the heat for 11-13 hours to prepare the gel solution.
5. The method of claim 1, wherein the black yttrium-stabilized zirconia powder is prepared by: washing the neutralized product on a plate and frame filter, filtering for dechlorination, putting the filter cake into a sagger, and calcining at 1100-1130 ℃ for 4-6 hours to prepare precursor powder.
6. The method of claim 1, wherein the black yttrium-stabilized zirconia powder is prepared by: the colorant in the step (2) is Fe2O3、MnO2、Co3O4NiO and Cr2O3A mixture of (a); the bonding agent is Al2O3(ii) a Adhesive agentThe release agent is a mixture of polyvinyl alcohol, polyethylene glycol, glycerol and polyacrylamide, and the release agent is a mixture of water-soluble wax emulsion and sodium carboxymethylcellulose; wherein: the polyvinyl alcohol is a mixture of polyvinyl alcohol PVA17-99 and PVA 17-88.
7. The method of claim 1, wherein the black yttrium-stabilized zirconia powder is prepared by: the dry material is a mixture of precursor powder, a coloring agent and a binder; the chemical composition of the dry material is as follows by mass percent: y is2O33.8～7.5％、Fe2O30.6～1.4％、MnO20.4～0.9％、Al2O30.2～0.5％、Co3O41.0～1.5％、NiO 0.5～1.5％，Cr2O30.5 to 1.5%, and the balance being zirconia containing hafnium oxide.
8. The method of claim 1, wherein the black yttrium-stabilized zirconia powder is prepared by: the black yttrium stabilized zirconia powder is a mixture of dry materials, a bonding agent and a release agent; the black yttrium-stabilized zirconia powder comprises the following raw materials in percentage by mass: polyvinyl alcohol PVA 17-990.8-1.0%, polyvinyl alcohol PVA 17-880.4-0.5%, polyethylene glycol PEG-4000.3-0.5%, glycerol 0.1-0.2%, water-soluble wax emulsion 0.2%, ammonium polyacrylate 0.1-0.2%, and sodium carboxymethylcellulose 0.2-0.4%.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61266307A (en) * | 1985-05-21 | 1986-11-26 | Sumitomo Chem Co Ltd | Production of partially stabilized zirconia powder |
| US4810680A (en) * | 1986-06-26 | 1989-03-07 | Corning Glass Works | Preparation of high purity, homogeneous zirconia mixtures |
| CN101172838A (en) * | 2006-05-18 | 2008-05-07 | 东曹株式会社 | Powder for black zirconia sintered body, production method thereof, and sintered body thereof |
| CN101704671A (en) * | 2009-11-27 | 2010-05-12 | 清华大学 | Method for preparing black zirconia ceramics at low temperature |
| CN101941836A (en) * | 2010-08-30 | 2011-01-12 | 济源市更新瓷料有限公司 | Low-temperature ceramic-firing high-density alumina ceramic granulation powder and preparation method thereof |
| CN102311264A (en) * | 2010-07-06 | 2012-01-11 | 上海同济南汇科技产业园有限公司 | Environment-protection and energy-saving nanometer zirconium oxide preparation method |
| CN102674834A (en) * | 2012-05-22 | 2012-09-19 | 江西理工大学 | Preparation method of zirconium oxide structural ceramics |
| CN105669191A (en) * | 2016-04-22 | 2016-06-15 | 潮州三环（集团）股份有限公司 | Black zirconia ceramic and preparation method thereof |
| CN106431394A (en) * | 2016-08-31 | 2017-02-22 | 山东国瓷功能材料股份有限公司 | Black zirconium-oxide sintered body and preparing method and application thereof |
| CN107628643A (en) * | 2017-09-27 | 2018-01-26 | 汉中市恒宝锆业科技有限责任公司 | A kind of nanometer yttrium stable zirconium oxide raw powder's production technology |
| CN108640678A (en) * | 2018-06-22 | 2018-10-12 | 东莞信柏结构陶瓷股份有限公司 | The preparation method and product of black zirconia ceramics material and black zirconia ceramics |
| CN110330333A (en) * | 2019-07-23 | 2019-10-15 | 安徽钛谷纳米材料有限公司 | A method of preparing nanoscale yttrium stable zirconium oxide composite granule |
-
2020
- 2020-02-12 CN CN202010087607.3A patent/CN111204802B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61266307A (en) * | 1985-05-21 | 1986-11-26 | Sumitomo Chem Co Ltd | Production of partially stabilized zirconia powder |
| US4810680A (en) * | 1986-06-26 | 1989-03-07 | Corning Glass Works | Preparation of high purity, homogeneous zirconia mixtures |
| CN101172838A (en) * | 2006-05-18 | 2008-05-07 | 东曹株式会社 | Powder for black zirconia sintered body, production method thereof, and sintered body thereof |
| CN101704671A (en) * | 2009-11-27 | 2010-05-12 | 清华大学 | Method for preparing black zirconia ceramics at low temperature |
| CN102311264A (en) * | 2010-07-06 | 2012-01-11 | 上海同济南汇科技产业园有限公司 | Environment-protection and energy-saving nanometer zirconium oxide preparation method |
| CN101941836A (en) * | 2010-08-30 | 2011-01-12 | 济源市更新瓷料有限公司 | Low-temperature ceramic-firing high-density alumina ceramic granulation powder and preparation method thereof |
| CN102674834A (en) * | 2012-05-22 | 2012-09-19 | 江西理工大学 | Preparation method of zirconium oxide structural ceramics |
| CN105669191A (en) * | 2016-04-22 | 2016-06-15 | 潮州三环（集团）股份有限公司 | Black zirconia ceramic and preparation method thereof |
| CN106431394A (en) * | 2016-08-31 | 2017-02-22 | 山东国瓷功能材料股份有限公司 | Black zirconium-oxide sintered body and preparing method and application thereof |
| CN107628643A (en) * | 2017-09-27 | 2018-01-26 | 汉中市恒宝锆业科技有限责任公司 | A kind of nanometer yttrium stable zirconium oxide raw powder's production technology |
| CN108640678A (en) * | 2018-06-22 | 2018-10-12 | 东莞信柏结构陶瓷股份有限公司 | The preparation method and product of black zirconia ceramics material and black zirconia ceramics |
| CN110330333A (en) * | 2019-07-23 | 2019-10-15 | 安徽钛谷纳米材料有限公司 | A method of preparing nanoscale yttrium stable zirconium oxide composite granule |
Non-Patent Citations (1)
| Title |
|---|
| 蔺玉胜,朱海涛: "用不同表面活性剂制备纳米ZrO_2粉体的TEM分析" * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825467A (en) * | 2020-07-21 | 2020-10-27 | 宁德三祥纳米新材料有限公司 | Method for preparing nano zirconia by using spray granulator |
| CN112500159A (en) * | 2020-12-28 | 2021-03-16 | 长裕控股集团有限公司 | Preparation method of high-toughness high-strength black zirconia ceramic material |
| CN112661504A (en) * | 2020-12-28 | 2021-04-16 | 长裕控股集团有限公司 | Preparation method of zirconia dental material |
| CN112679209A (en) * | 2020-12-28 | 2021-04-20 | 长裕控股集团有限公司 | Preparation method of black zirconia ceramic material |
| CN112679209B (en) * | 2020-12-28 | 2023-04-14 | 长裕控股集团股份有限公司 | Preparation method of black zirconia ceramic material |
| CN112661506A (en) * | 2021-01-21 | 2021-04-16 | 马鞍山云启金锐新材料有限公司 | Black zirconia powder for ceramic mobile phone shell and preparation method thereof |
| CN113480287A (en) * | 2021-06-24 | 2021-10-08 | 湖北三江航天红阳机电有限公司 | Preparation method of yttrium-stabilized zirconium dioxide aerogel/fiber composite material |
| WO2023041672A1 (en) * | 2021-09-17 | 2023-03-23 | Framatome | Method for producing a granulated metal oxide powder, and corresponding granulated metal oxide powder |
| FR3127212A1 (en) * | 2021-09-17 | 2023-03-24 | Framatome | Process for producing granulated metal oxide powder and corresponding granulated metal oxide powder |
| CN114408968A (en) * | 2022-01-25 | 2022-04-29 | 山东理工大学 | Rare earth stabilized zirconia nano powder and preparation method thereof |
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