CN100336730C - Preparation process for superfine powder of zirconium oxide - Google Patents
Preparation process for superfine powder of zirconium oxide Download PDFInfo
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- CN100336730C CN100336730C CNB2004100135575A CN200410013557A CN100336730C CN 100336730 C CN100336730 C CN 100336730C CN B2004100135575 A CNB2004100135575 A CN B2004100135575A CN 200410013557 A CN200410013557 A CN 200410013557A CN 100336730 C CN100336730 C CN 100336730C
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Abstract
The present invention relates to a preparation method for superfine zirconia (ZrO2) powder. Zirconia is an inorganic non-metal material having the advantages of high temperature resistance, abrasion resistance and corrosion resistance. Superfine zirconia powder with proper grain diameters is important chemical raw material for preparing high performance fine ceramics, such as electronic ceramics, functional ceramics, structural ceramics, etc. The application of the superfine zirconia powder is wide in the technical fields of aviation, spaceflight, machinery, chemical industry, electrons, automobiles, power sources, etc. The present invention adopts zirconium oxychloride and ammonium carbonate as precursor raw materials, utilizes a uniform coprecipitation method to prepare wet zirconia gel to obtain superfine zirconia powder through drying at a temperature of 100 to 150 DEG C and under the condition of 0.3 to 1.0MPa and through calcination at a temperature of 700 to 1000 DEG C. By utilizing the method provided by the present invention, superfine zirconia powder with the grain diameter of 0.1 to 0.5 mu m, the specific surface areas of 15 to 30m<2>/g and narrow grain size distribution range can be obtained. The superfine zirconia powder is suitable for chemical raw materials of fine ceramics.
Description
Technical field
The present invention relates to a kind of zirconium white (ZrO
2) preparation method of superfine powder.Zirconium white is a kind of high temperature resistant, wear-resistant, corrosion resistant ceramic, the suitable zirconia superfine powder of particle diameter is a preparation high-performance fine ceramics, as the important industrial chemicals of electronic ceramics, function ceramics and structural ceramics etc., more and more widely application is arranged in technical fields such as Aeronautics and Astronautics, machinery, chemical industry, electronics, automobile, the energy.
Background technology
Preparation zirconium white (ZrO
2) method of superfine powder is a lot, as sol-gel processing, rare gas element sedimentation, chemical Vapor deposition process, hydrothermal method, plasma method, induced with laser method etc.Sol-gel processing comprises chemical coprecipitation again, adds the moisture solution, alkoxide decomposition method etc.Wherein chemical coprecipitation is by the synthetic powder of liquid phase reaction.This method can accurately be controlled each components contents, and production process is simple relatively, is the method that generally adopts at present.
Prepare zirconium white (ZrO with chemical coprecipitation
2) process of superfine powder can be divided into three phases: precipitation (one-tenth glue), dry and calcining.Wherein can select different forerunner's raw materials for use in precipitation (one-tenth glue) stage; Drying stage can adopt high pressure water thermal treatment, lyophilize, spraying drying, normal pressure or methods (annotate: critical pressure value is 63amt, and critical temperature value is 243 ℃) such as decompression vaporizing and drying, supercritical fluid drying and non-supercritical fluid drying; And can choose different temperature at calcination stage.Adopt different technology and conditions will directly influence zirconium white (ZrO in the different stages
2) physical behavior of superfine powder.
King and Yi etc. select zirconium oxychloride and hexamethylenetetramine for use in " silicate circular " the 4th phase in 1999 " precipitation-emulsion process prepares the research of zirconium dioxide nanometer powder trifling skill art " literary composition be forerunner's raw material, through precipitation, filter, washing, 150 ℃ of dryings of normal pressure, 550 ℃ of processing condition such as thermal treatment obtain the zirconium dioxide nanometer powder end.The last particle diameter of the zirconium dioxide nanometer powder that adopts this method to prepare is less than 40 nanometers (nm).The shortcoming of this method is to use expensive hexamethylenetetramine and organic emulsifier, need in the preparation process to use high-shear emulsifying equipment, and thermal treatment temp is low, is difficult to guarantee can also obtain less particle under comparatively high temps.
" co-precipitation-supercritical fluid drying is synthesized CaO-ZrO to Liang Li duckweeds etc. in " silicate circular " the 3rd phase in 1998
2Composite oxides ultrafine powder and sintering character research thereof " be forerunner's raw material in the literary composition with Zircosol ZN and nitrocalcite, adopt co-precipitation, supercritical fluid drying, and the method for heat-treating is prepared CaO-ZrO under differing temps
2Ultrafine powder.The result shows, the ultra micro powder uniform particles of this method preparation, and particle is approximate spherical in shape, and is coupled to each other into spatial network shape structure between the particle, has kept the constitutional features of wet gel preferably.
The Chinese invention patent of applications such as Xu Baiqing " preparation method of zirconium dioxide " (publication number CN1260324A) has been reported to contain the commodity zirconium oxychloride (ZrOCl of crystal water
28H
2O) and commodity ammoniacal liquor obtain Zr (OH) for forerunner's raw material
4The water-sol, and behind absolute ethanol washing, obtain alcogel; With this alcogel or dry in normal pressure, 110～350 ℃, air atmosphere, or at normal pressure, 110～350 ℃, N
2Dry in the atmosphere, or place the autoclave supercritical drying; Its calcining temperature is 400～700 ℃.
The shortcoming of above-mentioned back two kinds of methods is required super critical conditions to the having relatively high expectations of equipment, and processing condition are harsh, and energy consumption is big, realizes that industrialization has certain difficulty; And because of the Zirconium oxide powder particle diameter that obtains is little, specific surface area is big, and benefit is not suitable for making fine ceramics as the catalyzer of various chemical reactions or support of the catalyst.
Summary of the invention
The invention provides a kind of zirconium white (ZrO
2) preparation method of superfine powder, adopting basic zirconium chloride and volatile salt is forerunner's raw material, at first synthesize zirconium carbonate ammonium solution, and then obtain the zirconium hydroxide alcogel by even coprecipitation method, and under lower temperature and pressure vaporizing and drying, 700～1000 ℃ of following calcination.
Specific operation process is as follows: purity is soluble in water greater than 99.5% basic zirconium chloride, employed water can be distilled water, it also can be deionized water, be made into the zirconium oxychloride solution that volumetric molar concentration is 0.05～5.0mol/L, other prepares volumetric molar concentration is 1～5mol/L sal volatile, this solution is under agitation joined in the zirconium oxychloride aqueous solution that oneself prepares, make zirconium carbonate ammonium solution; Under agitation adding massfraction then is 5%～25% alkaline substance solution, and alkaline matter can be ammoniacal liquor, sodium hydroxide or potassium hydroxide, and the pH value of control solution is 8～9, obtain white precipitate, filter, being washed with water to solution does not have chlorion, obtains filter cake after washing, the filtration; Filter cake is joined in the dehydrated alcohol, and the mass ratio of dehydrated alcohol and filter cake is 2～10: 1, is stirred to uniform state, filter, use soaked in absolute ethyl alcohol, the dehydrated alcohol that uses in the immersion process and the mass ratio of basic zirconium chloride are 2～5: 1, and stirring to make becomes emulsion;
Put into pressure reaction still, be heated to 100～150 ℃, pressure-controlling is between 0.3～1.0MPa, keep certain hour, when pressure is reduced to below the 0.3MPa fast the alcohol vapour emptying, with the residual ethanol of gas purging, employed gas can be air, nitrogen, obtains the loose white powder of reuniting that do not have at last.
Above-mentioned powder is placed in the High Temperature Furnaces Heating Apparatus 700～1000 ℃ of following calcination 1～8 hour, is cooled to room temperature, promptly obtain not having the white zirconia superfine powder of reunion.
Zirconia superfine powder even particle size distribution, the particle size range that adopts method provided by the invention to obtain is narrow, particle diameter is less, is fit to the preparation fine ceramics; Present method is lower to the requirement condition of equipment, and processing condition relax, and are easy to realize industrialization.
Embodiment
Provide preferred implementation method of the present invention below.
Taking by weighing 240g basic zirconium chloride (purity 99.5%) is dissolved in the 240ml water, be made into the 2.15mol/L zirconium oxychloride aqueous solution, other gets 1440ml distilled water, add the 588g volatile salt and make sal volatile, this solution is under agitation joined in the zirconium oxychloride aqueous solution that oneself prepares, make zirconium carbonate ammonium solution, under agitation add about 1200ml ammoniacal liquor, pH value to solution is 8～9, obtains white precipitate, filters, there is not chlorion with deionized water wash to solution, washing, filtration obtains filter cake, and filter cake is joined in the 1500ml dehydrated alcohol, is stirred to uniform state, filter, use the 600ml soaked in absolute ethyl alcohol again, stirring to make becomes emulsion, puts into pressure reaction still and adopts the non-supercritical desiccating method, slowly be heated to 130～140 ℃, pressure-controlling reduces pressure after keeping certain hour between 0.3～1.0MPa, when pressure is reduced to 0.3MPa when following, fast the alcohol vapour emptying, and, stop heating, the white powder that obtains loosening with the ethanol of nitrogen purging remnants; This powder 800 ℃ of following roastings 2 hours, is promptly obtained the zirconium oxide micro powder of 89.2g white hard aggregation-free.Weight yield 97.2%, median size 0.21 μ m, particle diameter are that the particle between 0.1～0.5 μ m accounts for 98%, specific surface area 23m
2/ g.
Control experiment 1: other conditions are constant, and the zirconium white alcogel that obtains is adopted decompression vaporizing and drying method, and pressure-controlling is at 0.095MPa, and 70～80 ℃ of temperature, obtain the Zirconium oxide powder that 88.6g white has hard aggregation at 24 hours time of drying after calcining.Weight yield 96.3%, median size 0.46 μ m, particle diameter are that the particle between 0.1～0.5 μ m accounts for 62%, and particle diameter is that the particle between 0.1～1.0 μ m accounts for 98%, specific surface area 8.6m
2/ g.
Control experiment 2: other conditions are constant, with the zirconium white alcogel 600ml soaked in absolute ethyl alcohol that obtains, stirring to make becomes emulsion, puts into pressure reaction still and adopts supercritical drying, logical nitrogen to still internal pressure is 8.0MPa, slowly be heated to 260 ℃, kept pressure release 4 hours, ethanol with nitrogen purging remnants, stop heating, the white powder that obtains loosening obtains the Zirconium oxide powder of 89.0g white hard aggregation-free after calcining.Weight yield 97.0%, median size 0.076 μ m, particle diameter are that the particle between 0.05～0.10 μ m accounts for 92.0%, specific surface area 42.3m
2/ g.
By the comparison test as can be seen: the diameter of particle that adopts decompression vaporizing and drying method to obtain is too big, and specific surface area is too little, and the grit of reunion is arranged; Adopt the zirconium oxide micro powder particle diameter of supercritical drying preparation too little, specific surface area is too big; And adopt the inventive method is that the Zirconia particles particle diameter of non-supercritical desiccating method preparation is moderate, and particle size distribution range is narrow and even, is suitable for the use of fine ceramics material.
Claims (4)
1. the preparation method of a zirconia superfine powder, it is characterized in that purity soluble in water greater than 99.5% basic zirconium chloride, be made into the zirconium oxychloride solution that volumetric molar concentration is 0.05～5.0mol/L, other prepares volumetric molar concentration is 1～5mol/L ammonium carbonate solution, this solution is joined in the zirconium oxychloride aqueous solution that has prepared under agitation condition, make zirconium carbonate ammonium solution; Adding massfraction then under agitation condition is 5%～25% alkaline substance solution, to the pH value of solution be 8～9, obtain white precipitate, filtration; Be washed with water in the solution not chloride ion-containing, filter and the filter cake that obtains is joined in the dehydrated alcohol, the mass ratio of dehydrated alcohol and filter cake is 2～10: 1, be stirred to uniform state, filter, use soaked in absolute ethyl alcohol again, the dehydrated alcohol that uses in the immersion process and the mass ratio of basic zirconium chloride are 2～5: 1, and stirring to make becomes emulsion; Put into pressure reaction still, be heated to 100～150 ℃, pressure-controlling is kept certain hour at 0.3～1.0MPa, when pressure is reduced to below the 0.3MPa fast the alcohol vapour emptying, with the residual ethanol of gas purging, obtains the loose white powder of reuniting that do not have; This powder is finally obtained zirconia superfine powder 700～1000 ℃ of following calcinings.
2. the preparation method of zirconia superfine powder as claimed in claim 1 is characterized in that the massfraction that adds is that alkaline matter in 5%～25% the alkaline substance solution is ammoniacal liquor, sodium hydroxide or potassium hydroxide.
3. the preparation method of zirconia superfine powder as claimed in claim 1 is characterized in that the water in the described preparation process is distilled water or deionized water.
4. the preparation method of zirconia superfine powder as claimed in claim 1, the gas that it is characterized in that being used to purging residual ethanol is air or nitrogen.
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| CNB2004100135575A CN100336730C (en) | 2004-02-17 | 2004-02-17 | Preparation process for superfine powder of zirconium oxide |
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| CN100336730C true CN100336730C (en) | 2007-09-12 |
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313417C (en) * | 2005-03-24 | 2007-05-02 | 上海大学 | Prepn process of spherical nanometer crystal zirconium dioxide powder for structural ceramic |
| CN100460335C (en) * | 2006-05-19 | 2009-02-11 | 中国科学院过程工程研究所 | Production of spherical zirconia powder by molecular thin-layer ammoni-ation |
| CN100478280C (en) * | 2006-05-19 | 2009-04-15 | 中国科学院过程工程研究所 | Method and apparatus for producing spherical zirconia powder continuously |
| CN101913650B (en) * | 2010-08-16 | 2011-10-26 | 河北工业大学 | Method for preparing ordered laminar nano/mesoporous structural zirconia polycrystalline powder |
| CN102826601A (en) * | 2011-06-15 | 2012-12-19 | 淄博市周村磊宝耐火材料有限公司 | Method for preparing high-purity zirconium oxide through purifying silicon removed zirconium |
| CN103803633B (en) * | 2012-11-14 | 2015-06-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of zinc oxide/titanium dioxide nanometer composite material |
| CN103058277B (en) * | 2013-02-05 | 2014-10-15 | 山东国瓷功能材料股份有限公司 | Supercritical hydrothermal synthesis method of nanometer zirconium oxide powder |
| CN103585026A (en) * | 2013-11-19 | 2014-02-19 | 南昌航空大学 | Submicron zirconium oxide base dental material |
| CN103771513B (en) * | 2014-01-25 | 2016-02-17 | 东莞市地大纳米材料有限公司 | A kind of high dispersion nanometer oxide zirconium raw powder's production technology |
| CN107445202B (en) * | 2017-08-30 | 2019-08-06 | 华能国际电力股份有限公司 | Preparation method of small-size ultra-dispersed nano zirconia-based coating powder |
| CN111517802B (en) * | 2020-04-28 | 2022-07-26 | 山东国瓷功能材料股份有限公司 | Aluminum nitride ceramic powder, preparation method thereof and packaging substrate |
| CN112374903A (en) * | 2020-12-21 | 2021-02-19 | 山东蓝合智能科技有限公司 | Preparation method for zirconia ceramic 3D printing material |
| CN112871148A (en) * | 2021-01-20 | 2021-06-01 | 陕西瑞科新材料股份有限公司 | Preparation method of zirconium dioxide carrier for noble metal catalyst |
| CN116262662A (en) * | 2021-12-14 | 2023-06-16 | 东莞市陶陶新材料科技有限公司 | Submicron spherical zirconia powder and preparation method thereof, and zirconia ceramic |
| CN114751451B (en) * | 2022-05-19 | 2024-01-30 | 美轲(广州)新材料股份有限公司 | Preparation method of nano zirconia |
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| CN1260324A (en) * | 2000-01-25 | 2000-07-19 | 清华大学 | Preparation method for zirconium dioxide |
| CN1267568A (en) * | 2000-03-31 | 2000-09-27 | 清华大学 | Preparation of superfine zirconia with large specific surface area |
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| CN1260324A (en) * | 2000-01-25 | 2000-07-19 | 清华大学 | Preparation method for zirconium dioxide |
| CN1267568A (en) * | 2000-03-31 | 2000-09-27 | 清华大学 | Preparation of superfine zirconia with large specific surface area |
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