CN101891471B - Method for preparing zirconium oxide nanopowder stabilized by yttrium oxide - Google Patents
Method for preparing zirconium oxide nanopowder stabilized by yttrium oxide Download PDFInfo
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Abstract
The invention relates to a method for preparing zirconium oxide nanopowder stabilized by yttrium oxide. The method comprises the following steps of: preparing mother salt solution from aqueous solution of inorganic salts of zirconium ions (Zr) and yttrium ions (Y) serving as a raw material; adding a proper amount of composite organic additive into the mother salt solution and stirring the mixture; placing the uniformly mixed solution into a reaction kettle with a previously designed structure; heating the solution under normal pressure by using a microwave as a heat source and boiling the liquor for a period of time; hydrothermally heating the solution for a period of time at a low temperature (the temperature is less than or equal to 100 DEG C by taking the normal pressure boiling of water as a metering end point) under the normal pressure by a conventional heating method; and after the PH value of the liquor reaches a range from 6.5 to 7.5, washing, filter-pressing, drying and calcining the obtained colloid to finally obtain the zirconium oxide nanopowder stabilized by the yttrium oxide. The method has the advantages of safety, high powder performance, short hydrothermal time, low cost, simple process and repeated and stable product quality.
Description
Technical field
The invention belongs to field of fine chemical, relate to a kind of preparation method through the yttria stabilized zirconia nano-powder.
Background technology:
Microwave (Microwave, MW) refers to wavelength from 1mm-1m, the hertzian wave of frequency between the 300MHz-300GHz scope.Microwave radiation can selectively activate some group, promotes chemical reaction.Since Oxonian Baghurst in 1888 etc. in reported first on the Nature magazine carry out mineral compound and superconducting material synthetic with microwave method after, also have successively with microwave technology synthesis zeolite, inorganic materials etc. and to report.Microwave just steps into chemical industry, novel material and other high-tech areas with the faster speed of expecting than people as a kind of energy.
Zirconium white is a kind of have high-melting-point, high boiling point, thermal conductivity is little, thermal expansivity is large, wear resistance is good, corrosion resistance is good ceramic, therefore can be used for refractory materials and structural ceramics, connect plug-in unit etc. such as mechanical part, measurer, cutter, never wornout watchcase member, bearing, medium of grinder, ceramic engine parts, wortle, high-temperature structural ceramics, optical fiber; In addition, zirconia ceramics has excellent ionic conductance when high temperature, thereby has high responsive unit for electrical property parameters, so zirconia ceramics also can be used for function ceramics, such as the chief component of oxygen sensor, oxygen detection instrument, Solid Oxide Fuel Cell (SOFC), cleaning catalyst for tail gases of automobiles, high temperature heating element etc.At present, the application of zirconia ceramics is more and more extensive, and industrial scale constantly enlarges.Make high performance zirconia ceramics, at first will make the Zirconium powder of excellent property.The powder of excellent property requires fine size and narrow distribution range, has good sinterability, can reach higher density etc. under lower temperature.
The method that prior art prepares nano zirconium oxide powder is a lot, common are coprecipitation method, alkoxide hydrolysis, hydrothermal method, sol-gel method, emulsion method, micro emulsion method etc., and these methods respectively have characteristics, but also exists a lot of not enough.There is considerable hard aggregation in the powder that makes such as coprecipitation method; Alkoxide hydrolysis raw material sources difficulty, price is higher; The hydrothermal method condition is harsh, cost is higher, the domestic suitability for industrialized production etc. that do not form so far.
Up to the present, the oxide powder of the synthetic preparation of microwave hydrothermal mainly contains cupric oxide, titanium oxide and zinc oxide nano-powder etc., but has no patent report with the document of the synthetic preparation of microwave hydrothermal nm-class powder of zirconium oxide.
Summary of the invention:
The object of the present invention is to provide a kind of industrialized production that is easy to, prepared powder characteristic good through yttria stabilized zirconia (Yttria Stabilized Zirconia, YSZ) preparation method of nano-powder has safety, powder characteristic is good and the hydro-thermal time is short, lower-cost characteristics.
The object of the present invention is achieved like this, take the inorganic salt solution of zirconium ion (Zr) and ruthenium ion (Y) as raw material makes female salts solution, add afterwards the compound organic additive of appropriate amount in this female salts solution and stir, then the above-mentioned solution that mixes is placed the reactor that designs in advance structure, also protect take microwave as the thermal source normal heating first and boil feed liquid for some time, and then with traditional heating mode (≤100 ℃ of lower temperature, take the atmospheric boiling of water as the metering terminal point) lower constant pressure hydro-thermal for some time, after the pH value of feed liquid reaches the scope of 6.5-7.5, again resulting colloid washing, press filtration, the oven dry calcining finally can obtain through the yttria stabilized zirconia nano-powder.
Its concrete preparation process is preferably as follows:
(1), in reactor, preparation zirconium ion concentration is the precursor body mother salt zirconyl chloride solution of (1.5-2.5) mol/L, add yttrium oxide according to the proportioning that accounts for zirconium ion total amount 3mol%, heating and stirring make the yttrium oxide dissolving, then this feed liquid are diluted to reaction density (0.3-0.8) mol/L;
(2), afterwards add the compound organic additive with respect to the 0-5% of zirconium white quality, and stir;
(3), at last this solution that stirs is protected take microwave as the thermal source normal heating first and boiled, microwave heating temperature is set to 100 ℃, and guarantor's time of boiling is 3-30min;
(4) protect and then with the traditional heating mode normal heating and to boil, its temperature control is take the atmospheric boiling of water as the metering terminal point, and it is 30-40h that hydro-thermal is protected the time of boiling, and stops the pH value and is controlled at 6.5-7.5;
(5) until zirconium ion and ruthenium ion precipitate fully, final prepared colloid namely gets through the yttria stabilized zirconia powder through washing, press filtration, oven dry calcining;
(6), the oven dry of filter cake and calcining are finished in the same operation of carrying out continuously; Calcining temperature is at 450-800 ℃, and the time is 2-5h; The primary particle size size of final prepared zirconia superfine powder is 5-10nm, aggregated particle size D
50＜0.20 μ m;
(7), described powder is dry-pressing formed under the pressure of 8MPa, then burn till through 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃ insulation 3h normal pressures respectively; Detect the density of sintered compact through Archimedes's method: the relative density when normal pressure burns till under 1250 ℃-3h condition is 97%, and normal pressure-sintered relative density can reach more than 99.5% under 1300 ℃-3h condition.
Used compound organic additive comprises polyvinyl alcohol, polyoxyethylene glycol, polyacrylic acid and TS series flocculants.
More than be the research of the present inventors' process, finally selected with ZrOCl
2(YCl
3) as precursor body mother salt, and found out suitable strength of solution, and worked out suitable compound organic additive and their add-on, designed the rational reactor of structure, find out rational heating curve, finally drawn the production method with the object of the invention.
The present invention has safety, powder characteristic is good and the hydro-thermal time short, lower-cost advantage, and the method technique is simple, quality product repeats to stablize.Specifically be:
1, avoided the harsh working condition of High Temperature High Pressure, production technique is simple, safety, cost are lower, and not high to equipment requirements, is easy to realize industrialized production.
2, more conventional hydro-thermal time shorten of hydro-thermal time more than 60%, saved production cost, reduced the discharging of waste gas, be a kind of environmentally friendly production method.
3, have with the YSZ powder of the method preparation that particle diameter is little, size-grade distribution concentrates and good dispersity, reunion less, characteristics that sintering activity is high.
Embodiment:
Further specify embodiment with following indefiniteness embodiment.
Embodiment 1:
(1), in reactor, preparation zirconium ion concentration is the precursor body mother salt zirconyl chloride solution of 2mol/L, add yttrium oxide according to the proportioning that accounts for zirconium ion total amount 3mol%, heating and stirring make the yttrium oxide dissolving, then this feed liquid are diluted to reaction density 0.5mol/L;
(2), afterwards add 3% compound organic additive with respect to the zirconium white quality, and stir;
(3), at last this solution that stirs is protected take microwave as the thermal source normal heating first and boiled, microwave heating temperature is set to 100 ℃, and protecting the set of time that boils is 5min;
(4) protect and then with the traditional heating mode normal heating and to boil, its temperature control is take the atmospheric boiling of water as the metering terminal point, and it is 32h that hydro-thermal is protected the time of boiling, and stops the pH value and is controlled at 6.5-7.5;
(5) until zirconium ion and ruthenium ion precipitate fully, final prepared colloid namely gets through the yttria stabilized zirconia powder through washing, press filtration, oven dry calcining;
(6), the oven dry of filter cake and calcining are finished in the same operation of carrying out continuously; Calcining temperature is 700 ℃, and the time is 5h; The primary particle size size of prepared zirconia superfine powder is 5-10nm, aggregated particle size D
50＜0.20 μ m;
(7), described powder is dry-pressing formed under the pressure of 8MPa, then burn till through 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃ insulation 3h normal pressures respectively; Detect the density of sintered compact through Archimedes's method: the relative density when normal pressure burns till under 1250 ℃-3h condition is 97%, and normal pressure-sintered relative density can reach more than 99.5% under 1300 ℃-3h condition.
Used compound organic additive comprises polyvinyl alcohol and TS series flocculants.
Embodiment 2:
(1), in reactor, preparation zirconium ion concentration is the precursor body mother salt zirconyl chloride solution of 1.5mol/L, add yttrium oxide according to the proportioning that accounts for zirconium ion total amount 3mol%, heating and stirring make the yttrium oxide dissolving, then this feed liquid are diluted to reaction density 0.3mol/L;
(2), afterwards add 2% compound organic additive with respect to the zirconium white quality, and stir;
(3), at last this solution that stirs is protected take microwave as the thermal source normal heating first and boiled, microwave heating temperature is set to 100 ℃, and protecting the set of time that boils is 10min;
(4) protect and then with the traditional heating mode normal heating and to boil, its temperature control is take the atmospheric boiling of water as the metering terminal point, and it is 35h that hydro-thermal is protected the time of boiling, and stops the pH value and is controlled at 6.5-7.5;
(5) until zirconium ion and ruthenium ion precipitate fully, final prepared colloid namely gets through the yttria stabilized zirconia powder through washing, press filtration, oven dry calcining;
(6), the oven dry of filter cake and calcining are finished in the same operation of carrying out continuously; Calcining temperature is 600 ℃, and the time is 4h; The primary particle size size of prepared zirconia superfine powder is 5-10nm, aggregated particle size D
50＜0.20 μ m;
(7), described powder is dry-pressing formed under the pressure of 8MPa, then burn till through 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃ insulation 3h normal pressures respectively; Detect the density of sintered compact through Archimedes's method: the relative density when normal pressure burns till under 1250 ℃-3h condition is 97%, and normal pressure-sintered relative density can reach more than 99.5% under 1300 ℃-3h condition.
Used compound organic additive comprises polyoxyethylene glycol and TS series flocculants.
Embodiment 3:
(1), in reactor, preparation zirconium ion concentration is the precursor body mother salt zirconyl chloride solution of 2.5mol/L, add yttrium oxide according to the proportioning that accounts for zirconium ion total amount 3mol%, heating and stirring make the yttrium oxide dissolving, then this feed liquid are diluted to reaction density 0.8mol/L;
(2), afterwards add 5% compound organic additive with respect to the zirconium white quality, and stir;
(3), at last this solution that stirs is protected take microwave as the thermal source normal heating first and boiled, its Heating temperature is set to 100 ℃, and protecting the set of time that boils is 25min;
(4) protect and then with the traditional heating mode normal heating and to boil, its temperature control is take the atmospheric boiling of water as the metering terminal point, and it is 38h that hydro-thermal is protected the time of boiling, and stops the pH value and is controlled at 6.5-7.5;
(5) until zirconium ion and ruthenium ion precipitate fully, final prepared colloid namely gets through the yttria stabilized zirconia powder through washing, press filtration, oven dry calcining;
(6), the oven dry of filter cake and calcining are finished in the same operation of carrying out continuously; Calcining temperature is 500 ℃, and the time is 3h; The primary particle size size of prepared zirconia superfine powder is 5-10nm, aggregated particle size D
50＜0.20 μ m;
(7), described powder is dry-pressing formed under the pressure of 8MPa, then burn till through 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃ insulation 3h normal pressures respectively; Detect the density of sintered compact through Archimedes's method: the relative density when normal pressure burns till under 1250 ℃-3h condition is 97%, and normal pressure-sintered relative density can reach more than 99.5% under 1300 ℃-3h condition.
Used compound organic additive comprises polyacrylic acid and TS series flocculants.
Claims (1)
1. the preparation method through the yttria stabilized zirconia nano-powder is characterized in that,
Concrete steps are as follows:
(1) in reactor, preparation zirconium ion concentration is the precursor body mother salt zirconyl chloride solution of (1.5-2.5) mol/L, add yttrium oxide according to the proportioning that accounts for zirconium ion total amount 3mol%, heating and stirring make the yttrium oxide dissolving, then this feed liquid are diluted to reaction density (0.3-0.8) mol/L;
(2) add afterwards with respect to the zirconium white quality greater than 0 less than or equal to 5% compound organic additive, and stir;
(3) at last first the guarantor take microwave as the thermal source normal heating of this solution that stirs boiled, microwave heating temperature is set to 100 ℃, and guarantor's time of boiling is 3-30min;
(4) protect and then with the traditional heating mode normal heating and to boil, its temperature control is take the atmospheric boiling of water as the metering terminal point, and it is 30-40h that hydro-thermal is protected the time of boiling, and stops the pH value and is controlled at 6.5-7.5;
(5) until zirconium ion and ruthenium ion precipitate fully, final prepared colloid namely gets through the yttria stabilized zirconia powder through washing, press filtration, oven dry calcining;
(6) oven dry of filter cake and calcining are finished in the same operation of carrying out continuously; Calcining temperature is at 450-800 ℃, and the time is 2-5h; The primary particle size size of final prepared zirconia superfine powder is 5-10nm, aggregated particle size D
50＜0.20 μ m;
Described compound organic additive comprises polyvinyl alcohol, polyoxyethylene glycol, polyacrylic acid and TS series flocculants.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106116569A (en) * | 2016-06-28 | 2016-11-16 | 郭舒洋 | A kind of preparation method of green antistatic zirconia ceramics |
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| CN102311265B (en) * | 2011-08-10 | 2013-03-06 | 东华大学 | Preparation method for monodisperse cubic phase yttrium-stabilized zirconium dioxide nanometer powder |
| CN107540017A (en) * | 2016-06-25 | 2018-01-05 | 张尚权 | A kind of preparation method of nanometer of doped yttrium zirconia powder |
| CN106396676A (en) * | 2016-08-31 | 2017-02-15 | 山东国瓷功能材料股份有限公司 | Light transmittance zirconium oxide sintered body, preparation method and application thereof |
| CN106431395A (en) * | 2016-08-31 | 2017-02-22 | 山东国瓷功能材料股份有限公司 | High-light transmittance zirconia sintered body, and preparation method and application thereof |
| CN107473737B (en) * | 2017-08-09 | 2020-12-15 | 三祥新材股份有限公司 | Composite zirconia powder for solid oxide fuel cell and preparation method thereof |
| CN108147814B (en) * | 2018-01-25 | 2021-01-08 | 山东国瓷功能材料股份有限公司 | Method for sintering zirconia ceramic at low temperature |
| CN112661504B (en) * | 2020-12-28 | 2023-01-31 | 长裕控股集团股份有限公司 | Preparation method of zirconia dental material |
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| CN101613123A (en) * | 2009-08-05 | 2009-12-30 | 邢长生 | The hydrothermal synthesis method of IVB family metal oxide |
| CN101708829A (en) * | 2009-11-24 | 2010-05-19 | 华东理工大学 | Method for preparing yttria-stabilized zirconia powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1636932A (en) * | 2004-12-03 | 2005-07-13 | 中国科学院新疆理化技术研究所 | Microwave hydrothermal synthesis process of nanometer yttrium oxide stabilized zirconium oxide material |
| CN101613123A (en) * | 2009-08-05 | 2009-12-30 | 邢长生 | The hydrothermal synthesis method of IVB family metal oxide |
| CN101708829A (en) * | 2009-11-24 | 2010-05-19 | 华东理工大学 | Method for preparing yttria-stabilized zirconia powder |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106116569A (en) * | 2016-06-28 | 2016-11-16 | 郭舒洋 | A kind of preparation method of green antistatic zirconia ceramics |
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Application publication date: 20101124 Assignee: JIANGXI SAICI MATERIALS CO., LTD. Assignor: JIANGXI FARMEIYA MATERIALS CO., LTD. Contract record no.: 2014360000088 Denomination of invention: Method for preparing zirconium oxide nanopowder stabilized by yttrium oxide Granted publication date: 20130313 License type: Exclusive License Record date: 20140603 |
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