CN102311265B - Preparation method for monodisperse cubic phase yttrium-stabilized zirconium dioxide nanometer powder - Google Patents
Preparation method for monodisperse cubic phase yttrium-stabilized zirconium dioxide nanometer powder Download PDFInfo
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- CN102311265B CN102311265B CN 201110228168 CN201110228168A CN102311265B CN 102311265 B CN102311265 B CN 102311265B CN 201110228168 CN201110228168 CN 201110228168 CN 201110228168 A CN201110228168 A CN 201110228168A CN 102311265 B CN102311265 B CN 102311265B
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Abstract
The invention relates to a preparation method for monodisperse cubic phase yttrium-stabilized zirconium dioxide nanometer powder. The method comprises the following steps: (1) dissolving zirconium alkoxide and yttrium salt in anhydrous lower alcohol to prepare an anhydrous lower alcohol solution of zirconium alkoxide and yttrium salt; (2) placing the anhydrous lower alcohol solution of zirconium alkoxide and yttrium salt in an enclosed container which is filled with distilled water in advance, enabling the distilled water not to directly contact with the anhydrous lower alcohol solution of zirconium alkoxide and yttrium salt, carrying out heat treatment, cooling an obtained product to room temperature, and carrying out washing and drying to obtain the monodisperse cubic phase yttrium-stabilized zirconium dioxide nanometer powder. The preparation method provided in the invention has the advantages of simple operation, low cost and low requirements for equipment; the monodisperse cubic phase yttrium-stabilized zirconium dioxide nanometer powder prepared in the invention has the characteristics of a small particle size, narrow distribution, good dispersibility, etc.
Description
Technical field
The invention belongs to the preparation field of Ions in nanocrystalline zirconia, particularly a kind of preparation method of yttrium-stabile zirconium dioxide nano-powder of single dispersed cubic phase.
Background technology
Zirconium dioxide has the physical and chemical performances such as good thermostability, macroion mobility and erosion resistance and is widely used in the fields such as function ceramics, sensor and catalysis because of it.Zirconium dioxide mainly contains monoclinic phase, Tetragonal and three kinds of crystal formations of Emission in Cubic, generally can experience following transition process:
The high-temperature-phase zirconium dioxide tends to the reduction of temperature be transformed into gradually low-temperature phase, and the Tetragonal and the monoclinic phase that are better than in actual applications low temperature are stablized, are difficult for undergoing phase transition to the Emission in Cubic zirconium dioxide because of it, is worth people to pay close attention to so how to obtain the Emission in Cubic zirconium dioxide of ambient-temp-stable.At present, people often adopt and mix various unit in the zirconium dioxide and usually improve its stability, for example, and Na
+, Y
3+, Ce
4+And Ti
4+Deng.And yttrium is most widely used as a kind of effectively stablizer.Yang etc. (J.Alloys Comp., 2008,458,474-478) prepared the yttrium-stabile zirconium dioxide powder of the Emission in Cubic of ambient-temp-stable by solvent thermal process take ethanol as solvent.
At present, the main method of preparation zirconium dioxide powder has microwave plasma method, chemical gas phase synthetic method, sol-gel method, coprecipitation method, hydrothermal method and solvent-thermal method etc.But the zirconium dioxide nanoparticles for preparing by above method all needs mostly through follow-up high-temperature heat treatment process, thereby the powder that obtains has bad dispersibility, size distribution is wide, specific surface area is low and the defective such as reunion highly.Therefore, seek a kind of controllable method and prepare the high Emission in Cubic Zirconium dioxide nano powder important in inhibiting of good dispersity, narrow diameter distribution and degree of crystallinity.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of yttrium-stabile zirconium dioxide nano-powder of single dispersed cubic phase, the method is simple to operate, cost is low, to equipment require lowly, the characteristics such as the Emission in Cubic Zirconium dioxide nano powder that obtains has that particle is little, narrowly distributing and good dispersity.
The preparation method of the yttrium-stabile zirconium dioxide nano-powder of a kind of single dispersed cubic phase of the present invention comprises:
(1) zirconium alkoxide and yttrium salt are dissolved in the anhydrous lower alcohol, make the anhydrous low-alcohol solution of zirconium alkoxide and yttrium salt, wherein the concentration of zirconium alkoxide is 0.003mmol/mL～1.1mmol/mL, the concentration of yttrium salt is 0.001mmol/mL～0.200mmol/mL, and yttrium is 0.0009～66.7 with the ratio of the amount of substance of zirconium;
(2) the anhydrous low-alcohol solution with above-mentioned zirconium alkoxide and yttrium salt is positioned in the encloses container that fills in advance distilled water, distilled water does not directly contact with the anhydrous low-alcohol solution of zirconium alkoxide and yttrium salt, then being heated to 70～250 ℃ heat-treats, be incubated 1～96 hour, cool to room temperature again, through washing, drying namely gets the yttrium-stabile zirconium dioxide nano-powder of single dispersed cubic phase.
Zirconium alkoxide described in the step (1) is one or both in zirconic acid four positive butyl esters, zirconic acid four isopropyl esters.
Yttrium salt described in the step (1) is one or both in six water Yttrium trinitrates, the six water Yttrium trichlorides.
Lower alcohol described in the step (1) is one or more in methyl alcohol, ethanol, n-propyl alcohol, the Virahol.
The ratio of the amount of substance of zirconium is 10～2000 in the anhydrous low-alcohol solution of the distilled water described in the step (2) and zirconium alkoxide and yttrium salt.
The degree of crystallinity of the yttrium-stabile zirconium dioxide nano-powder of single dispersed cubic phase of gained is high in the step (2), and grain-size is 5～10nm.
Parameter is done some concrete restrictions:
(1) consumption of water: water does not directly contact with the zirconium alkoxide in the bottom of encloses container, water start vaporizer during heating, and the zirconium alkoxide all is hydrolyzed.In the reaction of reality, the ratio of the amount of substance of water and zirconium is between 10 to 2000.
(2) concentration of zirconium alkoxide: the concentration of zirconium alkoxide in lower alcohol is in the scope of 0.003mmol/mL～1.1mmol/mL.
(3) concentration of yttrium salt: the concentration of yttrium salt in lower alcohol is in 0.001mmol/mL～0.200mmol/mL scope.
(4) yttrium and the ratio of the amount of substance of zirconium are in 0.0009～66.7 scope.
The present invention utilizes yttrium as stablizer, promotes the zirconium hydrolysis of alkoxide to obtain the zirconium dioxide powder by water vapour.The characteristics such as the yttrium-stabile zirconium dioxide nano-powder of the Emission in Cubic that the present invention prepares has that particle is little, narrowly distributing and good dispersity.
Beneficial effect
(1) preparation method of the present invention is simple to operate, and cost is low, to equipment require low;
(2) the Emission in Cubic Zirconium dioxide nano powder for preparing of the present invention have that particle is little, the characteristics such as narrowly distributing and good dispersity.
Description of drawings
Fig. 1 is the ZrO for preparing by the yttrium stablizer that adds different content under 200 ℃
2The X ray diffracting spectrum of nano-powder: (a) yttrium zirconium mol ratio be 0.06 and (b) yttrium zirconium mol ratio be 0.09.
Fig. 2 is at 200 ℃, and yttrium zirconium mol ratio is the ZrO for preparing under 0.09 condition
2The scanning electron microscope collection of illustrative plates of nano-powder and corresponding power spectrum result.
Fig. 3 is at 200 ℃, and yttrium zirconium mol ratio is the ZrO for preparing under 0.09 condition
2The transmission electron microscope of nano-powder, high-resolution-ration transmission electric-lens photo and corresponding selected area electron diffraction result.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
2.7mmol tetrabutyl zirconate and 0.07g six water Yttrium trinitrates are joined (yttrium zirconium mol ratio is 0.06) in the crucible that contains the 8mL dehydrated alcohol, stirred 2 minutes, the crucible that then this is contained tetrabutyl zirconate and sour yttrium alcoholic solution is transferred to the top of sealable container.Sealable container bottom is placed with 3mL distilled water in advance.After container is airtight, put into baking oven, begin to be heated to 200 ℃, temperature rise rate is 10～20 ℃/minute, and temperature reached after the temperature of setting insulation 10 hours.After insulation finishes, naturally cool to room temperature, open encloses container, take out crucible, pour out powder, respectively wash 3 times with distilled water and raw spirit, through 60 ℃ of vacuum dryings 8 hours, namely get Zirconium dioxide nano powder, its grain-size is 5～10nm.
Fig. 1 (a) has provided the X-ray diffraction result of the powder for preparing under this condition, can find except the Emission in Cubic zirconium dioxide, also to have occurred the zirconium dioxide of monoclinic phase because the addition of yttrium stablizer is few.
2.7mmol tetrabutyl zirconate and 0.07g six water Yttrium trinitrates are joined (yttrium zirconium mol ratio is 0.06) in the crucible that contains the 8mL dehydrated alcohol, stirred 10 minutes, the crucible that then this is contained tetrabutyl zirconate and sour yttrium alcoholic solution is transferred to the top of sealable container.Sealable container bottom is placed with 3mL distilled water in advance.After container is airtight, put into baking oven, begin to be heated to 240 ℃, temperature rise rate is 10～20 ℃/minute, and temperature reached after the temperature of setting insulation 30 hours.After insulation finishes, naturally cool to room temperature, open encloses container, take out crucible, pour out powder, respectively wash 3 times with distilled water and raw spirit, through 60 ℃ of vacuum dryings 8 hours, namely get Zirconium dioxide nano powder, its grain-size is 5～10nm.
Embodiment 3
2.7mmol tetrabutyl zirconate and 0.09g six water Yttrium trinitrates are joined (yttrium zirconium mol ratio is 0.09) in the crucible that contains the 8mL dehydrated alcohol, stirred 2 minutes, the crucible that then this is contained tetrabutyl zirconate and Yttrium trinitrate alcoholic solution is transferred to the top of sealable container.Sealable container bottom is placed with 3mL distilled water in advance.After container is airtight, put into baking oven, begin to be heated to 200 ℃, temperature rise rate is 10～20 ℃/minute, and temperature reached after the temperature of setting insulation 10 hours.After insulation finishes, naturally cool to room temperature, open encloses container, take out crucible, pour out powder, respectively wash 3 times with distilled water and raw spirit, through 60 ℃ of vacuum dryings 8 hours, namely get Zirconium dioxide nano powder, its grain-size is 5～10nm.
Fig. 1 (b) has provided the X ray diffracting spectrum of the Emission in Cubic Zirconium dioxide nano powder for preparing under this condition.Fig. 2 is scanning electron microscope collection of illustrative plates and the corresponding power spectrum result of the Emission in Cubic Zirconium dioxide nano powder for preparing under this condition.Fig. 3 has provided transmission electron microscope, high-resolution-ration transmission electric-lens photo and the corresponding selected area electron diffraction result of this powder; Fig. 3 (a) can see that the zirconium dioxide powder is single dispersed, and median size is at 5nm; Can significantly observe the lattice fringe of zirconium dioxide in the high-resolution electron microscopy photo of Fig. 3 (b), show that zirconium dioxide has good degree of crystallinity, wherein spacing of lattice corresponding to (111) and (200) face is 0.298nm and 0.254nm, and what this result had further confirmed to obtain is the Emission in Cubic zirconium dioxide; The selected area electron diffraction result that Fig. 3 (c) is corresponding is consistent with the result of XRD.
Embodiment 4
2.7mmol tetrabutyl zirconate and 0.09g six water Yttrium trinitrates are joined in the crucible that contains the 8mL dehydrated alcohol, stirred 2 minutes, the crucible that then this is contained tetrabutyl zirconate and Yttrium trinitrate alcoholic solution is transferred to the top of sealable container.Sealable container bottom is placed with 3mL distilled water in advance.After container is airtight, put into baking oven, begin to be heated to 240 ℃, temperature rise rate is 10～20 ℃/minute, and temperature reached after the temperature of setting insulation 30 hours.After insulation finishes, naturally cool to room temperature, open encloses container, take out crucible, pour out powder, respectively wash 3 times with distilled water and raw spirit, through 60 ℃ of vacuum dryings 8 hours, namely get Zirconium dioxide nano powder, its grain-size is 5～10nm.
4.4mmol tetrabutyl zirconate and 0.018g six water Yttrium trinitrates are joined (yttrium zirconium mol ratio is 0.01) in the crucible that contains the 5mL dehydrated alcohol, stirred 5 minutes, the crucible that then this is contained tetrabutyl zirconate and Yttrium trinitrate alcoholic solution is transferred to the top of sealable container.Sealable container bottom is placed with 5mL distilled water in advance.After container is airtight, put into baking oven, begin to be heated to 150 ℃, temperature rise rate is 10～15 ℃/minute, and temperature reached after the temperature of setting insulation 50 hours.After insulation finishes, naturally cool to room temperature, open encloses container, take out crucible, pour out powder, respectively wash 3 times with distilled water and raw spirit, through 50 ℃ of vacuum dryings 6 hours, namely get Zirconium dioxide nano powder, its grain-size is 5～10nm.
Claims (5)
1. the preparation method of the yttrium-stabile zirconium dioxide nano-powder of a single dispersed cubic phase comprises:
(1) zirconium alkoxide and yttrium salt are dissolved in the anhydrous lower alcohol, make the anhydrous low-alcohol solution of zirconium alkoxide and yttrium salt, wherein the concentration of zirconium alkoxide is 0.003mmol/mL～1.1mmol/mL, the concentration of yttrium salt is 0.001mmol/mL～0.200mmol/mL, and yttrium is 0.09 with the ratio of the amount of substance of zirconium;
(2) the anhydrous low-alcohol solution with above-mentioned zirconium alkoxide and yttrium salt is positioned in the encloses container that fills in advance distilled water, distilled water does not directly contact with the anhydrous low-alcohol solution of zirconium alkoxide and yttrium salt, then being heated to 70～250 ℃ heat-treats, be incubated 1～96 hour, cool to room temperature again, through washing, drying namely gets the yttrium-stabile zirconium dioxide nano-powder of single dispersed cubic phase; The ratio of the amount of substance of zirconium is 10～2000 in the anhydrous low-alcohol solution of the distilled water described in the step (2) and zirconium alkoxide and yttrium salt.
2. the preparation method of the yttrium-stabile zirconium dioxide nano-powder of a kind of single dispersed cubic phase according to claim 1, it is characterized in that: the zirconium alkoxide described in the step (1) is one or both in zirconic acid four positive butyl esters, zirconic acid four isopropyl esters.
3. the preparation method of the yttrium-stabile zirconium dioxide nano-powder of a kind of single dispersed cubic phase according to claim 1, it is characterized in that: the yttrium salt described in the step (1) is one or both in six water Yttrium trinitrates, the six water Yttrium trichlorides.
4. the preparation method of the yttrium-stabile zirconium dioxide nano-powder of a kind of single dispersed cubic phase according to claim 1, it is characterized in that: the lower alcohol described in the step (1) is one or more in methyl alcohol, ethanol, n-propyl alcohol, the Virahol.
5. the preparation method of the yttrium-stabile zirconium dioxide nano-powder of a kind of single dispersed cubic phase according to claim 1 is characterized in that: the grain-size of the yttrium-stabile zirconium dioxide nano-powder of single dispersed cubic phase of gained is 5～10nm in the step (2).
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| EP0200954A2 (en) * | 1985-04-13 | 1986-11-12 | Feldmühle Aktiengesellschaft | Sintered body, method of making it and its use |
| CN1374273A (en) * | 2001-03-08 | 2002-10-16 | 贵研铂业股份有限公司 | Production process of serial zirconia ceramic powder |
| CN101891471A (en) * | 2010-07-12 | 2010-11-24 | 江西泛美亚材料有限公司 | Method for preparing zirconium oxide nanopowder stabilized by yttrium oxide |
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| JP3736649B2 (en) * | 1996-01-12 | 2006-01-18 | 品川白煉瓦株式会社 | Zirconia sintered body, method for producing the same, and pulverized component material |
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| EP0200954A2 (en) * | 1985-04-13 | 1986-11-12 | Feldmühle Aktiengesellschaft | Sintered body, method of making it and its use |
| CN1374273A (en) * | 2001-03-08 | 2002-10-16 | 贵研铂业股份有限公司 | Production process of serial zirconia ceramic powder |
| CN102040381A (en) * | 2009-10-19 | 2011-05-04 | 大连路明纳米材料有限公司 | Method for preparing superfine zirconia powder |
| CN101891471A (en) * | 2010-07-12 | 2010-11-24 | 江西泛美亚材料有限公司 | Method for preparing zirconium oxide nanopowder stabilized by yttrium oxide |
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