CN102126752B - Method for preparing tetragonal phase zirconia nanorod - Google Patents
Method for preparing tetragonal phase zirconia nanorod Download PDFInfo
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- CN102126752B CN102126752B CN201110072496A CN201110072496A CN102126752B CN 102126752 B CN102126752 B CN 102126752B CN 201110072496 A CN201110072496 A CN 201110072496A CN 201110072496 A CN201110072496 A CN 201110072496A CN 102126752 B CN102126752 B CN 102126752B
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- nanorod
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Abstract
The invention provides a method for preparing a tetragonal phase zirconia nanorod. The method comprises the following steps of: adding a mineralizing agent into aqueous solution containing zirconium ions to obtain hydroxide suspension; and performing microwave hydrothermal reaction, washing and drying to obtain the tetragonal phase zirconia nanorod. The diameter and the length of the tetragonal phase zirconia nanorod can be controlled by controlling the temperature, the pressure and the time of the microwave hydrothermal reaction. The tetragonal phase zirconia nanorod prepared by the method has high crystallinity and higher purity; the diameter of a single nanorod is about 60 to 180nm; and the length of the nanorod is 0.5 to 4 mu m. The method for preparing the tetragonal phase zirconia nanorod has the advantages of high purity of a tetragonal phase product, short reaction time, low reaction temperature, high repeatability and the like and is easy to operate.
Description
Technical field
The invention belongs to the nano material preparation technical field, relate to a kind of method for preparing the tetragonal phase zirconium oxide nanometer rod.
Background technology
Excellent physics and chemical properties such as it is high temperature resistant, wear-resistant, corrosion-resistant that zirconium white has are widely used in fields such as electronic ceramics, function ceramics and structural ceramicss.Under differing temps, zirconium white mainly exists with three kinds of paramorphs, like monocline phase zircite (m-ZrO
2), tetragonal phase zirconium oxide (t-ZrO
2) and cubic phase zircite (c-ZrO
2).Wherein, four directions phase or cubic phase zircite have broad application prospects at aspects such as catalytic material, oxygen sensor and high-temperature fuel cells.
Nanometer grade tetragonal zirconium white such as nano particle, nanometer rod etc. have new physicals, have potential to use in a lot of fields, and the zirconic preparation method of nano level who proposes both at home and abroad comprises sol-gel method, co-electrodeposition method and hydrothermal synthesis method etc.China's invention bulletin patent discloses a kind of preparation method of high dispersion rod type nanometer zirconium oxide for No. 201010182571.3; This method contains zirconium oxyhydroxide white precipitate through preparation; Add amphene again and form slip, slip obtains monocline phase high dispersion rod type nanometer zirconium oxide after freeze forming and high-temperature calcination.Hee-Jin Noh etc. are at Synthesis and crystallization of anisotropic shaped ZrO
2Adopt hydrothermal synthesis method among the nanocrystalline powders by hydrothermal process [Materials Letters 57 (2003) 2425-2431], with ZrOCl
28H
20 is raw material, and 1-5mol/L NaOH solution is the hydro-thermal medium, at 250 ℃ of insulation 24h, prepares pure monocline phase zircite nanometer rod.Mostly the method products therefrom that more than prepares the zirconium white nanometer rod is the monocline phase, and needs high-temperature calcination, and preparation cost is high, efficient is low.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method for preparing the tetragonal phase zirconium oxide nanometer rod; This method is in containing the aqueous solution of zirconium ion, to add mineralizer; Obtain the oxyhydroxide suspension liquid,, obtain the zirconium white nanometer rod again through microwave hydrothermal reaction, washing, drying.The prepared product of this method is the tetragonal phase zirconium oxide nanometer rod, and have the reaction times short, temperature of reaction is low, and is simple to operate, advantages such as good reproducibility.
For realizing above-mentioned purpose, the invention provides a kind of method for preparing the tetragonal zircite nanometer rod, may further comprise the steps:
Step 1: select for use water-soluble zirconates to be dissolved in deionized water, be configured to solution, the concentration of zirconium ion is 0.2～0.8mol/L in the solution;
Step 2: with concentration is in the NaOH mineralizer adding step 1 gained solution of 0.1～0.4mol/L, and places constant temperature blender with magnetic force fully to stir at 50 ℃, and wherein, the volume ratio of said zirconium salt solution and mineralizer is 1: (3～9);
Step 3: the precursor liquid that step 2 is obtained adds in the micro-wave digestion jar; With carrying out building-up reactions in the micro-wave digestion jar immigration microwave hydrothermal synthesizer; Reaction naturally cools to room temperature after finishing, and wherein, the microwave hydrothermal synthesising reacting time is 40～55min; The microwave hydrothermal synthesis reaction temperature is 180～210 ℃, and microwave hydrothermal building-up reactions pressure is 1～4MPa;
Step 4: the product that step 3 obtains is collected through spinning, is 10% hydrochloric acid soln washing, deionized water and absolute ethanol washing through mass concentration respectively then, promptly obtains final product tetragonal phase zirconium oxide nanometer rod after the oven dry.
The tetragonal phase zirconium oxide nanometer rod advantages of good crystallization that the present invention obtains, purity is higher, and the diameter of single nanometer rod is about 60～180nm, and the length of nanometer rod is 0.5～4um.
As a kind of preferred version of the present invention, water-soluble zirconates is ZrOCl in the said step 1
28H
2O, ZrCl
4Or ZrO (NO
3)
22H
2O;
As a kind of preferred version of the present invention, the churning time of mineralising agent solution is 20～80min in the said step 2;
As a kind of preferred version of the present invention, bake out temperature is 50～80 ℃ in the said step 4.
The method that the present invention prepares the tetragonal phase zirconium oxide nanometer rod has the following advantages at least: the present invention adds the NaOH mineralizer in containing the aqueous solution of zirconium ion; Obtain the oxyhydroxide suspension liquid; Through microwave hydrothermal reaction, washing, drying, obtain the tetragonal phase zirconium oxide nanometer rod again.Through controlled microwave hydrothermal temperature, pressure and time can controlled oxidation zirconium nanometer rod diameter and length.The tetragonal phase zirconium oxide nanometer rod advantages of good crystallization that the present invention obtains, purity is higher, and the diameter of single nanometer rod is about 60～180nm, and the length of nanometer rod is 0.5～4um.The present invention provides the method for preparing the zirconium white nanometer rod to have that cubic phase product purity is high, the reaction times is short, temperature of reaction is low, and advantage such as simple to operate, good reproducibility.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates by the tetragonal phase zirconium oxide nanometer rod of the present invention's preparation;
Fig. 2 is ESEM (SEM) photo of the tetragonal phase zirconium oxide nanometer rod for preparing of the present invention.
Embodiment
Embodiment 1:
Step 1: select high-purity water dissolubility ZrOCl for use
28H
2O is dissolved in deionized water, is configured to solution, and the concentration of zirconium ion is 0.2mol/L in the solution;
Step 2: with concentration is in the NaOH mineralizer adding step 1 gained solution of 0.1mol/L, and places constant temperature blender with magnetic force fully to stir 20min at 50 ℃, and wherein, the volume ratio of said zirconium salt solution and mineralizer is 1: 3;
Step 3: the precursor liquid that step 2 is obtained adds in the micro-wave digestion jar; With carrying out building-up reactions in the micro-wave digestion jar immigration microwave hydrothermal synthesizer; The microwave hydrothermal synthesising reacting time is 40min; The microwave hydrothermal synthesis reaction temperature is 180 ℃, and microwave hydrothermal building-up reactions pressure is 1MPa, and reaction naturally cools to room temperature after finishing;
Step 4: the product that step 3 obtains is collected through spinning, respectively through 10% hydrochloric acid soln washing, deionized water and absolute ethanol washing, after 50 ℃ of oven dry, promptly obtained final product tetragonal phase zirconium oxide nanometer rod then.
The diameter of the single tetragonal phase zirconium oxide nanometer rod of present embodiment gained is about 60nm, and the length of zirconium white nanometer rod is 0.5um.
Embodiment 2:
Step 1: select high-purity water dissolubility ZrOCl for use
28H
2O is dissolved in deionized water, is configured to solution, and the concentration of zirconium ion is 0.4mol/L in the solution;
Step 2: with concentration is in the NaOH mineralizer adding step 1 gained solution of 0.2mol/L, and places constant temperature blender with magnetic force fully to stir 40min at 50 ℃, and wherein, the volume ratio of said zirconium salt solution and mineralizer is 1: 5;
Step 3: the precursor liquid that step 2 is obtained adds in the micro-wave digestion jar; With carrying out building-up reactions in the micro-wave digestion jar immigration microwave hydrothermal synthesizer; The microwave hydrothermal synthesising reacting time is 45min; The microwave hydrothermal synthesis reaction temperature is 190 ℃, and microwave hydrothermal building-up reactions pressure is 2MPa, and reaction naturally cools to room temperature after finishing;
Step 4: the product that step 3 obtains is collected through spinning, respectively through 10% hydrochloric acid soln washing, deionized water and absolute ethanol washing, after 60 ℃ of oven dry, promptly obtained final product tetragonal phase zirconium oxide nanometer rod then.
The diameter of the single tetragonal phase zirconium oxide nanometer rod of present embodiment gained is about 100nm, and the length of zirconium white nanometer rod is 1.5um.
Embodiment 3:
Step 1: select high-purity water dissolubility ZrCl for use
4Be dissolved in deionized water, be configured to solution, the concentration of zirconium ion is 0.6mol/L in the solution;
Step 2: with concentration is in the NaOH mineralizer adding step 1 gained solution of 0.3mol/L, and places constant temperature blender with magnetic force fully to stir 60min at 50 ℃, and wherein, the volume ratio of said zirconium salt solution and mineralizer is 1: 7;
Step 3: the precursor liquid that step 2 is obtained adds in the micro-wave digestion jar; With carrying out building-up reactions in the micro-wave digestion jar immigration microwave hydrothermal synthesizer; The microwave hydrothermal synthesising reacting time is 50min; The microwave hydrothermal synthesis reaction temperature is 200 ℃, and microwave hydrothermal building-up reactions pressure is 3MPa, and reaction naturally cools to room temperature after finishing;
Step 4: the product that step 3 obtains is collected through spinning, respectively through 10% hydrochloric acid soln washing, deionized water and absolute ethanol washing, after 70 ℃ of oven dry, promptly obtained final product tetragonal phase zirconium oxide nanometer rod then.
The diameter of the single tetragonal phase zirconium oxide nanometer rod of present embodiment gained is about 150nm, and the length of zirconium white nanometer rod is 2.6um.
Embodiment 4:
Step 1: select high-purity water dissolubility ZrO (NO for use
3)
22H
2O is dissolved in deionized water, is configured to solution, and the concentration of zirconium ion is 0.8mol/L in the solution;
Step 2: with concentration is in the NaOH mineralizer adding step 1 gained solution of 0.4mol/L, and places constant temperature blender with magnetic force fully to stir 80min at 50 ℃, and wherein, the volume ratio of said zirconium salt solution and mineralizer is 1: 9;
Step 3: the precursor liquid that step 2 is obtained adds in the micro-wave digestion jar; With carrying out building-up reactions in the micro-wave digestion jar immigration microwave hydrothermal synthesizer; The microwave hydrothermal synthesising reacting time is 55min; The microwave hydrothermal synthesis reaction temperature is 210 ℃, and microwave hydrothermal building-up reactions pressure is 4MPa, and reaction naturally cools to room temperature after finishing;
Step 4: the product that step 3 obtains is collected through spinning, respectively through 10% hydrochloric acid soln washing, deionized water and absolute ethanol washing, after 80 ℃ of oven dry, promptly obtained final product tetragonal phase zirconium oxide nanometer rod then.
The diameter of the single tetragonal phase zirconium oxide nanometer rod of present embodiment gained is about 180nm, and the length of zirconium white nanometer rod is 4um.
Below, see also shown in Figure 1ly, it is the XRD figure spectrum by the zirconium white nanometer rod of the inventive method preparation.Can be found out by figure: the product of the present invention's preparation is a tetragonal phase zirconium oxide.
See also shown in Figure 2ly, it is the SEM pattern of the zirconium white nanometer rod for preparing of the present invention.Can be found out by figure: the diameter of the zirconium white nanometer rod of the present invention's preparation is about 60～180nm, and the length of nanometer rod is about 0.5～4um.Contain part agglomerating particles impurity in the zirconium white nanometer rod.
Claims (4)
1. method for preparing the tetragonal phase zirconium oxide nanometer rod is characterized in that: may further comprise the steps:
Step 1: select for use water-soluble zirconates to be dissolved in deionized water, be configured to solution, the concentration of zirconium ion is 0.2～0.8mol/L in the solution;
Step 2: with concentration is in the NaOH mineralizer adding step 1 gained solution of 0.1～0.4mol/L, and places fully stirring on the constant temperature blender with magnetic force, and wherein, the volume ratio of said zirconium salt solution and mineralizer is 1: (3～9);
Step 3: the precursor liquid that step 2 is obtained adds in the micro-wave digestion jar; With carrying out building-up reactions in the micro-wave digestion jar immigration microwave hydrothermal synthesizer; Reaction naturally cools to room temperature after finishing, and wherein, the microwave hydrothermal synthesising reacting time is 40～55min; The microwave hydrothermal synthesis reaction temperature is 180～210 ℃, and microwave hydrothermal building-up reactions pressure is 1～4MPa;
Step 4: the product that step 3 obtains is collected through spinning, is 10% hydrochloric acid soln washing, deionized water and absolute ethanol washing through mass concentration respectively then, promptly obtains final product tetragonal phase zirconium oxide nanometer rod after the oven dry.
2. the method for preparing the tetragonal phase zirconium oxide nanometer rod as claimed in claim 1 is characterized in that: water-soluble zirconates is ZrOCl in the said step 1
28H
2O, ZrCl
4Or ZrO (NO
3)
22H
2O.
3. the method for preparing the tetragonal phase zirconium oxide nanometer rod as claimed in claim 1 is characterized in that: the churning time of mineralising agent solution is 20～80min in the said step 2.
4. the method for preparing the tetragonal phase zirconium oxide nanometer rod as claimed in claim 1 is characterized in that: bake out temperature is 50～80 ℃ in the said step 4.
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| CN103450899B (en) * | 2013-01-24 | 2014-12-17 | 深圳信息职业技术学院 | Preparation method of yttrium oxide doped nanometer fluorescent powder |
| CN103626490B (en) * | 2013-08-13 | 2015-05-13 | 郑州大学 | Microwave sintering method for m-ZrO2 ceramic |
| CN105502492B (en) * | 2015-12-18 | 2017-03-22 | 景德镇陶瓷大学 | Method for preparing stable zirconia ultrafine powder through non-water-precipitation method |
| CN107460545B (en) * | 2017-08-24 | 2019-07-26 | 台州学院 | A kind of preparation method of rodlike zirconium oxide whisker |
| CN109437296B (en) * | 2018-12-06 | 2021-03-30 | 洛阳理工学院 | Method for preparing tetragonal-phase zirconia nanorod by molten salt growth method |
| CN111056569B (en) * | 2020-01-21 | 2022-04-01 | 绵竹市金坤化工有限公司 | Method for preparing nano zirconium oxide by alcohol method |
| CN112605385B (en) * | 2020-12-16 | 2022-08-30 | 蚌埠飞宇轴承有限公司 | Processing method of bearing material for reducing friction loss of bearing |
| CN112808258A (en) * | 2020-12-25 | 2021-05-18 | 沈阳化工大学 | Preparation method of crystal form adjustable graphene composite material |
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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 |
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| Federica Bondioli，et al..Microwave-Hydrothermal Synthesis of Nanocrystalline Zirconia Powders.《Journal of the American Ceramic Society》.WILEY,2001,第84卷(第11期),2728. * |
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Application publication date: 20110720 Assignee: Jiangsu Jiujiujiu Technology Co., Ltd. Assignor: Shaanxi University of Science and Technology Contract record no.: 2013320010009 Denomination of invention: Method for preparing tetragonal phase zirconia nanorod Granted publication date: 20121010 License type: Exclusive License Record date: 20130225 |
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