CN108640677B - Preparation method of nano composite zirconia powder with controllable grain size - Google Patents
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Abstract
The invention provides a hydrothermal preparation method of nano composite zirconia powder with controllable grain size. Zirconium salt and yttrium salt are used as initial solutions, a precipitator is added into the solutions, aging and filtering are carried out, filter cakes are dispersed into water and transferred into a high-pressure reaction kettle for hydrothermal reaction, a composite mineralizer is added in the reaction process in a high-pressure injection mode, and after the reaction is finished, the nano composite zirconia powder with high crystallinity and controllable grain size is obtained through centrifugal separation and drying. The invention solves the problems of small grain size, wide distribution and uncontrollable grain size and easy agglomeration of grains in the existing hydrothermal synthesis process. The nano zirconia powder prepared by the invention has high dispersion and high crystallinity, the crystal form is tetragonal phase, the grain size is adjustable within the range of 5-100 nanometers, and the grain size distribution is narrow.
Description
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a preparation method of a nano composite zirconia powder with controllable grain size.
Background
Zirconia is a metal oxide material with high melting point (about 2700 ℃), high boiling point, high strength, high temperature resistance, good wear resistance and excellent corrosion resistance. The zirconium oxide is compounded with a small amount of yttrium oxide, so that the zirconium oxide powder can keep a tetragonal crystal structure at room temperature, and the structural defects caused by phase change in the ceramic sintering process are reduced. The nano-grade composite zirconia powder has a plurality of important purposes due to the nano-grade characteristics, and is widely applied to the fields of structural ceramics (such as bearings, valves, cutters, grinding materials and the like), functional ceramics (such as oxygen sensors, solid oxide fuel cells, mobile phone back shells, false teeth and the like), super-toughened ceramics, zirconium-cerium eutectic and the like. The nano composite zirconia powder with uniform grain size, high tetragonal crystal form proportion, high crystallinity and less agglomeration is the key for preparing high-quality zirconia products.
The common method for synthesizing the nano composite zirconia powder comprises the following steps: coprecipitation, hydrolytic precipitation, sol-gel, hydrothermal, microemulsion and spray pyrolysis. The hydrothermal method is a method of heating a reaction vessel to create a high-temperature and high-pressure reaction environment by using a solvent as a reaction medium in a specially-made closed reaction vessel (autoclave) to redissolve and recrystallize substances which are usually insoluble or insoluble, wherein the process conditions of the reaction vessel in the conventional hydrothermal method are generally that the temperature is 120-. Since 1982, the hydrothermal method is used for preparing ultrafine powder for the first time, and the hydrothermal method obtains wide attention at home and abroad by virtue of the advantages of no need of high-temperature calcination, fine product granularity, less agglomeration and the like, and is one of the preferred methods for preparing ultrafine ceramic powder with good crystallization and less agglomeration. However, in the prior art of synthesizing nano zirconia by using a hydrothermal method, such as CN200510045013 and CN200610053923, the grain size of the synthesized product is only smaller in the range of 5-15 nanometers and is uncontrollable. CN01130825 adopts reverse microemulsion method to realize the synthesis of nanometer zirconia with controllable grain size, but the controllable range of the final product grain size is small, and is only 4.1-18.8 nm.
The powder product obtained by the existing nano-zirconia hydrothermal synthesis method has an uncontrollable or very small controllable range of grain size, and cannot meet the requirement of downstream products on grain size diversification, so that the development of a nano-zirconia hydrothermal synthesis method with a wide controllable range of grain size is needed.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a hydrothermal preparation method of nano zirconia powder with controllable grain size and wide controllable range (wide range and narrow distribution).
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of grain size controllable nano composite zirconia powder comprises the following steps:
(1) adding soluble zirconium salt and yttrium salt into water, stirring and dissolving, adding a precipitator solution, adjusting the pH value, quickly stirring to obtain white emulsion, and aging;
(2) after aging is finished, filtering and washing to obtain a filter cake, re-dispersing the filter cake into water (preferably deionized water), and performing high-speed dispersion pulping to obtain zirconium precursor slurry;
(3) transferring the zirconium precursor slurry to a high-pressure reaction kettle for hydro-thermal treatment, adding a composite mineralizer into the kettle in a high-pressure injection mode during the hydro-thermal treatment, cooling after the reaction is finished, separating and drying to obtain the nano composite zirconium oxide powder.
In the step (1) of the present invention, the pH value is adjusted to 8-10, and the stirring speed is 300-1000 rpm.
In the step (1), the aging condition is 25-90 ℃ and the aging time is 2-6 h.
In the step (2) of the invention, the pulping rotation speed is 300-1000rpm, and the concentration of the zirconium hydroxide in the slurry is 0.2-1.5 mol/L.
In the step (3) of the invention, the volume filling amount of the slurry in the kettle is 70-80%, the hydrothermal treatment temperature is 100-.
In the invention, the mineralizer is added at 0.5-4h, preferably 1-2h during the hydrothermal treatment, and the injection pressure of the mineralizer is 0.05MPa higher than the pressure in the reaction kettle. And (3) controlling the grain size and the distribution of the zirconia by controlling the concentration and the adding time of the mineralizer.
In the invention, the zirconium salt is zirconium oxychloride and/or zirconium nitrate, and the yttrium salt is yttrium chloride and/or yttrium nitrate; preferably, in the step (1), the concentration of the zirconium salt in the aqueous solution is 0.1-1.5mol/L, and the concentration of the yttrium salt in the aqueous solution is 0.004-0.24 mol/L.
In the invention, the precipitant is two or more of ammonia water, urea, ammonium bicarbonate and ammonium carbonate; the concentration of the precipitant solution is preferably 5 to 15 mol/L.
The composite mineralizer comprises a mineralizer A and a mineralizer B, wherein the mineralizer A is triisopropanolamine and/or diisopropanolamine, and the mineralizer B is one or two of malonamide, succinamide and butyramide; preferably, the concentration of mineralizer A in the system is 0.1-0.5mol/L, more preferably 0.2-0.4mol/L, and the concentration of mineralizer B is 0.1-1mol/L, more preferably 0.3-0.8 mol/L.
In the invention, the nano composite zirconia powder with wide range and narrow distribution of the grain diameter of 5-100 nm can be obtained by the method.
When the nano composite zirconia is prepared by a hydrothermal method, because the small surface energy of the crystal grains of the nano zirconia is high, part of the small crystal grains can be gradually dissolved into a solution system in the Ostwald curing process and grow to the surface of the adjacent crystal grains again to promote the growth of the crystal grains. The mechanism for realizing the controllable grain size of the zirconia powder is as follows:
(1) regulating and controlling the concentration of a mineralizer: the mineralizer with different concentrations has different sizes of ordered aggregates in the reaction system, and the addition of the mineralizer plays a role of a crystal growth soft template, so that the controllable growth of the grain size is realized.
(2) Adding mode of mineralizer: in the initial stage of the hydrothermal reaction, when the zirconium precursor grows into small zirconium oxide grains in a crystallization way, a mineralizer is added in a high-pressure injection way, and the grain size is controlled by controlling the injection time and the injection amount (concentration); in the prior art, the mineralizer and the precursor are added into the reaction kettle together, the crystallization process of the zirconium precursor is influenced by the mineralizer, and the prepared grains have different sizes and poor dispersion effect.
(3) Selecting the type of a mineralizer: compared with the traditional mineralizer (sodium chloride, ammonium chloride, triethanolamine and the like), the alcohol amine/amide composite mineralizer has stronger dispersity due to the steric hindrance effect, and the prepared nano composite zirconia powder has no obvious agglomeration phenomenon.
Compared with the prior art, the invention has the advantages that:
1. the invention can realize that the grain size of the product is randomly controllable from the range of 5-100 nanometers by adjusting the concentration and the injection time of the composite mineralizer, and the grain size distribution is narrow;
2. the nano zirconia powder prepared by the invention is pure tetragonal crystal form, has no monoclinic crystal form, and has uniform dispersion and less agglomeration;
3. the reaction temperature in the invention is lower, only 100-;
4. the preparation method has the advantages of low cost, stable quality and easy large-scale production.
Drawings
FIG. 1: the XRD pattern of the nano composite zirconia powder in example 1;
FIG. 2: SEM photograph of the nanocomposite zirconia powder in example 1;
FIG. 3: SEM photograph of the nanocomposite zirconia powder in example 2;
FIG. 4: SEM photograph of the nanocomposite zirconia powder in example 3;
FIG. 5: SEM photograph of the nano composite zirconia powder in comparative example 1.
Detailed description of the invention
The technical solution of the present invention is further described with reference to specific examples, which show specific implementation manners and specific operation procedures, but the scope of the present invention is not limited by the following examples.
The examples and comparative examples were as follows:
raw material tables of examples and comparative examples
| Name (R) | Purity of | Manufacturer(s) |
| Zirconium oxychloride | ZrO2≥36.0％ | GUANGDONG ORIENT ZIRCONIC IND SCI & TECH Co.,Ltd. |
| Zirconium nitrate | Analytical purity | Chemical reagent limit of Chinese medicine groupCompany(s) |
| Yttrium chloride | 99.999％ | King of King New materials Ltd |
| Yttrium nitrate | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Aqueous ammonia | 25-28wt％ | XILONG SCIENTIFIC Co.,Ltd. |
| Urea | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Ammonium bicarbonate | Analytical purity | XILONG SCIENTIFIC Co.,Ltd. |
| Ammonium carbonate | Analytical purity | XILONG SCIENTIFIC Co.,Ltd. |
| Sodium hydroxide | Analytical purity | XILONG SCIENTIFIC Co.,Ltd. |
| Triisopropanolamine | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Diisopropanolamine | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Malonamide | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Succinamides | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Butylamide | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
The crystal form and the grain size of the nano composite zirconia powder are calculated by an X-ray diffraction pattern (XRD, D8 Advance, Bruke AXS company); the crystal morphology of the nanocomposite zirconia powder was observed by a scanning electron microscope (SEM, SU8010, hitachi, japan).
Example 1
32.06g of zirconium oxychloride and 1.41g of yttrium chloride are added into 900ml of water, and stirred for 15 minutes until the zirconium oxychloride and the yttrium chloride are completely dissolved, and the stirring speed is 400 rpm. Slowly dripping a mixed solution of 5mol/L ammonia water, urea and ammonium bicarbonate into an aqueous solution of zirconium oxychloride/yttrium chloride, quickly stirring at the stirring speed of 400rpm, adjusting the pH value to 8.0, aging at the aging temperature of 30 ℃, and aging for 3 hours.
Pouring the aged reaction emulsion into a Buchner funnel for suction filtration, and washing with deionized water until the filtrate does not become turbid after reacting with 0.1mol/L silver nitrate solution. The filter cake was taken out, and water was added thereto and stirred at a stirring speed of 400rpm to disperse the mixture into 700ml of a zirconium precursor slurry (the concentration of zirconium hydroxide in the slurry was 0.26 mol/L).
Transferring the zirconium precursor slurry into a polytetrafluoroethylene-lined high-pressure reaction kettle with the volume of 1000ml, filling 70%, reacting at 110 ℃ for 3.5 hours (the pressure in the kettle is about 0.25MPa), adding triisopropanolamine and butanediamide into the reaction system until the concentrations of the triisopropanolamine and the butanediamide in the system reach 0.15mol/L and 0.2mol/L respectively, and the injection pressure is 0.3MPa, and continuously reacting for 12.5 hours. Stirring was continued during the reaction at 400 rpm. After the reaction is finished, after the temperature of the reaction kettle is reduced to room temperature, the solid-liquid separation of the product is realized by a centrifugal machine. And (5) freeze-drying the solid product to obtain the nano composite zirconia powder.
FIG. 1 is an XRD (X-ray diffraction) pattern of the nano composite zirconia powder, and as can be seen from the pattern, the uppermost test diffraction peak is completely coincided with the lowermost standard tetragonal zirconia peak (JCPDS No.50-1089), no monoclinic phase mixed peak is generated, and the crystal form of the product is a tetragonal phase. FIG. 2 is a scanning electron micrograph of the nano-composite zirconia powder, from which it can be seen that the average grain size of the nano-composite zirconia powder is about 20 nm, the grain size distribution is narrow, the dispersion is high, and the crystallinity is high.
Example 2
128.25g of zirconium oxychloride and 22.52g of yttrium chloride are added into 900ml of water, and stirred for 15 minutes until the zirconium oxychloride and the yttrium chloride are completely dissolved, and the stirring speed is 600 rpm. Slowly dripping a mixed solution of 10mol/L ammonia water and ammonium bicarbonate into an aqueous solution of zirconium oxychloride/yttrium chloride, quickly stirring at the stirring speed of 600rpm, adjusting the pH value to 9.0, aging at the aging temperature of 60 ℃, and aging for 4 hours.
Pouring the aged reaction emulsion into a Buchner funnel for suction filtration, and washing with deionized water until the filtrate does not become turbid after reacting with 0.1mol/L silver nitrate solution. The filter cake was taken out, stirred with water at a stirring speed of 600rpm, and dispersed to 750ml of a zirconium precursor slurry (the concentration of zirconium hydroxide in the slurry was 0.96 mol/L).
Transferring the zirconium precursor slurry into a polytetrafluoroethylene lining high-pressure reaction kettle with the volume of 1000ml, filling the zirconium precursor slurry with the filling amount of 75%, reacting at 135 ℃ for 2.5 hours (the pressure in the kettle is about 0.35MPa), adding triisopropanolamine and butanediamide into the reaction system until the concentrations of the triisopropanolamine and the butanediamide in the system reach 0.3mol/L and 0.5mol/L respectively, and the injection pressure is 0.4MPa, and continuously reacting for 18 hours. Stirring was continued during the reaction at 600 rpm. After the reaction is finished, after the temperature of the reaction kettle is reduced to room temperature, the solid-liquid separation of the product is realized by a centrifugal machine. And (5) freeze-drying the solid product to obtain the nano composite zirconia powder.
FIG. 3 is a scanning electron micrograph of the nano-composite zirconia powder, from which it can be seen that the average grain size of the nano-composite zirconia powder is about 50 nm, the grain size distribution is narrow, the dispersion is high, and the crystallinity is high.
Example 3
463.67g of zirconium nitrate and 66.19g of yttrium nitrate were added to 900ml of water, and stirred for 15 minutes until the zirconium nitrate and yttrium nitrate were completely dissolved, at a stirring speed of 800 rpm. Slowly dripping 12mol/L ammonia water, urea and ammonium carbonate mixed solution into zirconium nitrate/yttrium nitrate water solution, rapidly stirring at the stirring speed of 800rpm, adjusting the pH value to 10.0, aging at the temperature of 90 ℃, and aging for 5 hours.
Pouring the aged reaction emulsion into a Buchner funnel for suction filtration, and washing with deionized water until the filtrate does not become turbid after reacting with 0.1mol/L silver nitrate solution. The filter cake was taken out, stirred with water at a stirring speed of 800rpm, and dispersed into 800ml of a zirconium precursor slurry (the concentration of zirconium hydroxide in the slurry was 1.35 mol/L).
Transferring the zirconium precursor slurry into a polytetrafluoroethylene lining high-pressure reaction kettle with the volume of 1000ml, filling the zirconium precursor slurry with the filling amount of 80%, adding diisopropanolamine and a mixed solution of malonamide and butyramide into a reaction system after reacting for 1 hour at 160 ℃ (the pressure in the kettle is about 0.6MPa) until the concentrations of the diisopropanolamine and the malonamide and the butyramide in the system respectively reach 0.45mol/L and 0.9mol/L, and the injection pressure is 0.65MPa, and continuously reacting for 22.5 hours. Stirring was continued during the reaction at 800 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, and performing solid-liquid separation on the product by a centrifugal machine. And (5) freeze-drying the solid product to obtain the nano composite zirconia powder.
FIG. 4 is a scanning electron micrograph of the nano-composite zirconia powder, from which it can be seen that the average grain size of the nano-composite zirconia powder is about 85 nm, the grain size distribution is narrow, the dispersion is high, and the crystallinity is high. Comparative example 1
32.06g of zirconium oxychloride and 1.41g of yttrium chloride are added into 900ml of water, and stirred for 15 minutes until the zirconium oxychloride and the yttrium chloride are completely dissolved, and the stirring speed is 400 rpm. Slowly dripping a mixed solution of 5mol/L ammonia water, urea and ammonium bicarbonate into an aqueous solution of zirconium oxychloride/yttrium chloride, quickly stirring at the stirring speed of 400rpm, adjusting the pH value to 8.0, aging at the aging temperature of 60 ℃, and aging for 3 hours.
Pouring the aged reaction emulsion into a Buchner funnel for suction filtration, and washing with deionized water until the filtrate does not become turbid after reacting with 0.1mol/L silver nitrate solution. The filter cake was taken out, and water was added thereto and stirred at a stirring speed of 400rpm to disperse the mixture into 700ml of a zirconium precursor slurry (the concentration of zirconium hydroxide in the slurry was 0.26 mol/L).
Transferring the zirconium precursor slurry into a polytetrafluoroethylene lining high-pressure reaction kettle with the volume of 1000ml, filling 70 percent, simultaneously adding a mineralizer ammonium chloride to ensure that the concentration of the mineralizer in the system is 0.3mol/L, mechanically stirring for 5 minutes, uniformly mixing, and rotating at the speed of 400 rpm. The reaction kettle is closed, the reaction lasts for 12.5 hours at the temperature of 200 ℃, and the pressure in the reaction kettle is about 1.43 MPa. Stirring was continued during the reaction at 400 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, and performing solid-liquid separation on the product by a centrifugal machine. And (5) freeze-drying the solid product to obtain the nano composite zirconia powder.
FIG. 5 is a scanning electron micrograph of the nano-composite zirconia powder, from which it can be seen that the average grain size of the nano-composite zirconia powder is about 5 nm, the grain size distribution is very wide, and the agglomeration among the particles is relatively severe.
Claims (15)
1. A preparation method of grain size controllable nano composite zirconia powder comprises the following steps:
(1) adding soluble zirconium salt and yttrium salt into water, stirring and dissolving, adding a precipitator solution, adjusting the pH value, quickly stirring to obtain white emulsion, and aging;
(2) after aging is finished, filtering and washing to obtain a filter cake, re-dispersing the filter cake into water, and performing high-speed dispersion and pulping to obtain zirconium precursor slurry;
(3) transferring the zirconium precursor slurry to a high-pressure reaction kettle for hydro-thermal treatment, adding a composite mineralizer into the kettle in a high-pressure injection mode during the hydro-thermal treatment, cooling after the reaction is finished, separating and drying to obtain nano composite zirconium oxide powder;
wherein, a mineralizer is added in 0.5-4h during the hydrothermal treatment in the step (3); the composite mineralizer comprises a mineralizer A and a mineralizer B, wherein the mineralizer A is triisopropanolamine and/or diisopropanolamine, and the mineralizer B is one or two of malonamide, succinamide and butyramide.
2. The method for preparing zirconia powder as claimed in claim 1, wherein the pH value in step (1) is adjusted to 8-10, and the stirring speed is 300-1000 rpm.
3. The method for preparing zirconia powder according to claim 1, wherein the aging condition in the step (1) is 25 to 90 ℃ and the aging time is 2 to 6 hours.
4. The method for preparing zirconia powder as claimed in claim 1, wherein in the step (2), the beating rotation speed is 300-1000rpm, and the concentration of the zirconium hydroxide in the slurry is 0.2-1.5 mol/L.
5. The method for preparing zirconia powder as claimed in claim 1, wherein in step (3), the volume filling amount of the slurry in the kettle is 70-80%, the hydrothermal treatment temperature is 100-.
6. The method according to claim 5, wherein the hydrothermal treatment temperature in step (3) is 120-150 ℃.
7. The method of claim 1 or 5, wherein the mineralizer is injected at a pressure higher than the pressure in the reaction tank by 0.05 MPa.
8. The method for preparing zirconia powder according to claim 7, wherein a mineralizer is added at 1 to 2 hours during the hydrothermal treatment.
9. The method according to any one of claims 1 to 3, wherein the zirconium salt is zirconium oxychloride and/or zirconium nitrate, and the yttrium salt is yttrium chloride and/or yttrium nitrate.
10. The method for preparing zirconium oxide powder according to claim 9, wherein in the step (1), the concentration of zirconium salt in the aqueous solution is 0.1-1.5mol/L, and the concentration of yttrium salt is 0.004-0.24 mol/L.
11. The method for producing the zirconium oxide powder according to any one of claims 1 to 3, wherein the precipitant is two or more of ammonia water, urea, ammonium bicarbonate and ammonium carbonate.
12. The method according to claim 11, wherein the precipitant solution has a concentration of 5 to 15 mol/L.
13. The method for preparing zirconia powder according to claim 1, wherein the concentration of mineralizer A is 0.1-0.5mol/L and the concentration of mineralizer B is 0.1-1 mol/L.
14. The method for preparing zirconia powder according to claim 13, wherein the concentration of mineralizer a is 0.2-0.4mol/L and the concentration of mineralizer B is 0.3-0.8mol/L in the composite mineralizer.
15. The method for producing a zirconia powder according to any one of claims 1 to 6, wherein a nanocomposite zirconia powder having a wide range and a narrow distribution of particle diameters of 5 to 100 nm can be obtained by the method.
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| CN112266244A (en) * | 2020-10-14 | 2021-01-26 | 安徽元琛环保科技股份有限公司 | Preparation method of high-sintering-activity zirconium oxide powder |
| CN113461051B (en) * | 2021-08-17 | 2023-02-03 | 焦作市维纳科技有限公司 | Preparation method of nano zirconia powder |
| CN114014651B (en) * | 2021-09-10 | 2023-10-24 | 王必庆 | Method for producing nano composite zirconia powder by hydrothermal method |
| CN115490263B (en) * | 2022-09-23 | 2023-10-17 | 上海大学 | Preparation method of nano zirconia powder |
| CN115611641B (en) * | 2022-10-19 | 2023-10-13 | 中国科学院赣江创新研究院 | Magnesia yttrium oxide powder and preparation method and application thereof |
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| RU2013112815A (en) * | 2013-03-25 | 2014-09-27 | Вячеслав Викторович Сирота | METHOD FOR PRODUCING NANOSIZED POWDER OF STABILIZED ZIRCONIUM DIOXIDE |
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