CN112125663A - Preparation method of monodisperse yttria-stabilized zirconia nano powder - Google Patents
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Abstract
The invention discloses a preparation method of monodisperse yttria-stabilized zirconia nano powder. The preparation method comprises the following steps: (1) adding a complexing agent and a dispersing agent into an aqueous solution containing zirconium salt and yttrium salt to obtain a solution of a zirconium-yttrium complex, carrying out water bath on the solution of the zirconium-yttrium complex, and adding a neutralizing agent into the solution of the zirconium-yttrium complex under the stirring condition to obtain an aqueous solution of zirconium-yttrium sol; (2) atomizing the aqueous solution of the zirconium-yttrium sol, freeze-drying the aqueous solution by liquid nitrogen, and then carrying out vacuum freeze-drying to obtain zirconium-yttrium precursor powder, and carrying out heat treatment on the zirconium-yttrium precursor powder in air atmosphere to obtain monodisperse yttria-stabilized zirconia nano powder. The crystal form of the yttria-stabilized zirconia nano powder provided by the invention is a tetragonal crystal form, the secondary particle size is 50-500 nm, and the specific surface area is 10-400 m2The specific molar ratio of the zirconium oxide/g is applicable to the fields of electrolyte materials of solid fuel cells, dental zirconia ceramics and the like.
Description
Technical Field
The invention relates to the technical field of powder material preparation, in particular to a preparation method of monodisperse yttria-stabilized zirconia nano powder.
Background
Stabilized zirconia is a functional ceramic material with wide industrial application, and common stabilizers include yttria, magnesia, calcia, scandia and the like, and particularly, yttria is used as a majority. The performance of the yttria-stabilized zirconia functional ceramic material for industrial application is influenced by the initial yttria-stabilized zirconia powder, and generally comprises the factors of the particle size of the initial powder, the distribution uniformity of the stabilizing agent, the monodispersity of particles and the like, and the factors are closely related to the preparation method of the initial powder.
At present, the preparation methods of yttria-stabilized zirconia powder are more, and mainly comprise the following steps: chemical coprecipitation, hydrothermal, sol-gel, mechanical mixing, and the like. (1) The chemical coprecipitation method is one of the most commonly used methods in industry, and generally comprises dissolving inorganic salts of zirconium element and yttrium element in water, adding a precipitant to precipitate zirconium yttrium ions from the solution, collecting and washing the precipitate, and calcining to obtain yttria-stabilized zirconia powder. The chemical coprecipitation method has the advantages of simple process, low cost and the like, but the prepared yttria-stabilized zirconia powder has the defects of large secondary particle size, poor particle size dispersibility, serious agglomeration, poor sintering activity and the like. (2) The preparation of yttria-stabilized zirconia by a hydrothermal method is divided into a hydrothermal hydrolysis method and a hydrothermal precipitation method, wherein a hydrothermal precipitation method generally used in industrial production adopts high-temperature-resistant and high-pressure-resistant reaction kettle equipment, and is characterized in that an aqueous solution containing a zirconium source, an yttrium source and a precipitant is heated and pressurized, after a long reaction time, a reaction precipitate undergoes a dissolution-recrystallization process, and finally, yttrium oxide-stabilized zirconia powder is obtained after washing and drying. The powder material prepared by the hydrothermal precipitation method has the advantages of good crystal form, high purity, smaller secondary particle size, less agglomeration degree and good sintering activity, but has the defects of high requirements on equipment, difficult control of process parameters, long production period and the like. (3) The sol-gel method is also a common method for preparing yttria-stabilized zirconia, and generally comprises the steps of adding a complexing agent into an aqueous solution containing zirconium and yttrium elements, forming a sol solution under a certain condition, then obtaining a zirconium-yttrium precursor after gelation, and obtaining yttria-stabilized zirconia powder after calcination. The method has the advantages that the prepared powder has good crystal form, small secondary particle size, narrow particle size distribution and high activity, and has the defects of long period, high shrinkage rate caused by easy agglomeration during drying, complex operation and the like in the gel process of the sol.
Disclosure of Invention
The invention provides a method for preparing monodisperse yttria-stabilized zirconia nano powder, which aims to solve the problems in the prior art, and the method comprises the steps of complexing zirconium yttrium ions by using a complexing agent, uniformly distributing the zirconium yttrium ions in a solution under the action of a dispersing agent, adding a neutralizing agent at a slow dripping acceleration rate to control the pH value of the solution, rapidly forming ice crystals from solvent water by atomization and liquid nitrogen rapid freeze-drying so as not to cause segregation of the zirconium yttrium ions, obtaining hard-agglomeration-free zirconium yttrium precursor powder under vacuum freeze-drying, and finally obtaining the monodisperse yttria-stabilized zirconia nano powder through a calcination process.
The invention provides a preparation method of monodisperse yttria-stabilized zirconia nano powder, which comprises the following steps:
(1) adding a complexing agent and a dispersing agent into an aqueous solution containing zirconium salt and yttrium salt to obtain a solution of a zirconium-yttrium complex, carrying out water bath on the solution of the zirconium-yttrium complex at the temperature of 60-80 ℃, and adding a neutralizing agent into the solution of the zirconium-yttrium complex under the condition of stirring to obtain an aqueous solution of zirconium-yttrium sol;
(2) atomizing the aqueous solution of the zirconium-yttrium sol obtained in the step (1), freeze-drying the aqueous solution by liquid nitrogen to obtain zirconium-yttrium precursor powder, and carrying out heat treatment on the zirconium-yttrium precursor powder at 600-900 ℃ in an air atmosphere to obtain the monodisperse yttria-stabilized zirconia nano powder.
Preferably, in the aqueous solution containing a zirconium salt and an yttrium salt in step (1), the zirconium salt is selected from one of zirconium sulfate, zirconium nitrate and zirconium oxychloride octahydrate, and the yttrium salt is yttrium chloride or yttrium nitrate hexahydrate, wherein the molar ratio of zirconium element to yttrium element is 4.5-49.5: 1, and the molar concentration of zirconium element is 0.1-2 mol/L.
More preferably, the molar ratio of the zirconium element to the yttrium element is 97:6 to 92:16, and the molar concentration of the zirconium element is 0.5 to 1 mol/L.
Preferably, the complexing agent in the step (1) is citric acid or oxalic acid, and the added molar weight of the complexing agent is 50-120% of the sum of the molar weights of the zirconium element and the yttrium element.
Preferably, the dispersant in the step (1) is selected from one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and polyethylene glycol 3000, and the molar concentration of the dispersant is 0.006-0.012 mol/L.
Preferably, the neutralizing agent in the step (1) is selected from one of ammonia water, ammonium bicarbonate and urea, the concentration of the neutralizing agent solution is 0.5-2 mol/L, and the neutralizing agent solution is dripped into the zirconium yttrium complex solution at the dripping rate of 1-10 mL/min until the pH value of the obtained zirconium yttrium sol aqueous solution is 4-5.
Further preferably, the dropping rate of the neutralizer solution is 2-5 mL/min.
Preferably, the step (2) of obtaining the zirconium-yttrium precursor powder by atomizing the aqueous solution of the zirconium-yttrium sol obtained in the step (1) and freeze-drying the atomized aqueous solution with liquid nitrogen comprises the following specific steps: and (2) spraying liquid drops formed by the aqueous solution of the zirconium-yttrium sol obtained in the step (1) through an atomizing nozzle into liquid nitrogen for supercooling and freeze-drying, and then carrying out vacuum freeze-drying to obtain zirconium-yttrium precursor powder, wherein the vacuum degree of the vacuum freeze-drying is 1-20 Pa.
Preferably, the step (2) of heat-treating the zirconium-yttrium precursor powder at 600-900 ℃ in an air atmosphere comprises the following specific steps: heating zirconium yttrium precursor powder to 500 ℃ at the speed of 5 ℃/min in the air atmosphere, preserving heat for 1-2 hours, heating to 600-900 ℃ at the speed of 1-5 ℃/min, and preserving heat for 1-3 hours.
The invention has the beneficial effects that:
1. the invention uses complexing agent to complex zirconium yttrium ions, then evenly distributes the zirconium yttrium ions in solution under the action of dispersing agent, controls the pH value of zirconium yttrium complex solution by slowly dripping neutralizing agent, enables solvent water to rapidly form ice crystal without causing zirconium yttrium ion segregation by atomization and liquid nitrogen rapid freeze-drying, then obtains zirconium yttrium precursor powder without hard agglomeration under vacuum freeze-drying, and finally obtains monodisperse yttria stabilized zirconia nano powder by calcining process.
2. The crystal form of the yttria-stabilized zirconia nano powder provided by the invention is a tetragonal crystal form, the secondary particle size is 50-500 nm, and the specific surface area is 10-400 m2The specific molar ratio of the zirconium oxide/g is applicable to the fields of electrolyte materials of solid fuel cells, dental zirconia ceramics and the like.
Drawings
FIG. 1 is a graph showing a secondary particle size distribution measured by a laser dynamic light scattering method of yttria-stabilized zirconia prepared in example 1;
FIG. 2 is a powder X-ray diffraction spectrum of yttria-stabilized zirconia prepared in example 1;
FIG. 3 is a nitrogen adsorption-desorption isotherm plot of the yttria-stabilized zirconia prepared in example 1;
FIG. 4 is a graph showing a secondary particle size distribution measured by a laser dynamic light scattering method of yttria-stabilized zirconia prepared in comparative example 1;
FIG. 5 is a powder X-ray diffraction spectrum of yttria-stabilized zirconia prepared in comparative example 1;
FIG. 6 is a nitrogen adsorption-desorption isotherm graph of the yttria-stabilized zirconia prepared in comparative example 1.
Detailed Description
The following examples are intended to further illustrate, but not limit, the present invention (the following examples, unless otherwise specified, do not contain other components not specifically indicated except for unavoidable impurities). The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art.
Example 1
A preparation method of monodisperse yttria-stabilized zirconia nano powder comprises the following steps:
(1) weighing 32.23g of zirconium oxychloride octahydrate and 1.17g of yttrium chloride under room temperature and normal pressure, dissolving in deionized water, wherein the total volume of the solution after complete dissolution is 100mL, and preparing a solution containing yttrium and zirconium ions, wherein the molar concentration of the zirconium ions is 1mol/L, and the molar concentration of the yttrium ions is 0.06 mol/L; adding 0.25g of sodium dodecyl sulfate and 12.61g of citric acid monohydrate into the yttrium zirconium ion-containing solution in sequence, and magnetically stirring the mixture in a water bath at the temperature of 60 ℃ for 0.5 hour until the mixed solution is colorless, clear and transparent; slowly dripping ammonia water with the molar concentration of 1mol/L into the mixed solution by using a syringe pump, wherein the dripping speed is 3mL/min until the pH value of the mixed solution is within the range of 4-5; after the dropwise addition is stopped, the mixture is continuously stirred by magnetic force for 0.5 hour, taken out from the water bath and kept stand for 0.5 hour to obtain milky colloidal solution (the aqueous solution of zirconium yttrium sol);
(2) temporarily installing a proper amount of liquid nitrogen on a stainless steel plate, spraying the colloidal solution obtained in the step (1) into the stainless steel plate in an atomizing mode to obtain granular freeze-dried substances, removing redundant liquid nitrogen, and drying the freeze-dried substances for 6 hours (the vacuum degree is 10Pa) by a vacuum freeze-drying machine to obtain white powder with good fluidity; heating the white powder from room temperature to 500 ℃ at a heating rate of 5 ℃/min in an air atmosphere, and keeping the temperature for 1 hour; then heating to 800 ℃ at the speed of 1 ℃/min, preserving the heat for 2 hours, then cooling to room temperature along with the furnace, and taking out to obtain the monodisperse yttria-stabilized zirconia nano powder.
The distribution diagram of the secondary particle size of the yttria-stabilized zirconia nanopowder prepared in this example measured by the laser dynamic light scattering method is shown in FIG. 1, the X-ray diffraction diagram of the yttria-stabilized zirconia powder is shown in FIG. 2, and the nitrogen adsorption-desorption isotherm graph of the yttria-stabilized zirconia is shown in FIG. 3The following can be obtained from fig. 1 to 3: the crystal form of the yttria-stabilized zirconia nano powder prepared by the embodiment is a tetragonal crystal form, and the secondary particle diameter of the powder particles is D500.127 μm, monodisperse distribution, and specific surface area 342.21m2In g, the mean particle size was 24.15 nm.
Comparative example 1
Weighing 32.23g of zirconium oxychloride octahydrate and 1.17g of yttrium chloride under room temperature and normal pressure, dissolving in deionized water, wherein the total volume of the solution after complete dissolution is 100mL, and preparing a solution containing yttrium and zirconium ions, wherein the molar concentration of the zirconium ions is 1mol/L, and the molar concentration of the yttrium ions is 0.06 mol/L; adding 0.25g of sodium dodecyl sulfate and 12.61g of citric acid monohydrate into the yttrium zirconium ion-containing solution in sequence, and magnetically stirring the mixture in a water bath at the temperature of 60 ℃ for 0.5 hour until the mixed solution is colorless, clear and transparent; slowly dripping ammonia water with the molar concentration of 1mol/L into the mixed solution by using a syringe pump, wherein the dripping speed is 3mL/min until the pH value of the mixed solution is within the range of 4-5; after the dropwise addition is stopped, the mixture is continuously stirred by magnetic force for 0.5 hour, taken out from the water bath and kept stand for 0.5 hour to obtain milky colloidal solution (the aqueous solution of zirconium yttrium sol); then placing the obtained zirconium-yttrium sol aqueous solution in a drying oven at 70 ℃ for drying for 12 hours to obtain a blocky white solid, grinding the blocky white solid into powder, heating the powder from room temperature to 500 ℃ at the heating rate of 5 ℃/min in the air atmosphere, and keeping the temperature for 1 hour; and then heating to 800 ℃ at the speed of 1 ℃/min, preserving the heat for 2 hours, cooling to room temperature along with the furnace, and taking out to obtain the yttria-stabilized zirconia powder.
The powder has a secondary particle diameter of D obtained by dynamic light scattering5036.7 μm. The powder is subjected to powder X-ray diffraction measurement, and the result contains two crystal forms, namely a tetragonal crystal form and a monoclinic crystal form. The powder had a specific surface area of 16.51m as measured by the nitrogen adsorption/desorption BET method2(iv)/g, average particle size 363.46 nm.
Example 2
A preparation method of monodisperse yttria-stabilized zirconia nano powder comprises the following steps:
(1) weighing 14.17g of zirconium sulfate and 1.92g of yttrium nitrate hexahydrate to dissolve in deionized water at room temperature and normal pressure, wherein the total volume of the solution is 100mL after complete dissolution, and preparing a solution containing yttrium and zirconium ions, wherein the molar concentration of the zirconium ions is 0.5mol/L, and the molar concentration of the yttrium ions is 0.05 mol/L; 0.31g of sodium dodecylbenzenesulfonate and 10.51g of citric acid monohydrate were added to the yttrium zirconium ion-containing solution in this order; magnetically stirring the solution in a water bath at 80 ℃ for 0.5 hour until the mixed solution is colorless, clear and transparent; slowly dripping a urea solution with the molar concentration of 1mol/L into the mixed solution by using an injection pump, wherein the dripping speed is 5mL/min until the pH value of the mixed solution is within the range of 4-5; after the dropwise addition is stopped, the mixture is continuously stirred by magnetic force for 0.5 hour, taken out from the water bath and kept stand for 0.5 hour to obtain milky colloidal solution (the aqueous solution of zirconium yttrium sol);
(2) temporarily installing a proper amount of liquid nitrogen on a stainless steel plate, spraying the colloidal solution obtained in the step (1) into the stainless steel plate in an atomizing mode to obtain granular freeze-dried substances, removing redundant liquid nitrogen, and drying the freeze-dried substances for 12 hours (the vacuum degree is 10Pa) by a vacuum freeze-drying machine to obtain white powder with good fluidity; heating the white powder from room temperature to 500 ℃ at a heating rate of 5 ℃/min in an air atmosphere, and keeping the temperature for 2 hours; then heating to 900 ℃ at the speed of 1 ℃/min, preserving the heat for 2 hours, then cooling to room temperature along with the furnace, and taking out to obtain the monodisperse yttria-stabilized zirconia nano powder.
The crystal form of the yttria-stabilized zirconia prepared in the example is a tetragonal crystal form determined by a powder X-ray diffraction method, and the secondary particle size of the powder particles is D determined by a laser dynamic light scattering method500.371 μm, and has monodispersion distribution, and the powder has specific surface area of 59.24m measured by nitrogen adsorption/desorption BET method2In terms of/g, the mean particle size was 74.32 nm.
Comparative example 2
Weighing 14.17g of zirconium sulfate and 1.92g of yttrium nitrate hexahydrate to dissolve in deionized water at room temperature and normal pressure, wherein the total volume of the solution is 100mL after complete dissolution, and preparing a solution containing yttrium and zirconium ions, wherein the molar concentration of the zirconium ions is 0.5mol/L, and the molar concentration of the yttrium ions is 0.05 mol/L; 0.31g of zirconium ion was added to the yttrium-containing solutionSodium dodecylbenzenesulfonate and 10.51g citric acid monohydrate; magnetically stirring the solution in a water bath at 80 ℃ for 0.5 hour until the mixed solution is colorless, clear and transparent; slowly dripping a urea solution with the molar concentration of 1mol/L into the mixed solution by using an injection pump, wherein the dripping speed is 5mL/min until the pH value of the mixed solution is within the range of 4-5; after the dropwise addition is stopped, the mixture is continuously stirred by magnetic force for 0.5 hour, taken out from the water bath and kept stand for 0.5 hour to obtain milky colloidal solution (the aqueous solution of zirconium yttrium sol); then placing the obtained zirconium-yttrium sol aqueous solution in a drying oven at 90 ℃ for drying for 6 hours to obtain a blocky white solid, grinding the blocky white solid into powder, heating the white powder from room temperature to 500 ℃ at the heating rate of 5 ℃/min in the air atmosphere, and keeping the temperature for 2 hours; then heating to 900 ℃ at the speed of 1 ℃/min, preserving the heat for 2 hours, then cooling to room temperature along with the furnace, and taking out to obtain the yttria-stabilized zirconia powder. The powder has a secondary particle diameter of D obtained by dynamic light scattering50＝41.6μm。
The powder is subjected to powder X-ray diffraction measurement, and the result contains two crystal forms, namely a tetragonal crystal form and a monoclinic crystal form. The powder had a specific surface area of 10.14m as measured by the nitrogen adsorption/desorption BET method2(iv)/g, average particle size 372.17 nm.
Example 3
A preparation method of monodisperse yttria-stabilized zirconia nano powder comprises the following steps:
(1) weighing 32.23g of zirconium oxychloride octahydrate and 15.64g of yttrium chloride under room temperature and normal pressure, dissolving in deionized water, wherein the total volume of the solution after complete dissolution is 200mL, and preparing a solution containing yttrium and zirconium ions, wherein the molar concentration of the zirconium ions is 0.5mol/L of zirconium ion solution, and the molar concentration of the yttrium ions is 0.08 mol/L; adding 3.6g of polyethylene glycol 3000 and 24.38g of citric acid monohydrate to the yttrium zirconium ion containing solution; magnetically stirring the solution in a water bath at 80 ℃ for 0.5 hour until the mixed solution is colorless, clear and transparent; slowly dripping ammonia water with the molar concentration of 2mol/L into the mixed solution by using a syringe pump, wherein the dripping speed is 2mL/min until the pH value of the mixed solution is within the range of 4-5; after the dropwise addition is stopped, the mixture is continuously stirred by magnetic force for 0.5 hour, taken out from the water bath and kept stand for 0.5 hour to obtain milky colloidal solution (the aqueous solution of zirconium yttrium sol);
(2) temporarily installing a proper amount of liquid nitrogen on a stainless steel plate, spraying the colloidal solution obtained in the step (1) into the stainless steel plate in an atomizing mode to obtain granular freeze-dried substances, removing redundant liquid nitrogen, and drying the freeze-dried substances for 12 hours (the vacuum degree is 10Pa) by a vacuum freeze-drying machine to obtain white powder with good fluidity; heating the white powder from room temperature to 500 ℃ at a heating rate of 5 ℃/min in an air atmosphere, and keeping the temperature for 2 hours; then heating to 900 ℃ at the speed of 1 ℃/min, preserving the heat for 2 hours, then cooling to room temperature along with the furnace, and taking out to obtain the monodisperse yttria-stabilized zirconia nano powder.
The crystal form of the yttria-stabilized zirconia prepared in the example is tetragonal form measured by a powder X-ray diffraction method, and the secondary particle size of the powder particles measured by a laser dynamic light scattering method is D500.312 mu m, and the powder has a specific surface area of 34.15m by nitrogen adsorption/desorption BET method2(iv)/g, average particle size 147.24 nm.
Comparative example 3
Weighing 32.23g of zirconium oxychloride octahydrate and 15.64g of yttrium chloride under room temperature and normal pressure, dissolving in deionized water, wherein the total volume of the solution after complete dissolution is 200mL, and preparing a solution containing yttrium and zirconium ions, wherein the molar concentration of the zirconium ions is 0.5mol/L of zirconium ion solution, and the molar concentration of the yttrium ions is 0.08 mol/L; adding 3.6g of polyethylene glycol 3000 and 24.38g of citric acid monohydrate to the yttrium zirconium ion containing solution; magnetically stirring the solution in a water bath at 80 ℃ for 0.5 hour until the mixed solution is colorless, clear and transparent; slowly dripping ammonia water with the molar concentration of 2mol/L into the mixed solution by using a syringe pump, wherein the dripping speed is 2mL/min until the pH value of the mixed solution is within the range of 4-5; after the dropwise addition is stopped, the mixture is continuously stirred by magnetic force for 0.5 hour, taken out from the water bath and kept stand for 0.5 hour to obtain milky colloidal solution (the aqueous solution of zirconium yttrium sol); then placing the obtained zirconium-yttrium sol aqueous solution in a drying oven at 110 ℃ for fast drying for 4 hours to obtain a blocky white solid, grinding the blocky white solid into powder, and placing the white powder in an air atmosphereHeating from room temperature to 500 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 2 hours; then heating to 900 ℃ at the speed of 1 ℃/min, preserving the heat for 2 hours, then cooling to room temperature along with the furnace, and taking out to obtain the yttria-stabilized zirconia powder. The powder has a secondary particle diameter of D obtained by dynamic light scattering50＝62.9μm。
The powder is subjected to powder X-ray diffraction measurement, and the result contains two crystal forms, namely a tetragonal crystal form and a monoclinic crystal form. The powder had a specific surface area of 8.05m as measured by the nitrogen adsorption/desorption BET method2(iv)/g, average particle size 364.71 nm.
The reaction conditions and test results of the yttria-stabilized zirconia powder of each of examples 1 to 3 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1
As can be seen from examples 1 to 3 and comparative examples 1 to 3 in Table 1, in comparative examples 1 to 3, the zirconium yttrium sol solution is dried by a conventional drying method, under the condition of high temperature and long-time drying, a zirconium yttrium complex can be separated out and gradually form hard aggregates due to volatilization of a solvent, and finally the hard aggregates are agglomerated into a block-shaped solid, so that the particle size of the final product is not uniformly dispersed, the specific surface area is smaller, and the sintering activity of the material is affected. In examples 1 to 3, a zirconium yttrium complex sol solution is uniformly dispersed in liquid nitrogen by atomization, so that the purpose of rapidly freeze-drying solvent water without causing sol segregation is achieved, ice is rapidly sublimated by a vacuum freeze-drying method to achieve the purpose of drying, the powder obtained by the method is fine, and yttria-stabilized zirconia nano-powder with monodispersity in secondary particle size can be obtained in subsequent heat treatment.
Example 4
The same as example 1, except that:
in the step (1), the zirconium salt is zirconium nitrate, the molar ratio of zirconium element to yttrium element is 4.5:1, the molar concentration of zirconium element is 0.1mol/L, the molar concentration of sodium dodecyl sulfate is 0.006mol/L, the molar concentration of ammonia water is 0.5mol/L, and the dropping rate is 10 mL/min;
in the step (2), the zirconium yttrium precursor powder is heated to 500 ℃ at the speed of 5 ℃/min in the air atmosphere, and is kept at the temperature for 1 hour, and then heated to 600 ℃ at the speed of 5 ℃/min, and is kept at the temperature for 3 hours.
Example 5
The same as example 1, except that:
in the step (1), the zirconium salt is zirconium nitrate, the molar ratio of zirconium element to yttrium element is 49.5:1, the molar concentration of zirconium element is 2mol/L, the molar concentration of sodium dodecyl sulfate is 0.012mol/L, the molar concentration of ammonia water is 2mol/L, and the dropping rate is 1 mL/min;
in the step (2), the zirconium yttrium precursor is heated to 500 ℃ at the speed of 5 ℃/min in the air atmosphere, and is kept at the temperature for 2 hours, and then heated to 900 ℃ at the speed of 1 ℃/min, and is kept at the temperature for 1 hour.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (9)
1. A preparation method of monodisperse yttria-stabilized zirconia nano powder is characterized by comprising the following steps:
(1) adding a complexing agent and a dispersing agent into an aqueous solution containing zirconium salt and yttrium salt to obtain a solution of a zirconium-yttrium complex, carrying out water bath on the solution of the zirconium-yttrium complex at the temperature of 60-80 ℃, and adding a neutralizing agent into the solution of the zirconium-yttrium complex under the condition of stirring to obtain an aqueous solution of zirconium-yttrium sol;
(2) atomizing the aqueous solution of the zirconium-yttrium sol obtained in the step (1), freeze-drying the aqueous solution by liquid nitrogen to obtain zirconium-yttrium precursor powder, and carrying out heat treatment on the zirconium-yttrium precursor powder at 600-900 ℃ in an air atmosphere to obtain the monodisperse yttria-stabilized zirconia nano powder.
2. The method according to claim 1, wherein the aqueous solution containing a zirconium salt and an yttrium salt in step (1) is characterized in that the zirconium salt is selected from one of zirconium sulfate, zirconium nitrate and zirconium oxychloride octahydrate, the yttrium salt is yttrium chloride or yttrium nitrate hexahydrate, the molar ratio of zirconium element to yttrium element is 4.5-49.5: 1, and the molar concentration of zirconium element is 0.1-2 mol/L.
3. The method according to claim 2, wherein the molar ratio of zirconium to yttrium is 97:6 to 92:16, and the molar concentration of zirconium is 0.5 to 1 mol/L.
4. The method for preparing the monodisperse yttria-stabilized zirconia nano-powder according to claim 1, wherein the complexing agent in the step (1) is citric acid or oxalic acid, and the molar weight of the complexing agent is 50-120% of the sum of the molar weights of the zirconium element and the yttrium element.
5. The method for preparing the monodisperse yttria-stabilized zirconia nanopowder according to claim 1, wherein the dispersant in the step (1) is one selected from sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and polyethylene glycol 3000, and the molar concentration of the dispersant is 0.006-0.012 mol/L.
6. The method for preparing monodisperse yttria-stabilized zirconia nanopowder according to claim 1, wherein the neutralizer in step (1) is one selected from ammonia water, ammonium bicarbonate and urea, the concentration of the neutralizer solution is 0.5-2 mol/L, and the neutralizer solution is dropwise added into the solution of the zirconium yttrium complex at a dropping rate of 1-10 mL/min until the pH value of the obtained aqueous solution of the zirconium yttrium sol is 4-5.
7. The method for preparing the monodisperse yttria-stabilized zirconia nanopowder according to claim 6, wherein the dropping rate of the neutralizer solution is 2-5 mL/min.
8. The method for preparing the monodisperse yttria-stabilized zirconia nano-powder according to claim 1, wherein the step (2) of obtaining the zirconium yttrium precursor powder by atomizing the aqueous solution of the zirconium yttrium sol obtained in the step (1) and freeze-drying the atomized aqueous solution with liquid nitrogen comprises the following specific steps: and (2) spraying liquid drops formed by the aqueous solution of the zirconium-yttrium sol obtained in the step (1) through an atomizing nozzle into liquid nitrogen for supercooling and freeze-drying, and then carrying out vacuum freeze-drying to obtain zirconium-yttrium precursor powder, wherein the vacuum degree of the vacuum freeze-drying is 1-20 Pa.
9. The method for preparing the monodisperse yttria-stabilized zirconia nano-powder according to claim 1, wherein the step (2) of heat-treating the zirconium yttrium precursor powder at 600-900 ℃ in an air atmosphere comprises the following specific steps: heating zirconium yttrium precursor powder to 500 ℃ at the speed of 5 ℃/min in the air atmosphere, preserving heat for 1-2 hours, heating to 600-900 ℃ at the speed of 1-5 ℃/min, and preserving heat for 1-3 hours.
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