CN113200567A - High-sintering-activity zirconium oxide powder and preparation method thereof - Google Patents

High-sintering-activity zirconium oxide powder and preparation method thereof Download PDF

Info

Publication number
CN113200567A
CN113200567A CN202110581412.9A CN202110581412A CN113200567A CN 113200567 A CN113200567 A CN 113200567A CN 202110581412 A CN202110581412 A CN 202110581412A CN 113200567 A CN113200567 A CN 113200567A
Authority
CN
China
Prior art keywords
powder
zirconia
solution
zirconia powder
sintering activity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110581412.9A
Other languages
Chinese (zh)
Inventor
张波
王权
朱刘
童培云
何坤鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pilot Film Materials Co ltd
Original Assignee
Pilot Film Materials Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Pilot Film Materials Co ltd filed Critical Pilot Film Materials Co ltd
Priority to CN202110581412.9A priority Critical patent/CN113200567A/en
Publication of CN113200567A publication Critical patent/CN113200567A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00Compounds of zirconium
    • C01G25/02Oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/10Solid density

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention provides high-sintering-activity zirconium oxide powder and a preparation method thereof, and relates to the technical field of ceramic powder preparation. The preparation method provided by the invention comprises the following steps: (1) mixing a zirconium oxychloride solution and a yttrium nitrate solution to obtain a mixed solution, mixing the mixed solution with ammonia water, stirring and aging to obtain hydroxide precursor slurry; (2) washing and drying the hydroxide precursor slurry to obtain dry gel; (3) crushing the xerogel, adding water and carrying out ball milling to obtain wet gel; (4) adding a mineralizer and water into the wet gel, and performing hydrothermal reaction to obtain precursor powder; (5) and calcining the precursor powder to obtain the zirconia powder with high sintering activity. The zirconia powder prepared by the preparation method of the invention is in a tetragonal crystal form, the particle size of the powder is 50-150nm, and the particle size is 1350-The sintered density at the temperature of 6.051-6.083g/cm DEG C3

Description

High-sintering-activity zirconium oxide powder and preparation method thereof
Technical Field
The invention relates to the technical field of ceramic powder preparation, in particular to zirconia powder with high sintering activity and a preparation method thereof.
Background
Zirconium oxide, as an important oxide ceramic material, has the characteristics of high melting point, high strength, corrosion resistance, wear resistance, low thermal conductivity, semiconductors, phase change toughening and the like, and is widely applied to the fields of structural ceramics, functional ceramics, refractory materials and the like. In addition, the zirconium oxide after being stabilized by the crystal form stabilizer can also be applied to the production of ceramic capacitors, gas sensitive elements, catalysts and the like. Thus, there is an increasing demand in the industry for zirconia.
The preparation of zirconia ceramics usually comprises three parts of powder preparation, prepressing forming and blank sintering, wherein the particle size, the uniformity, the purity and the dispersibility of the prepared powder are decisive factors of the physicochemical properties of the ceramic sintering. At present, the preparation methods of the zirconium oxide in China are various, and among the methods, the solid phase method, the liquid phase method and the gas phase method are mostly adopted. Patent document CN110550952A discloses a zirconia ceramic powder and a preparation method thereof, which adopts a mixed oxide method to mix a rare earth nitric acid compound, zirconia, alumina, absolute ethyl alcohol and water, and stir uniformly to obtain a mixture; performing ball milling treatment on the mixture to obtain uniform slurry; drying the uniform slurry to obtain coarse bulk zirconia ceramic powder; grinding the coarse grinding powder of the blocky zirconia ceramics into powder, and then heating the powder for roasting treatment to obtain roasted zirconia ceramic powder; and (4) finely grinding the roasted zirconia ceramic powder, and sieving to obtain a final product. The method is simple to operate, the product purity is high, but the prepared product has nonuniform appearance and size, poor dispersibility and low sintering activity.
Patent document CN104528823A discloses a method for preparing zirconia powder, which comprises subjecting a zirconium-containing precursor solution with a certain concentration to hydrolysis reaction at a specific temperature and pressure to generate a precipitate, collecting the precipitate, centrifugally washing, adding a certain molar amount of yttrium chloride to prepare slurries with different concentrations, drying and calcining to obtain tetragonal zirconia powder. The powder prepared by the method has high purity, the mechanical property of the pressed sintered body is good, and the relative density is high (reaching about 99.5%). However, the hydrolysis reaction time in the whole preparation process is long, the particle size distribution range of the product is wide, and the introduction of chloride ions in the additive can cause the increase of energy consumption in the subsequent washing process.
Patent document CN105503178A discloses a method for preparing fully stabilized zirconia powder by low-temperature normal-pressure rapid sintering, which comprises mixing a soluble zirconium salt solution with a stabilizer solution according to a certain ratio, then precipitating with an alkali solution, washing and drying the precipitate to obtain a precursor, mixing the precursor with a molten salt solution, drying, grinding and sieving to obtain the product. The product prepared by the method has larger particle size and poorer uniformity and dispersibility, and the relative density after sintering is lower than 99.3 percent.
Disclosure of Invention
The invention mainly aims to provide high-sintering-activity zirconium oxide powder and a preparation method thereof, and aims to prepare pure tetragonal-phase zirconium oxide powder which is small in particle size, good in uniformity and high in sintering activity by combining a liquid-phase precipitation method and a hydrothermal method.
In order to achieve the above object, the present invention provides a method for preparing a high sintering activity zirconia powder, comprising the following steps:
(1) mixing a zirconium oxide solution and a yttrium nitrate solution to obtain a mixed solution, mixing the mixed solution with ammonia water, stirring and aging to obtain hydroxide precursor slurry;
(2) washing and drying the hydroxide precursor slurry to obtain dry gel;
(3) crushing the xerogel, adding water and carrying out ball milling to obtain wet gel;
(4) adding a mineralizer and water into the wet gel, diluting the mineralizer to 0.5-2mol/L, and performing hydrothermal reaction to obtain precursor powder;
(5) and calcining the precursor powder to obtain the zirconia powder with high sintering activity.
In the step (1), the mixed solution is mixed with ammonia water, and liquid phase precipitation reaction is carried out in the processes of stirring and aging to obtain hydroxide precursor slurry; centrifugally washing the hydroxide precursor slurry with deionized water in the step (2) until the conductivity of the supernatant is less than 100 mus/cm, and drying the precipitate to obtain dry gel; crushing the dry gel into powder by using a powder grinding machine, and adding water into the powder for ball milling to obtain wet gel; then adding a mineralizer to carry out hydrothermal reaction so as to prepare the zirconium oxide powder.
Pure tetragonal zirconia is difficult to exist alone at normal temperature, and internal stress can be balanced and eliminated by doping a certain amount of metal yttrium ions to replace crystal lattice vacancies occupied, so that a stable doped tetragonal structure is obtained. Experiments prove that the synthesis of tetragonal zirconia can be ensured only when the lowest doping amount of yttrium is 1.7 mol%, and meanwhile, the small-particle tetragonal zirconia is more favorable for improving the properties such as strength, toughness, wear resistance and the like. The invention adopts the idea of combining the liquid phase precipitation method and the hydrothermal method, and carries out the conversion of dry gel and wet gel after the liquid phase precipitation and before the hydrothermal reaction, so that metal ions are more easily and uniformly dissolved into crystal lattices of the zirconium oxide in the preparation process, and the uniformly dispersed tetragonal zirconium oxide powder is prepared. The particle size of the zirconia powder prepared by the technical scheme of the invention is 50-150nm, the uniformity is good, the minimum doping amount of yttrium can reach 1.7% mol, and the sintering activity is high.
In the preparation process, the raw materials only comprise zirconium oxychloride, yttrium nitrate and ammonia water, and no other additives exist, so that the purchase cost and the subsequent washing and treatment cost of the nitrogen-containing wastewater are reduced. In addition, the procedures of neutralization and precipitation, washing and drying, crushing and ball milling and the like in the process have low requirements on equipment and operation, are simple and easy to control, have low potential danger and are suitable for large-scale industrial production.
As a preferred embodiment of the method for preparing the high sintering activity zirconia powder of the present invention, in the step (1), the concentration of the zirconia solution is 2 to 5mol/L, the concentration of the yttrium nitrate solution is 0.5 to 4mol/L, and the volume ratio of the zirconia solution to the yttrium nitrate solution is the zirconia solution: yttrium nitrate solution 8-100: 1.
Through a large number of experimental researches, the inventor finds that the zirconia powder prepared by adopting the raw materials with the concentrations and the volume ratios has better uniformity of particles and better sintering activity.
As a preferable embodiment of the method for producing a highly sintered active zirconia powder of the present invention, the concentration of the aqueous ammonia in the step (1) is 2 to 6 mol/L.
As a preferred embodiment of the preparation method of the high sintering activity zirconia powder, in the step (1), the stirring temperature is 25-60 ℃, the aging temperature is 30-50 ℃, the aging time is 2-24h, and the pH value of the hydroxide precursor slurry is 7.0-10.
The inventor researches and discovers that under the process conditions, the nucleation rate and the growth rate of the hydroxide particles are higher, so that the sizes of the obtained hydroxide particles are more uniform, and the precipitation is complete.
As a preferred embodiment of the preparation method of the high sintering activity zirconia powder of the invention, the drying temperature in the step (2) is 115-125 ℃.
The inventor finds that the drying dehydration rate can influence the agglomeration effect among the particles, when the drying temperature is controlled to be 115-125 ℃, the higher drying efficiency can be ensured, and the agglomeration among the particles can be avoided at the drying temperature.
As a preferable embodiment of the method for preparing the high sintering activity zirconia powder of the present invention, the mineralizer in step (4) includes at least one of concentrated ammonia water, ammonium carbonate, and sodium carbonate.
The principle of hydrothermal preparation is the process of dissolving solute firstly and then separating out, and the addition of mineralizer can accelerate the dissolution and separation rate and balance the dissolution and separation rates of different ions. The inventor finds that the uniformity and sintering activity of the finally prepared tetragonal zirconia powder particles can be improved by selecting at least one of concentrated ammonia water, ammonium carbonate and sodium carbonate as a mineralizer.
As a preferred embodiment of the method for preparing the high sintering activity zirconia powder of the present invention, the conditions of the hydrothermal reaction in the step (4) are as follows: the reaction temperature is 150 ℃ and 170 ℃, and the reaction time is 22-30 h.
The hydrothermal process is a reaction process of dissolving the solute first and then precipitating the solute, and the inventor finds that under the reaction conditions, the reaction process can be accelerated, and excessive energy waste can not be caused.
As a preferred embodiment of the method for preparing a highly sintered active zirconia powder according to the present invention, the calcination conditions in step (5) are: the calcination temperature is 900-1000 ℃, and the calcination time is 2.5-4 h.
The inventors have found that, by controlling the calcination conditions within the above range, the powder particles can be sintered to a certain extent while ensuring removal of water in the powder, and a suitable specific surface area can be achieved, so that the subsequent green body can be sintered better after molding.
In a second aspect, the invention further provides a high sintering activity zirconia powder prepared by the preparation method of any one of the above.
As a preferred embodiment of the high sintering activity zirconia powder, the zirconia powder is in a tetragonal crystal form, the particle size of the powder is 50-150nm, and the sintering density at 1350-1450 ℃ is 6.051-6.083g/cm3
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts the idea of combining the liquid phase precipitation method and the hydrothermal method, and carries out the conversion of dry gel and wet gel after the liquid phase precipitation and before the hydrothermal reaction, so that metal ions are more easily and uniformly dissolved into crystal lattices of the zirconium oxide in the preparation process, and the uniformly dispersed tetragonal zirconium oxide powder is prepared. The particle size of the zirconia powder prepared by the technical scheme of the invention is 50-150nm, the uniformity is good, the minimum doping amount of yttrium can reach 1.7% mol, and the sintering activity is high.
(2) In the preparation process, the raw materials only comprise zirconium oxychloride, yttrium nitrate and ammonia water, and no other additives exist, so that the purchase cost and the subsequent washing and treatment cost of the nitrogen-containing wastewater are reduced. In addition, the procedures of neutralization and precipitation, washing and drying, crushing and ball milling and the like in the process have low requirements on equipment and operation, are simple and easy to control, have low potential danger and are suitable for large-scale industrial production.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of high sintering activity zirconia powder according to the present invention;
FIG. 2 is an XRD spectrum of zirconia powders prepared in examples 1, 3, 4 and 6 of the present invention;
FIG. 3 is an SEM photograph of a zirconia powder prepared in example 3 of the present invention;
FIG. 4 is an SEM photograph of the zirconia powder prepared in example 4 of the invention.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Example 1
The preparation method of the zirconium oxide powder in the embodiment comprises the following steps:
(1) mixing a 2mol/L zirconia solution and a 0.5mol/L yttrium nitrate solution to obtain a mixed solution, wherein the volume ratio of the zirconia solution to the yttrium nitrate solution in the mixed solution is zirconia solution: heating the mixed solution to 35 ℃, pouring the mixed solution into 2mol/L ammonia water, stirring for 1h until the pH value of the mixture system is 7.5, aging for 12h at 35 ℃, and removing the supernatant to obtain hydroxide precursor slurry;
(2) centrifugally washing the hydroxide precursor slurry by using deionized water until the conductivity of the supernatant is less than 100 mu s/cm, and drying at 120 ℃ to obtain dry gel;
(3) crushing the dried gel, adding water and carrying out ball milling to obtain wet gel with the solid content of 65%;
(4) adding concentrated ammonia water as a mineralizer into the wet gel, adding water to dilute the concentrated ammonia water to 1mol/L, carrying out hydrothermal reaction at 150 ℃ for 24h, washing and drying to obtain precursor powder;
(5) and calcining the precursor powder at 900 ℃ for 3h to obtain the high-sintering-activity zirconium oxide powder.
The XRD spectrum of the sample prepared in this example is shown in fig. 2, and it can be seen from fig. 2 that the zirconia powder prepared in this example is pure tetragonal zirconia.
Example 2
The preparation method of the zirconium oxide powder in the embodiment comprises the following steps:
(1) mixing a 3mol/L zirconia solution and a 1mol/L yttrium nitrate solution to obtain a mixed solution, wherein the volume ratio of the zirconia solution to the yttrium nitrate solution in the mixed solution is zirconia solution: heating the mixed solution to 35 ℃, pouring the mixed solution into 2mol/L ammonia water, stirring for 1h until the pH value of the mixture system is 8.5, aging for 12h at 35 ℃, and removing the supernatant to obtain hydroxide precursor slurry;
(2) centrifugally washing the hydroxide precursor slurry by using deionized water until the conductivity of the supernatant is less than 100 mu s/cm, and drying at 120 ℃ to obtain dry gel;
(3) crushing the dried gel, adding water and carrying out ball milling to obtain wet gel with the solid content of 65%;
(4) adding concentrated ammonia water as a mineralizer into the wet gel, adding water to dilute the concentrated ammonia water to 2mol/L, carrying out hydrothermal reaction at 150 ℃ for 24h, washing and drying to obtain precursor powder;
(5) and calcining the precursor powder at 950 ℃ for 3h to obtain the high-sintering-activity zirconium oxide powder.
Example 3
The preparation method of the zirconium oxide powder in the embodiment comprises the following steps:
(1) mixing a 4mol/L zirconia solution and a 2mol/L yttrium nitrate solution to obtain a mixed solution, wherein the volume ratio of the zirconia solution to the yttrium nitrate solution in the mixed solution is zirconia solution: heating the mixed solution to 55 ℃, pouring the mixed solution into 4mol/L ammonia water, stirring for 1h until the pH value of the mixture system is 9.0, aging for 24h at 35 ℃, and removing the supernatant to obtain hydroxide precursor slurry;
(2) centrifugally washing the hydroxide precursor slurry by using deionized water until the conductivity of the supernatant is less than 100 mu s/cm, and drying at 120 ℃ to obtain dry gel;
(3) crushing the dried gel, adding water and carrying out ball milling to obtain wet gel with the solid content of 65%;
(4) adding ammonium carbonate as a mineralizer into the wet gel, adding water to dilute the ammonium carbonate to 1mol/L, carrying out hydrothermal reaction at 160 ℃ for 24h, washing and drying to obtain precursor powder;
(5) and calcining the precursor powder at 1000 ℃ for 3h to obtain the high-sintering activity zirconium oxide powder.
The XRD spectrum of the sample prepared in this example is shown in fig. 2, and it can be seen from fig. 2 that the zirconia powder prepared in this example is pure tetragonal zirconia;
the SEM photograph of the sample prepared in this example is shown in fig. 3, and it can be seen from fig. 3 that the zirconia powder prepared in this example has uniform particles.
Example 4
The preparation method of the zirconium oxide powder in the embodiment comprises the following steps:
(1) mixing a 2mol/L zirconia solution and a 4mol/L yttrium nitrate solution to obtain a mixed solution, wherein the volume ratio of the zirconia solution to the yttrium nitrate solution in the mixed solution is zirconia solution: heating the mixed solution to 55 ℃ and then pouring the mixed solution into 5mol/L ammonia water to stir for 1h until the pH value of the mixture system is 9.5, then aging for 24h at 35 ℃, and removing the supernatant to obtain hydroxide precursor slurry;
(2) centrifugally washing the hydroxide precursor slurry by using deionized water until the conductivity of the supernatant is less than 100 mu s/cm, and drying at 120 ℃ to obtain dry gel;
(3) crushing the dried gel, adding water and carrying out ball milling to obtain wet gel with the solid content of 65%;
(4) adding ammonium carbonate as a mineralizer into the wet gel, adding water to dilute the ammonium carbonate to 2mol/L, carrying out hydrothermal reaction at 160 ℃ for 24h, washing and drying to obtain precursor powder;
(5) and calcining the precursor powder at 1000 ℃ for 3h to obtain the high-sintering activity zirconium oxide powder.
The XRD spectrum of the sample prepared in this example is shown in fig. 2, and it can be seen from fig. 2 that the zirconia powder prepared in this example is pure tetragonal zirconia;
the SEM photograph of the sample prepared in this example is shown in fig. 4, and it can be seen from fig. 4 that the zirconia powder prepared in this example has uniform particles.
Example 5
The preparation method of the zirconium oxide powder in the embodiment comprises the following steps:
(1) mixing a 2mol/L zirconia solution and a 4mol/L yttrium nitrate solution to obtain a mixed solution, wherein the volume ratio of the zirconia solution to the yttrium nitrate solution in the mixed solution is zirconia solution: heating the mixed solution to 60 ℃ and then pouring the mixed solution into 5mol/L ammonia water to stir for 1h until the pH value of the mixture system is 9.5, then aging for 24h at 50 ℃, and removing the supernatant to obtain hydroxide precursor slurry;
(2) centrifugally washing the hydroxide precursor slurry by using deionized water until the conductivity of the supernatant is less than 100 mu s/cm, and drying at 120 ℃ to obtain dry gel;
(3) crushing the dried gel, adding water and carrying out ball milling to obtain wet gel with the solid content of 65%;
(4) adding sodium carbonate as a mineralizer into the wet gel, adding water to dilute the sodium carbonate to 0.5mol/L, carrying out hydrothermal reaction at 150 ℃ for 24h, washing and drying to obtain precursor powder;
(5) and calcining the precursor powder at 1000 ℃ for 3h to obtain the high-sintering activity zirconium oxide powder.
Example 6
The preparation method of the zirconium oxide powder in the embodiment comprises the following steps:
(1) mixing a 3mol/L zirconia solution and a 4mol/L yttrium nitrate solution to obtain a mixed solution, wherein the volume ratio of the zirconia solution to the yttrium nitrate solution in the mixed solution is zirconia solution: heating the mixed solution to 60 ℃ and then pouring the mixed solution into 6mol/L ammonia water to stir for 1h until the pH value of the mixture system is 9.5, then aging for 24h at 50 ℃, and removing the supernatant to obtain hydroxide precursor slurry;
(2) centrifugally washing the hydroxide precursor slurry by using deionized water until the conductivity of the supernatant is less than 100 mu s/cm, and drying at 120 ℃ to obtain dry gel;
(3) crushing the dried gel, adding water and carrying out ball milling to obtain wet gel with the solid content of 65%;
(4) adding sodium carbonate as a mineralizer into the wet gel, adding water to dilute the sodium carbonate to 1mol/L, carrying out hydrothermal reaction at 170 ℃ for 24h, washing and drying to obtain precursor powder;
(5) and calcining the precursor powder at 1000 ℃ for 3h to obtain the high-sintering activity zirconium oxide powder.
The XRD spectrum of the sample prepared in this example is shown in fig. 2, and it can be seen from fig. 2 that the zirconia powder prepared in this example is pure tetragonal zirconia.
Comparative example 1
This comparative example differs from example (3) in that: no mineralizer was added in step (4) of this comparative example.
Comparative example 2
This comparative example differs from example (4) in that: in the step (2) of the comparative example, the hydroxide precursor slurry is centrifugally washed by deionized water until the conductivity of the supernatant is less than 100 mus/cm, and then the step (4) and the subsequent operation processes are directly carried out.
Effect example 1
The zirconia powders prepared in examples 1 to 6 and comparative examples 1 to 2 were subjected to an analysis test, and the test results are shown in table 1 below.
TABLE 1 results of performance test of zirconia powders prepared in examples 1 to 6 and comparative examples 1 to 2
Figure BDA0003083892230000081
Figure BDA0003083892230000091
As is clear from the data in Table 1, the crystal phases of the zirconia powders prepared in examples 1 to 6 were tetragonal phases, but the zirconia powders having pure tetragonal phases could not be prepared in comparative examples 1 and 2.
Effect example 2
The zirconia powder prepared in the examples 1-6 and the comparative examples 1-2 is pressed into tablets, is subjected to cold isostatic pressing treatment at 180MPa, and is sintered and insulated for 3 hours at 1450 ℃ in a muffle furnace to prepare a sintered body. The density of the sintered body was measured as shown in table 2 below.
TABLE 2 sintered density of the zirconia powders obtained in examples 1 to 6 and comparative examples 1 to 2
Sintering temperature/. degree.C Sintered density/(g/cm)3)
Example 1 1350 6.075
Example 2 1400 6.083
Example 3 1420 6.079
Example 4 1420 6.072
Example 5 1450 6.064
Example 6 1450 6.051
Comparative example 1 1350 5.013
Comparative example 2 1420 5.436
As can be seen from the data in Table 2, the sintering density of the zirconia powder prepared in the embodiments 1-6 of the present application at 1350-.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. A preparation method of high sintering activity zirconia powder is characterized by comprising the following steps:
(1) mixing a zirconium oxide solution and a yttrium nitrate solution to obtain a mixed solution, mixing the mixed solution with ammonia water, stirring and aging to obtain hydroxide precursor slurry;
(2) washing and drying the hydroxide precursor slurry to obtain dry gel;
(3) crushing the xerogel, adding water and carrying out ball milling to obtain wet gel;
(4) adding a mineralizer and water into the wet gel, diluting the mineralizer to 0.5-2mol/L, and performing hydrothermal reaction to obtain precursor powder;
(5) and calcining the precursor powder to obtain the zirconia powder with high sintering activity.
2. The method for preparing a zirconia powder with high sintering activity according to claim 1, wherein the concentration of the zirconia solution in step (1) is 2 to 5mol/L, the concentration of the yttrium nitrate solution is 0.5 to 4mol/L, and the volume ratio of the zirconia solution to the yttrium nitrate solution is the zirconia solution: yttrium nitrate solution 8-100: 1.
3. The method for preparing a zirconia powder having a high sintering activity according to claim 1, wherein the concentration of the aqueous ammonia in the step (1) is 2 to 6 mol/L.
4. The method for preparing zirconia powder with high sintering activity according to claim 1, wherein in the step (1), the stirring temperature is 25-60 ℃, the aging temperature is 30-50 ℃, the aging time is 2-24h, and the pH value of the hydroxide precursor slurry is 7.0-10.
5. The method for preparing zirconia powder with high sintering activity as claimed in claim 1, wherein the drying temperature in step (2) is 115-125 ℃.
6. The method for preparing a high sintering activity zirconia powder according to claim 1 wherein the mineralizer in step (4) comprises at least one of concentrated aqueous ammonia, ammonium carbonate and sodium carbonate.
7. The method for preparing zirconia powder with high sintering activity according to claim 1, wherein the hydrothermal reaction conditions in the step (4) are as follows: the reaction temperature is 150 ℃ and 170 ℃, and the reaction time is 22-30 h.
8. The method for preparing a zirconia powder with high sintering activity according to claim 1, wherein the calcination conditions in the step (5) are as follows: the calcination temperature is 900-1000 ℃, and the calcination time is 2.5-4 h.
9. The zirconia powder with high sintering activity prepared by the preparation method according to any one of claims 1 to 8.
10. The zirconia powder with high sintering activity as claimed in claim 9, wherein the zirconia powder is tetragonal type, the particle size of the powder is 50-150nm, and the sintering density at 1350-1450 ℃ is 6.051-6.083g/cm3
CN202110581412.9A 2021-05-26 2021-05-26 High-sintering-activity zirconium oxide powder and preparation method thereof Pending CN113200567A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110581412.9A CN113200567A (en) 2021-05-26 2021-05-26 High-sintering-activity zirconium oxide powder and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110581412.9A CN113200567A (en) 2021-05-26 2021-05-26 High-sintering-activity zirconium oxide powder and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113200567A true CN113200567A (en) 2021-08-03

Family

ID=77023375

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110581412.9A Pending CN113200567A (en) 2021-05-26 2021-05-26 High-sintering-activity zirconium oxide powder and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113200567A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113461051A (en) * 2021-08-17 2021-10-01 焦作市维纳科技有限公司 Preparation method of nano zirconia powder
CN113894112A (en) * 2021-09-14 2022-01-07 先导薄膜材料有限公司 Indium foil surface treatment method
CN114014651A (en) * 2021-09-10 2022-02-08 王必庆 Method for producing nano composite zirconia powder by hydrothermal method
CN116573934A (en) * 2023-05-30 2023-08-11 先导薄膜材料(淄博)有限公司 Recycling method of zirconia substrate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102337085A (en) * 2011-10-10 2012-02-01 上海华明高纳稀土新材料有限公司 Preparation method of composite cerium-zirconium oxide polishing powder
CN105967687A (en) * 2016-07-14 2016-09-28 上海纳米技术及应用国家工程研究中心有限公司 Grain-composition zirconia powder preparation and ceramic sintering method
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102337085A (en) * 2011-10-10 2012-02-01 上海华明高纳稀土新材料有限公司 Preparation method of composite cerium-zirconium oxide polishing powder
CN105967687A (en) * 2016-07-14 2016-09-28 上海纳米技术及应用国家工程研究中心有限公司 Grain-composition zirconia powder preparation and ceramic sintering method
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

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TIAN MA ET AL.: "Preparation of spherical zirconia powder in microemulsion system and its densification behavior", 《MATERIALS & DESIGN》 *
马洋洋等: "液相法制备纳米ZrO2粉体的研究进展", 《粉末冶金工业》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113461051A (en) * 2021-08-17 2021-10-01 焦作市维纳科技有限公司 Preparation method of nano zirconia 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
CN114014651A (en) * 2021-09-10 2022-02-08 王必庆 Method for producing nano composite zirconia powder by hydrothermal method
CN113894112A (en) * 2021-09-14 2022-01-07 先导薄膜材料有限公司 Indium foil surface treatment method
CN116573934A (en) * 2023-05-30 2023-08-11 先导薄膜材料(淄博)有限公司 Recycling method of zirconia substrate

Similar Documents

Publication Publication Date Title
CN113200567A (en) High-sintering-activity zirconium oxide powder and preparation method thereof
CN103708831B (en) Yttria-stabilized zirconia powder and preparation method thereof
CN101302019B (en) Method for preparing rare earth-doped yag nano-powder by partial liquid phase precipitation method
CN110203969A (en) A kind of high dispersive cubic phase nano zirconium oxide and preparation method thereof
CN110668452A (en) Preparation of SiO from fly ash2-Al2O3Method of compounding aerogel materials
CN109704731B (en) Preparation method of nano yttrium-stabilized zirconia-alumina composite powder
CN102807243B (en) Aluminum hydroxide gel
CN110629288B (en) Method for preparing whisker-shaped gadolinium aluminate powder material by hydrothermal technology
CN114988886B (en) Preparation method of high-purity alpha-alumina powder capable of being sintered at low temperature
CN108511797B (en) Li7La3Zr2O12Solid electrolyte preparation method
CN112266244A (en) Preparation method of high-sintering-activity zirconium oxide powder
CN104557041A (en) Preparation method of yttria-base transparent ceramic
CN109721357A (en) A kind of Zirconium oxide powder and its preparation method and application that the nanometer yttrium that monodisperse granularity is controllable is stable
CN102241516A (en) Method for preparing Li4SiO4 ceramic powder by water-based sol-gel process
CN103496727B (en) Preparation method for microcrystal alpha-Al2O3 aggregation
CN105693243A (en) Preparation method of medium-dielectric-constant high-performance microwave dielectric ceramic
Li et al. Sc2O3 nanopowders via hydroxyl precipitation: effects of sulfate ions on powder properties
CN105129834B (en) A kind of nanometer level RE oxide raw powder's production technology
JP2868176B2 (en) Method for producing rare earth element oxide powder
CN112573570A (en) Scandium-cerium-doped zirconium oxide superfine powder and preparation method thereof
CN116199270B (en) Treatment process for reducing wastewater in cobalt oxide production process
CN103614139B (en) Reverse co-precipitation is adopted to prepare Gd 2ti 2o 7: the method for Ce nano-luminescent powder body
CN115196970A (en) Preparation method of high-fluidity AlON spherical powder
CN106635007B (en) A kind of preparation method of extra small scale rare earth doped yttrium oxide base nano-phosphor
CN101525151B (en) Manufacturing technique for high-purity electronic grade strontium titanate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20210803

RJ01 Rejection of invention patent application after publication