CN112266244A - Preparation method of high-sintering-activity zirconium oxide powder - Google Patents
Preparation method of high-sintering-activity zirconium oxide powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 66
- 238000005245 sintering Methods 0.000 title claims abstract description 45
- 230000000694 effects Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 title description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 108
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000000498 ball milling Methods 0.000 claims abstract description 19
- 239000002244 precipitate Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 15
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims description 34
- 239000002002 slurry Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000012467 final product Substances 0.000 claims description 9
- 229910001410 inorganic ion Inorganic materials 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- KKTCWAXMXADOBB-UHFFFAOYSA-N azanium;hydrogen carbonate;hydrate Chemical compound [NH4+].O.OC([O-])=O KKTCWAXMXADOBB-UHFFFAOYSA-N 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 150000003754 zirconium Chemical class 0.000 claims description 5
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 11
- 238000001514 detection method Methods 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- -1 rare earth nitric acid compound Chemical class 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of high-sintering activity zirconia powder, relates to the technical field of ceramic powder preparation, and is provided based on the problems that the existing zirconia powder is easy to agglomerate, unstable in crystal form and difficult to sinter. The invention comprises the following steps: zirconium inorganic salt is used as a main raw material, metal M nitrate is used as an addition auxiliary agent to prepare basic precipitated salt containing zirconium and M, and then the zirconium oxide nano powder with high dispersion tetragonal phase is prepared through ball milling, hydrothermal reaction and high-temperature calcination. The white precipitate obtained by the method is non-colloidal, contains less water, has small capillary force effect in the drying process, and is easy to obtain loose precursor powder with less agglomeration; and through a two-step synthesis method, the dried gel is crushed and ball-milled and then is subjected to hydrothermal treatment, and the auxiliary agent metal ions are more easily and uniformly dissolved in the crystal lattice of the zirconia in a high-pressure low-temperature environment, so that the prepared zirconia powder has uniform particles and good dispersibility, and the sintering performance of the zirconia powder is obviously improved compared with that of industrial zirconia.
Description
Technical Field
The invention relates to the technical field of ceramic powder preparation, in particular to a preparation method of high-sintering activity zirconium oxide powder.
Background
Zirconia, 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, so that zirconia is widely applied to the fields of structural ceramics, functional ceramics, refractory materials and the like. Moreover, zirconia stabilized by the crystal form stabilizer can be applied to ceramic capacitors, gas sensitive elements, catalysts and the like, so that the demand of the zirconia is increasing in society. 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 are mostly a solid phase method, a liquid phase method, a gas phase method and a hydrothermal method, but the powder prepared by the former three methods has the problems of serious agglomeration, uneven distribution, uncontrollable crystal structure, poor sintering activity and the like.
Patent CN110550952A discloses a zirconia ceramic powder and a preparation method thereof. Mixing a rare earth nitric acid compound, zirconia, alumina, absolute ethyl alcohol and water by adopting a mixed oxide method, uniformly stirring to obtain a mixture, and performing ball milling treatment on the mixture to obtain uniform slurry. And drying the uniform slurry to obtain blocky zirconia ceramic coarse grinding powder, grinding the blocky zirconia ceramic coarse grinding powder into powder, heating to roast the powder to obtain roasted zirconia ceramic powder, 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. Chinese patent CN104787801A discloses a method for preparing zirconium oxide, which comprises mixing zirconium oxychloride with sodium hydroxide, reacting in ionic liquid sodium trifluoromethanesulfonate at 260-300 deg.C for 4-20h, washing and drying to obtain the final product. The product prepared by the method has uniform particle size and good dispersibility, but has large energy consumption of high-temperature reaction and higher equipment requirement, and does not introduce sintering activity. Patent CN1524795A discloses a method for preparing zirconium oxide, which adopts a precipitation method to uniformly mix and hydrolyze a soluble zirconium salt aqueous solution and a soluble strong alkaline aqueous solution to obtain a zirconium hydroxide hydrosol, and then the zirconium hydroxide hydrosol is subjected to aging treatment, filtration, washing, drying and roasting to obtain a final product. The method has simple process operation, can prepare powder with higher specific surface, but does not analyze and introduce the final sintering performance of the powder. Patent CN109809482A discloses a method for preparing zirconia, which adopts a hydrothermal method, and prepares powders with different morphologies by adding a borofluoride mineralizer into a zirconium oxychloride solution and then regulating the concentration of the mineralizer. The method is simple in synthesis, and the prepared product is dispersed and does not agglomerate. But no analysis is made on the final sintering activity of the product.
The research adopts a single method to prepare the zirconia powder, and the steps are relatively complicated, the powder is easy to agglomerate, the crystal form is unstable, and the sintering is difficult.
Disclosure of Invention
The invention solves the technical problems that the zirconia powder prepared by the existing zirconia powder preparation method has more complicated steps, the powder is easy to agglomerate, the crystal form is unstable and the sintering is difficult.
The invention adopts the following technical scheme to solve the technical problems:
the invention provides a preparation method of high-sintering activity zirconium oxide powder, which comprises the following steps:
(1) preparation of Zr and M basic precipitated salts: taking inorganic zirconium salt as a main raw material, metal M nitrate as an addition auxiliary agent and ammonium bicarbonate as a precipitator, and respectively preparing aqueous solutions with certain concentrations; uniformly mixing a zirconium inorganic salt aqueous solution and a metal M nitrate aqueous solution according to the mass ratio of 16:1 to prepare a Zr-M salt mixed solution;
(2) according to the mass ratio of 1:1, dropwise adding the prepared Zr-M salt mixed solution into the ammonium bicarbonate water solution while stirring, and aging for 0-24h at 10-60 ℃ to obtain white precipitate;
(3) carrying out suction filtration washing on the prepared white precipitate by using deionized water to remove residual inorganic ions, transferring the filtered and washed precipitate into an oven, and drying at the temperature of 100 ℃ and 160 ℃ to prepare dry gel;
(4) and carrying out ball milling and crushing on the prepared xerogel to prepare slurry, and reserving for later use.
(5) Hydrothermal reaction: and (4) adding deionized water into the slurry prepared in the step (4) for dilution to obtain a feed liquid with the solid content of 25%, adding an ammonia water solution into the feed liquid according to the volume ratio of 3:1, fully stirring, injecting into a reaction kettle, and reacting at 100-200 ℃ for 12-48h to obtain the hydrothermal powder.
(6) High-temperature calcination: calcining the prepared hydrothermal powder at high temperature of 800-1100 ℃ for 1-5h to obtain the final product t-ZrO2。
The white precipitate obtained by the method is non-colloidal, contains less water, has small capillary force effect in the drying process, and is easy to obtain loose precursor powder with less agglomeration; and through a two-step synthesis method, the dried gel is crushed and ball-milled and then is subjected to hydrothermal treatment, and the auxiliary agent metal ions are more easily and uniformly dissolved into the crystal lattice of the zirconia in a high-pressure low-temperature environment, so that the prepared zirconia powder has uniform particles and good dispersibility, and the sintering performance of the zirconia powder is obviously improved compared with that of industrial zirconia.
Because the high and low calcination temperature has great influence on the particle size and sintering performance of the obtained zirconia powder, the calcination temperature is controlled to be between 800 ℃ and 1100 ℃, and the obtained zirconia powder is completely converted into a tetragonal phase and has a primary grain below 200nm, so that the zirconia powder has high sintering performance.
Preferably, the inorganic salt of zirconium in step (1) includes one of zirconium tetrachloride, zirconium oxychloride and zirconium nitrate.
Preferably, M in the metal M nitrate in the step (1) includes one of Ca, Mg and Y.
Preferably, the inorganic salt of zirconium in the step (1) is prepared into an aqueous solution with a concentration of 0.2-2 g/mol.
Preferably, the metal M nitrate in step (1) is prepared into an aqueous solution with a concentration of 0.1-1 g/mol.
Preferably, the ammonium bicarbonate in the step (1) is prepared into an aqueous solution with the concentration of 2-4 g/mol.
Preferably, the suction filtration and washing times in the step (2) are 6-8, and the concentration of inorganic ions is controlled to be below 10 ppm; the existence of inorganic ions is easy to cause hard agglomeration of precipitates in the drying process, thereby influencing subsequent sintering, so repeated washing is needed, and the concentration of the inorganic ions is controlled to be below 10 ppm.
Preferably, the mass ratio of the materials crushed by ball milling in the step (4) is 1-1.5, and the material ball ratio is 0.2-0.6.
Preferably, the ball milling rotation speed of the ball milling crushing in the step (4) is 200-; .
Preferably, the concentration of the ammonia water in the step (5) is 1-2 mol/L.
The invention has the beneficial effects that:
(1) the white precipitate obtained by the method is non-colloidal, contains less water, has small capillary force effect in the drying process, and is easy to obtain loose precursor powder with less agglomeration; and through a two-step synthesis method, the dried gel is crushed and ball-milled and then is subjected to hydrothermal treatment, and the auxiliary agent metal ions are more easily and uniformly dissolved into the crystal lattice of the zirconia in a high-pressure low-temperature environment, so that the prepared zirconia powder has uniform particles and good dispersibility, and the sintering performance of the zirconia powder is obviously improved compared with that of industrial zirconia.
(2) Because the high and low calcination temperature has great influence on the particle size and sintering performance of the obtained zirconia powder, the calcination temperature is controlled to be between 800 ℃ and 1100 ℃, and the obtained zirconia powder is completely converted into a tetragonal phase and has a primary grain below 200nm, so that the zirconia powder has high sintering performance.
(3) The raw materials used in the method are industrial raw materials, the raw materials are easy to obtain, the cost is low, the process is simple, the equipment requirement is low, the product purity is high, the quality of the obtained zirconia product is high, and the method is suitable for preparing high-end zirconia products, so the method has good market prospect.
Drawings
FIG. 1 shows t-ZrO which is a product of examples 1 and 3 of the present invention2XRD spectrum of (1);
FIG. 2 shows t-ZrO which is a product of examples 1 and 3 of the present invention2SEM picture of (1);
FIG. 3 is a graph showing sintering curves of the products prepared in examples 1 to 3 of the present invention and comparative example 1.
Detailed Description
The present invention will be described in further detail below.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
A preparation method of high sintering activity zirconia powder comprises the following steps:
(1) preparation of Zr and M basic precipitated salts: zirconium oxychloride is used as a main raw material, magnesium nitrate is used as an addition agent, and ammonium bicarbonate is used as a precipitator, and a zirconium inorganic salt aqueous solution with the concentration of 0.2g/mol, a metal M nitrate aqueous solution with the concentration of 0.1g/mol and an aqueous solution with the concentration of 2g/mol are respectively prepared; uniformly mixing a zirconium inorganic salt aqueous solution and a metal M nitrate aqueous solution according to the mass ratio of 16:1 to prepare a Zr-M salt mixed solution;
(2) according to the mass ratio of 1:1, dropwise adding the prepared Zr-M salt mixed solution into the ammonium bicarbonate water solution while stirring, and aging for 6-18h at the temperature of 20-40 ℃ to obtain white precipitate;
(3) carrying out suction filtration and washing on the prepared white precipitate by using deionized water to remove residual inorganic ions, transferring the filtered and washed precipitate into an oven, and drying at 120 ℃ to prepare xerogel;
(4) carrying out ball milling and crushing on the prepared xerogel, controlling the mass ratio of material to water to be 1.2, the material-ball ratio to be 0.3, the ball milling rotation speed to be 200r/min, and the ball milling time to be 12h, thus preparing slurry which is reserved for later use;
(5) hydrothermal reaction: and (4) adding deionized water into the slurry prepared in the step (3) for dilution to obtain a feed liquid with the solid content of 25%, adding an aqueous solution with the concentration of 1mol/L ammonia solution into the feed liquid according to the volume ratio of 3:1, fully stirring, injecting into a reaction kettle, and reacting at 130 ℃ for 12 hours to obtain the hydrothermal powder.
(6) High temperature calcinationAnd (3) burning: calcining the prepared hydrothermal powder at the high temperature of 900 ℃ for 3 hours to obtain a final product t-ZrO2。
The t-ZrO prepared in this example2Carrying out XRD pattern detection analysis, scanning electron microscope analysis and sintering temperature curve test: the XRD pattern detection analysis and detection result is shown in fig. 1(a), which shows that the prepared hydrothermal powder prepared in this example has been crystallized into t-ZrO 2; the results of the scanning electron microscope analysis are shown in FIG. 2(A), and the results show that t-ZrO produced in this example2The crystal grains have good sintering property at about 100 nm; as shown in FIG. 3, it can be seen from the results of the sintering profile that t-ZrO was produced in this example2Substantially complete densification was achieved at 1370 ℃.
Example 2
A preparation method of high sintering activity zirconia powder comprises the following steps:
(1) preparation of Zr and M basic precipitated salts: zirconium oxychloride is used as a main raw material, magnesium nitrate is used as an addition agent, and ammonium bicarbonate is used as a precipitator, and a zirconium inorganic salt aqueous solution with the concentration of 0.2g/mol, a metal M nitrate aqueous solution with the concentration of 0.1g/mol and an aqueous solution with the concentration of 2g/mol are respectively prepared; uniformly mixing a zirconium inorganic salt aqueous solution and a metal M nitrate aqueous solution according to the mass ratio of 16:1 to prepare a Zr-M salt mixed solution;
(2) according to the mass ratio of 1:1, dropwise adding the prepared Zr-M salt mixed solution into the ammonium bicarbonate water solution while stirring, and aging for 6-18h at the temperature of 20-40 ℃ to obtain white precipitate;
(3) carrying out suction filtration and washing on the prepared white precipitate by using deionized water to remove residual inorganic ions, transferring the filtered and washed precipitate into an oven, and drying at 140 ℃ to prepare dry gel;
(4) carrying out ball milling and crushing on the prepared xerogel, controlling the mass ratio of material to water to be 1.2, the material-ball ratio to be 0.4, the ball milling rotation speed to be 300r/min, and the ball milling time to be 12h, thus preparing slurry which is reserved for later use;
(5) hydrothermal reaction: and (4) adding deionized water into the slurry prepared in the step (3) for dilution to obtain a feed liquid with the solid content of 25%, adding an aqueous solution with the concentration of 1mol/L ammonia solution into the feed liquid according to the volume ratio of 3:1, fully stirring, injecting into a reaction kettle, and reacting at 150 ℃ for 24 hours to obtain the hydrothermal powder.
(6) High-temperature calcination: calcining the prepared hydrothermal powder at the high temperature of 800 ℃ for 5 hours to obtain a final product t-ZrO2。
The product prepared in this example was t-ZrO2Sintering analysis was conducted, and as shown in FIG. 3, it can be seen from the results of the sintering profile that t-ZrO produced in this example2Substantially complete densification is possible at 1400 ℃.
Example 3
A preparation method of high sintering activity zirconia powder comprises the following steps:
(1) preparation of Zr and M basic precipitated salts: zirconium oxychloride is used as a main raw material, magnesium nitrate is used as an addition agent, and ammonium bicarbonate is used as a precipitator, and a zirconium inorganic salt aqueous solution with the concentration of 0.2g/mol, a metal M nitrate aqueous solution with the concentration of 0.1g/mol and an aqueous solution with the concentration of 2g/mol are respectively prepared; uniformly mixing a zirconium inorganic salt aqueous solution and a metal M nitrate aqueous solution according to the mass ratio of 16:1 to prepare a Zr-M salt mixed solution;
(2) according to the mass ratio of 1:1, dropwise adding the prepared Zr-M salt mixed solution into the ammonium bicarbonate water solution while stirring, and aging for 6-18h at the temperature of 20-40 ℃ to obtain white precipitate;
(3) carrying out suction filtration and washing on the prepared white precipitate by using deionized water to remove residual inorganic ions, transferring the filtered and washed precipitate into an oven, and drying at 160 ℃ to prepare dry gel;
(4) carrying out ball milling and crushing on the prepared xerogel, controlling the mass ratio of material to water to be 1.5, the material-ball ratio to be 0.6, the ball milling rotation speed to be 500r/min, and the ball milling time to be 24h, thus preparing slurry which is reserved for later use;
(5) hydrothermal reaction: and (4) adding deionized water into the slurry prepared in the step (3) for dilution to obtain a feed liquid with the solid content of 25%, adding an aqueous solution with the concentration of 1.5mol/L ammonia solution into the feed liquid according to the volume ratio of 3:1, fully stirring, injecting into a reaction kettle, and reacting at 180 ℃ for 24 hours to obtain the hydrothermal powder.
(6) High temperatureAnd (3) calcining: calcining the prepared hydrothermal powder at the high temperature of 1000 ℃ for 2 hours to obtain a final product t-ZrO2。
The t-ZrO prepared in this example2Carrying out XRD pattern detection analysis, scanning electron microscope analysis and sintering analysis: the XRD pattern detection analysis and detection result is shown in fig. 1(B), which shows that the prepared hydrothermal powder prepared in this example has been crystallized into t-ZrO 2; the scanning electron microscope analysis result is shown in FIG. 2(B), and the result shows that the t-ZrO2 crystal grains prepared in the embodiment have good sintering property at about 100 nm; as shown in FIG. 3, it can be seen from the results of the sintering profile that t-ZrO was produced in this example2Substantially complete densification is possible at 1400 ℃.
Comparative example 1
The procedure of example 1 was repeated in this comparative example except that zirconium oxychloride was used as the main raw material, ammonium bicarbonate was used as the precipitant, the aqueous solution of 0.2g/mol zirconium inorganic salt and the aqueous solution of 2g/mol were prepared, the high temperature calcination temperature was 1100 ℃ and the high temperature calcination time was 2 hours, respectively, to obtain the final product t-ZrO2。
The product t-ZrO prepared in this comparative example2The sintering property test is carried out, and the result is shown in figure 3, and the t-ZrO prepared under the process condition of the comparative example can be seen2Is not easy to sinter.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and various process schemes having no substantial difference from the concept of the present invention are within the protection scope of the present invention.
Claims (10)
1. A preparation method of high sintering activity zirconia powder is characterized by comprising the following steps:
(1) preparation of Zr and M basic precipitated salts: taking inorganic zirconium salt as a main raw material, metal M nitrate as an addition auxiliary agent and ammonium bicarbonate as a precipitator, and respectively preparing aqueous solutions with certain concentrations; uniformly mixing a zirconium inorganic salt aqueous solution and a metal M nitrate aqueous solution according to the mass ratio of 16:1 to prepare a Zr-M salt mixed solution;
(2) according to the mass ratio of 1:1, dropwise adding the prepared Zr-M salt mixed solution into the ammonium bicarbonate water solution while stirring, and aging for 0-24h at 10-60 ℃ to obtain white precipitate;
(3) carrying out suction filtration washing on the prepared white precipitate by using deionized water to remove residual inorganic ions, transferring the filtered and washed precipitate into an oven, and drying at the temperature of 100 ℃ and 160 ℃ to prepare dry gel;
(4) carrying out ball milling and crushing on the prepared xerogel to prepare slurry, and reserving for later use;
(5) hydrothermal reaction: and (4) adding deionized water into the slurry prepared in the step (4) for dilution to obtain a feed liquid with the solid content of 25%, adding an ammonia water solution into the feed liquid according to the volume ratio of 3:1, fully stirring, injecting into a reaction kettle, and reacting at 100-200 ℃ for 12-48h to obtain the hydrothermal powder.
(6) High-temperature calcination: calcining the prepared hydrothermal powder at high temperature of 800-1100 ℃ for 1-5h to obtain the final product t-ZrO2。
2. The method for preparing zirconia powder with high sintering activity according to claim 1, wherein the method comprises the following steps: the inorganic zirconium salt in the step (1) comprises one of zirconium tetrachloride, zirconium oxychloride and zirconium nitrate.
3. The method for preparing zirconia powder with high sintering activity according to claim 1, wherein the method comprises the following steps: m in the metal M nitrate in the step (1) comprises one of Ca, Mg and Y.
4. The method for preparing zirconia powder with high sintering activity according to claim 3, wherein the method comprises the following steps: the inorganic zirconium salt in the step (1) is prepared into an aqueous solution with the concentration of 0.2-2 g/mol.
5. The method for preparing zirconia powder with high sintering activity according to claim 1, wherein the method comprises the following steps: the metal M nitrate in the step (1) is prepared into an aqueous solution with the concentration of 0.1-1 g/mol.
6. The method for preparing zirconia powder with high sintering activity according to claim 1, wherein the method comprises the following steps: and (2) preparing the ammonium bicarbonate in the step (1) into an aqueous solution with the concentration of 2-4 g/mol.
7. The method for preparing zirconia powder with high sintering activity according to claim 1, wherein the method comprises the following steps: and (3) performing suction filtration and washing in the step (2) for 6-8 times, and controlling the concentration of inorganic ions to be below 10 ppm.
8. The method for preparing zirconia powder with high sintering activity according to claim 1, wherein the method comprises the following steps: the mass ratio of the materials crushed by ball milling in the step (4) to water is 1-1.5, and the material-ball ratio is 0.2-0.6.
9. The method for preparing zirconia powder with high sintering activity according to claim 1, wherein the method comprises the following steps: the ball milling rotation speed of the ball milling crushing in the step (4) is 200-.
10. The method for preparing zirconia powder with high sintering activity according to claim 1, wherein the method comprises the following steps: the concentration of the ammonia water in the step (5) is 1-2 mol/L.
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